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WO1999067225A1 - Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers - Google Patents

Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers Download PDF

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Publication number
WO1999067225A1
WO1999067225A1 PCT/US1999/013708 US9913708W WO9967225A1 WO 1999067225 A1 WO1999067225 A1 WO 1999067225A1 US 9913708 W US9913708 W US 9913708W WO 9967225 A1 WO9967225 A1 WO 9967225A1
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Prior art keywords
hydrocarbyl
alkyl
functional
formula
hydrogen
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PCT/US1999/013708
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French (fr)
Inventor
Ram B. Gupta
Dennis J. Jakiela
Robert G. Fischer
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Cytec Technology Corp.
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Publication date
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Priority to CA002335572A priority Critical patent/CA2335572A1/en
Priority to JP2000555879A priority patent/JP2002518487A/en
Priority to AU50831/99A priority patent/AU5083199A/en
Priority to IL14044799A priority patent/IL140447A0/en
Priority to EP99935328A priority patent/EP1089987A1/en
Priority to KR1020007014518A priority patent/KR20010053056A/en
Priority to BR9911400-3A priority patent/BR9911400A/en
Publication of WO1999067225A1 publication Critical patent/WO1999067225A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966—Triazines or their condensed derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/20—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with no nitrogen atoms directly attached to a ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • This invention relates generally to novel benzocycle-substituted pyrimidines and triazines and their use as protectants against degradation by environmental forces, including ultraviolet light, actinic radiation, oxygen, moisture, atmospheric pollutants and combinations thereof.
  • Exposure to sunlight and other sources of ultraviolet radiation is known to cause degradation of a variety of materials, especially polymeric materials.
  • polymeric materials such as plastics often discolor and may become brittle as a result of exposure to ultraviolet light.
  • a large body of art has been developed directed towards materials such as ultraviolet light absorbers and stabilizers which are capable of inhibiting such degradation.
  • a class of materials known to be ultraviolet light absorbers are o- hydroxyphenyltriazines, in which at least one substituent on the 1 , 3 or 5 carbon on the triazine ring is a phenyl group with a hydroxyl group ortho to the point of attachment to the triazine ring. In general this class of materials is well known in the art.
  • United States Patent No. 3,843,371 discloses hydroxyphenyltriazines for use in photographic materials.
  • the triazines in this patent show poor solubilities and poor stabilities.
  • hydroxyphenyltriazines alone or in combination with other light stabilizers such as hydroxyphenylbenzotriazoles, benzophenones, oxanilides, cyanoacrylates, salicylates, and hindered amine light stabilizers (HALS), for the stabilization of polymers is also well known.
  • light stabilizers such as hydroxyphenylbenzotriazoles, benzophenones, oxanilides, cyanoacrylates, salicylates, and hindered amine light stabilizers (HALS)
  • HALS hindered amine light stabilizers
  • the aforementioned aryl ring with the hydroxyl group ortho to the point of attachment to the triazine ring is based on resorcinol and, consequently, this aryl ring also « « « , ,, * PCT/US99/
  • Patents No. 3,1 18,837 and 3,244,708 disclose /?-alkoxy- ⁇ -hydroxyphenyl triazines with improved UV protection, but many embodiments of such triazines exhibit poor compatibility and solubility, and poor yellowing performance.
  • This para- substituent can be "non-reactive,” as in the case of an alkyloxy group, or “reactive” as in the case of a hydroxyalkyloxy (active hydrogen reactive site) or (meth)acryloyl (ethylenic unsaturation reactive site) group.
  • the former are referred to as “non-bondable” benzocycle-substituted pyrimidines and triazines and the latter are referred to as “bondable” benzocycle-substituted pyrimidines and triazines.
  • Low volatility is an important characteristic of stabilizers used in any applications where high temperatures are encountered. High temperatures are used in the processing of thermoplastics and in the curing of thermoset resins and coatings. High temperatures are also often present in the end-use applications for the stabilized material. Low volatility will prevent loss of the stabilizer during processing, curing, and high temperature end-uses. Besides reducing losses of stabilizer during processing or curing, low volatility will minimize processing problems such as die lip build-up and plate-out.
  • Bondable triazines are well known in the art.
  • United States Patent Nos. 3,423,360, 4,962,142 and 5,189,084 disclose various bondable and the incorporation of these compounds into polymers by chemical bonding.
  • Bondable stabilizers have a potential advantage in this respect in that, depending on the bondable functionality and the particular polymer system to be stabilized, they can be chemically incorporated into a polymer structure via reaction of the bondable functionality either during polymer formation (such as in the case of polymerizing monomers or a crosslinking polymer system) or subsequently with a preformed polymer having appropriate reactive functionality. Accordingly, due to such bonding, migration of these UV absorbers between layers of multi-layer coatings and into polymer substrates is greatly reduced.
  • the present invenlion provides a new class ol ' benzocycle-substiluted pyrimidines and triazines depicted below, in which a substituent attached to the triazine or pyrimidine ring is a fused benzocyclic group:
  • A can be a nitrogen or optionally substituted methine
  • the fused ring designated by S is a non-aromatic 4 to 12 membered ring, optionally containing one or more heteroatoms; any of the three rings may bear one or more additional substituents.
  • fused benzocyclic-substituted triazines and pyrimidines have the advantage of being highly soluble in and compatible; of having extremely low volatility, and therefore low losses during high temperature processing or curing; of being highly effective in inhibiting yellowing; and of being highly effective in preventing degradation of polymers and coatings due to the action of actinic radiation, heat, oxygen, and moisture.
  • the benzocyclic substituted triazine and pyrimidine UV absorbers of the present invention possess exceptionally low volatility, lower than most current art UV absorbers. Furthermore these benzocyclic triazine UV absorbers, impart improved weatherability and yellowing resistance to polymers compared to current art UV absorbers. None of the previously available triazine UV stabilizers and absorbers combine the unexpected low volatility along with the weatherability, yellowing resistance, solubility, and compatibility of the benzocyclic substituted triazine and pyrimidine absorbers and stabilizers of the present invention.
  • each A is independently nitrogen or methine optionally substituted with R 2 , and at least two A are nitrogen; each of T and T' is independently a direct bond, carbon, oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or functional groups containing these elements.
  • X is independently selected from hydrogen and a blocking group; each of R 1 and R 2 is independently a hydrocarbyl group, a functional hydrocarbyl group, hydroxy, alkoxy, hydrogen, halogen, cyano, or isocyano; each of Y, Z, R 3 and R 4 are independently a hydrogen, hydrocarbyl group, a functional hydrocarbyl group, halogen, hydroxyl, cyano, -O(hydrocarbyl), -O(functional hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl), -N(hydrocarbyl)(functional hydrocarbyl), -S(hydrocarbyl),
  • each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous, boron, silicon, selenium, tellurium, or functional groups containing these elements; each of m, n, and o is independently an integer between 0 and 4, provided that when both G are direct bonds, the sum of m, n and o is between 2 and 10, and that when one G is a direct bond, the sum of m, n and o is between 1 and 9,
  • T' is an oxygen atom and Y is a group L, to give a mono-resorcinol derived benzocycle-substituted pyrimidine or triazine of formula (II):
  • TZ in formula (II) is a resorcinol derivative of formula (Ilia) or (Illb):
  • each L in formulas III and IV are independently selected from the group consisting of : hydrogen; an alkyl of 1 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; an aralkyl of 7 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, chloro, cyano, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms or nitrogen
  • D 7 is -OR 25 , -NHCOR 24 or -OCH 2 CH 2 OR 25 ;
  • R 21 is hydrogen or C,-C 16 alkyl;
  • R 22 is halogen or -O-R 23 ;
  • R 23 is hydrogen, C,-C 6 alkyl, C 3 -C 6 alkenyl, aryl, or aryl-C,-C 4 -alkyl;
  • R 24 is hydrogen, C,-C 12 alkyl or aryl;
  • R 25 is C,-C 16 alkyl, C 5 -C 12 cycloalkyl, C 3 -C 6 alkenyl,
  • R 26 is hydrogen or C,-C 4 alkyl
  • R 27 is hydrogen, C,-C 18 alkyl, C 3 -C 6 alkenyl, C,-C 18 alkoxy, halogen or aryl-C,-C 4 - alkyl
  • R 28 and R 29 independently of one another are hydrogen
  • R 30 is hydrogen, C,-C 4 alkyl or CN; YY is unsubstituted or substituted C 2 -C 20 alkyl; kk is zero or an integer from 1-16; B, is O or NH; mm is an integer from 2 to 60; nn is an integer from 2 to 6; u is an integer from 1 to 4.
  • L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms;
  • X is independently selected from hydrogen and a blocking group
  • R 3 and R 4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO 2 (hydrocarbyl), -SO 3 (hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO 2 (functional hydrocarbyl), -SO 3 (functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano.
  • the benzocycle-substituted pyrimidines and triazines of the present invention further comprise oligomeric species of formulas (VI)
  • A, T, T', Y, Z, R 1 - R 4 , G, m-q, and X, are as defined above; r is an integer between 2 and 4;
  • D when r is 2 is selected from the group consisting of C 2 -C 16 alkyl, C 4 -C 12 alkenyl, xylylene, C 3 -C 20 alkyl which is interrupted by one or more oxygen atoms, hydroxy-substituted C 3 -C 20 alkyl which is interrupted by one or more oxygen atoms, — CH 2 CH(OH)CH 2 O— R 15 — OCH 2 CH(OH)CH 2 ,
  • R 23 is hydrogen, C,-C 6 alkyl, C 3 -C 6 alkenyl, aryl, or aryl-C,-C 4 -alkyl
  • R 24 is hydrogen, C,-C 12 alkyl or aryl
  • R 25 is C,-C 16 alkyl, C 5 -C 12 cycloalkyl, C 3 -C 6 alkenyl
  • R 26 is hydrogen or C,-C 4 alkyl
  • R 27 is hydrogen, C,-C, g alkyl, C 3 -C 6 alkenyl, C,-C )g alkoxy, halogen or aryl-C,-C 4 alkyl
  • R 28 and R 29 independently of one another are hydrogen, C,-C, 8 alkyl, C 3 -C 6 alkenyl, or C,-C 18 alkoxy, or halogen
  • R 30 is hydrogen, C,-C 4 alkyl or CN
  • YY is unsubstituted or substituted C 2 -C 20 alkyl
  • kk is zero or an integer from 1-16
  • B is O or NH
  • mm is an integer from 2 to 60
  • nn is an integer from 2 to 6
  • u is an integer from 1 to 4; when r is 3, D is
  • R 19 is C 3 -C 10 alkanetriyl and R 20 is C 4 -C 10 alkanetetryl; and s is 1-6;
  • R 15 is C 2 -C l0 alkyl, C 2 -C 10 oxaalkyl or C 2 -C 10 dithiaalkyl, phenyl, naphthyl, diphenyl, or C 2 -C 6 alkenyl, or phenylene-XX-phenylene wherein XX is — O— , — S— , — SO 2 — , — CH 2 — , or — C(CH 3 ) 2 — ; R' 6 is C 2 -C !0 alkyl, C 2 -C 10 oxaalkyl or C 2 -C, 0 dithiaalkyl, phenyl, naphthyl, diphenyl, or C 2 -C 6 alkenyl provided that when r is 3 the alkenyl has at least 3 carbons; R' 7 is C 2 -C 10 alkyl, phenyl, naphthyl, diphenyl, or C 2
  • R 16 , R 17 , R 18 , and R 19 are as defined above.
  • benzocycle-substituted pyrimidines and triazines of the present invention also comprise oligomeric species of the formulas (VIII) and (IX):
  • A, T, , Y, Z, R 1 through R 3 , G, m through q, and X, are as defined above;
  • R 4 is selected from the group consisting of straight chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkyl substituted by phenylene, alkyl interrupted by phenylene,
  • E is selected from the group consisting of alkyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by cyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8 to 12 carbon atoms; and r is an integer between 2 and 4.
  • each A is independently nitrogen or methine optionally substituted with R 2 , and at least two A are nitrogen; each of T and T' is independently a direct bond, carbon, oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or a functional group containing these elements; each of Y, Z, R 1 , and R 2 is independently a hydrocarbyl group, a functional hydrocarbyl group, hydrogen, halogen, cyano, or isocyano; each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous, boron, silicon, selenium, tellurium, or functional groups containing these elements; each of m, n, and o is independently an integer between 0 and 4, provided that when both G are direct bonds, the sum of m, n and o is between 2 and 10, and that when one G is a direct bond, the sum of m, n and o is between 1 and 9, and when neither G is a direct bond, the sum of m, n and
  • R 3 and R 4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO 2 (hydrocarbyl), -SO 3 (hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO 2 (functional hydrocarbyl), -SO 3 (functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano; r is an integer between 2 and 4; D, when r is 2, is selected from the group consisting of C 2 -C ]6 alkylene,
  • R 19 is C 3 -C 10 alkanetriyl and R 20 is C 4 -C 10 alkanetetryl; s is 1-6; r is an integer between 2 and 4;
  • D when r is 2, is selected from the group consisting of C 2 -C 16 alkylene, C 4 -C 12 alkenylene, xylylene, C 3 -C 20 alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C 3 -C 20 alkylene which is interrupted by one or more oxygen atoms, — CH 2 CH(OH)CH 2 O— R 15 — OCH 2 CH(OH)CH 2 , — CO— R 16 — CO— , —CO— NH— R 17 — NH— CO— , and — (CH 2 ) — COO— R 18 — OCO— (CH 2 ) — ; and when r is 3, D is selected from the group consisting of C 2 -C 16 alkylene, C 4 -C 12 alkenylene, xylylene, C 3 -C 20 alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C 3 -C 20
  • R 19 is C 3 -C ⁇ 0 alkanetriyl and R 20 is C 4 -C, 0 alkanetetryl; s is 1-6;
  • R 8 is C,-C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 20 alkyl, which is interrupted by O, N, or S, and/or substituted by OH, C,-C 4 alkyl which is substituted by — P(O)(OR 14 ) 2 , — N(R 9 ) (R 10 ), or — OCOR", and/or OH, or is glycidyl, cyclohexyl or C 7 -C complicat pheny lalkyl; R 9 and R 10 are each independently of the other, C,-C l2 alkyl, C 3 -C 12 alkoxyalkyl, C 4 -
  • R" is C,-C 18 alkyl, C 2 -C 18 alkenyl or phenyl;
  • R 12 is C,-C, 8 alkyl, C 2 -C 18 alkenyl, phenyl, C,-C )2 alkoxy, phenoxy, C,-C, 2 alkylamino; phenylamino, tolylamino or naphthylamino;
  • R 13 is C,-C 12 alkyl, phenyl, naphthyl or C 7 -C 14 alkylphenyl;
  • R 14 is C,-C 12 alkyl or phenyl;
  • R' 5 is C 2 -C 10 alkylene phenylene or a phenylene-x-phenylene- group, wherein X is — O— , — S— , — SO 2 — , — CH 2 — , or — C(CH 3 ) 2 — ;
  • R 16 is C 2 -C 10 alkylene, C 2 -C, 0 oxaalkylene or C 2 -C I0 dithiaalkylene, phenylene, naphthylene, diphenylene or C 2 -C 6 alkenylene;
  • R 17 is C 2 -C 10 alkylene, phenylene, naphthylene, methylenediphenylene or C 7 -C )5 alkylphenylene, and
  • R 18 is C 2 -C I0 alkylene or C 4 -C 20 alkylene which is interrupted by one or more oxygen atoms.
  • the benzocycle-substituted pyrimidines and triazines of the present invention may optionally have the added benefit of being capable of being chemically bonded to appropriate polymer systems via functionality attached to the benzocycle, pyrimidine and triazine groups (e.g., by a hydroxyl, ethylenic unsaturated and/or activated unsaturated group in one or more of R 1 , R 2 , Y or Z).
  • These benzocycle-substituted pyrimidines and triazines may in general be prepared via a number of procedures well known in the art, for example, those described in Brunetti, H; Luethi, C; Helv. ChemicaActa, 55 (1972) pp.
  • novel benzocycle-substituted pyrimidines and triazines of the present invention are particularly useful as ultraviolet light absorber agents for stabilizing a wide variety of materials including, for example, organic compounds, oils, fats, waxes, cosmetics, dyes and biocides, and particularly various organic polymers (both crosslinked and non-crosslinked) used in applications such as photographic materials, plastics, fibers or dyed fibers, rubbers, paints and other coatings, and adhesives.
  • the present invention consequently, also relates to (1) a method of stabilizing a material which is subject to degradation by actinic radiation (e.g., an organic material such as an organic polymer in the form of a film, fiber, shaped article or coating) by incorporating into said material an amount of an actinic radiation stabilizer composition effective to stabilize the material against the effects of actinic radiation, wherein the actinic radiation stabilizer composition comprises the inventive benzocycle-substituted 1,3, 5 -triazine or pyrimidine; and (2) the material so stabilized.
  • actinic radiation e.g., an organic material such as an organic polymer in the form of a film, fiber, shaped article or coating
  • an actinic radiation stabilizer composition comprises the inventive benzocycle-substituted 1,3, 5 -triazine or pyrimidine
  • novel benzocycle-substituted pyrimidines and triazines of the present invention are also effective as ultraviolet light screening agents in applications such as sunscreens and other cosmetic preparations, capstock layers for extruded polymers, dyed fibers and laminated UV-screening window films, among others.
  • the present invention consequently, also relates (1) to a method of protecting a substrate against degradation by actinic radiation by applying to the substrate an actinic radiation screening layer (e.g., a coating film or capstock layer) containing an actinic radiation screening composition in an amount effective to reduce the amount of actinic radiation impinging on the substrate, wherein the actinic radiation screening composition comprises the inventive benzocycle-substituted pyrimidines and triazines; and (2) the substrate so protected.
  • an actinic radiation screening layer e.g., a coating film or capstock layer
  • an actinic radiation screening composition comprises the inventive benzocycle-substituted pyrimidines and triazines
  • Such light stabilizing compositions may include a variety of other components known in the art including other ultraviolet light absorbers of the triazine class, other ultraviolet light absorbers of different classes (e.g. benzotriazoles, benzophenones), hindered amine light stabilizers, radical scavengers, antioxidants and the like.
  • UV light absorbers of the triazine class e.g. benzotriazoles, benzophenones
  • hindered amine light stabilizers e.g. benzotriazoles, benzophenones
  • radical scavengers e.g. benzotriazoles, benzophenones
  • antioxidants e.g. benzotriazoles, benzophenones
  • benzocycle-substituted pyrimidines and triazines broadly refers to any compound of formulas (I) through (IX), above.
  • benzocycle broadly refers to any compound or substituent of general formula (X):
  • hydrocarbyl in the context of the present invention, and in the above formulas, broadly refers to a monovalent hydrocarbon group in which the valency is derived by abstraction of a hydrogen from a carbon atom.
  • Hydrocarbyl includes, for example, aliphatics (straight and branched chain), cycloaliphatics, aromatics and mixed character groups (e.g., aralkyl and alkaryl). Hydrocarbyl also includes such groups with internal unsaturation and activated unsaturation.
  • hydrocarbyl includes (but is not limited to) such groups as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl and alkynyl, preferably having up to 24 carbon atoms.
  • a hydrocarbyl may optionally contain a carbonyl group or groups (which is/are included in the carbon count) and/or a heteroatom or heteroatoms (such as at least one oxygen, sulfur, nitrogen or silicon), in the chain or ring.
  • hydrocarbyl in the context of the present invention, and in the above formulas, broadly refers to a hydrocarbyl possessing pendant and/or terminal reactive and/or latent reactive functionality and/or leaving groups.
  • Reactive functionality refers to functionality which is reactive with common monomer/polymer functionality under normal conditions well understood by those persons of ordinary skill in the relevant art.
  • reactive functionality may be mentioned active hydrogen-containing groups such as hydroxyl, amino, carboxyl, thio, amido, carbamoyl and activated methylene; isocyanato; cyano; epoxy; ethylenically unsaturated groups such as allyl and methallyl; and activated unsaturated groups such acryloyl and methacryloyl, and maleate and maleimido (including the Diels-Alder adducts thereof with dienes such as butadiene).
  • “Latent reactive” functionality within the meaning of the present invention and, as would clearly be understood by those persons of ordinary skill in the art, refers to reactive functionality which is blocked or masked to prevent premature reaction.
  • latent reactive functionality may be mentioned ketimines and aldimines (amines blocked, respectively, with ketones and aldehydes); amine-carboxylate salts; and blocked isocyanates such as alcohol (carbamates), oxime and caprolactam blocked variations.
  • a "leaving" group within the meaning of the present invention is a substituent attached to the hydrocarbyl chain or ring which during reaction is dislodged or displaced to create a valency on a carbon or heteroatom in the hydrocarbyl chain or ring, said valency being filled by a nucleophile.
  • leaving groups may be mentioned halogen atoms such as chlorine, bromine and iodine; hydroxyl groups (protonated and unprotonated); quaternary ammonium salts (NT 4 + ); sulfonium salts (ST 3 + ); and sulfonates (-OSO 3 T); where T is, e.g., methyl or para-tolyl.
  • halogen atoms such as chlorine, bromine and iodine
  • NT 4 + quaternary ammonium salts
  • ST 3 + sulfonium salts
  • -OSO 3 T sulfonates
  • T is, e.g., methyl or para-tolyl.
  • R 5 is selected from hydrogen and a hydrocarbyl (preferably of up to 24 carbon atoms); and R 6 is selected from hydrogen and an alkyl of 1 to 4 carbon atoms (preferably hydrogen and methyl).
  • hydrocarbylene in the context of the present invention refers to a species of hydrocarbylene possessing pendant reactive functionality, latent reactive functionality and/or leaving groups.
  • non-functional hydrocarbylene in the context of the present invention refers generally to a hydrocarbylene other than a functional hydrocarbylene.
  • the benzocycle-substituted pyrimidines and triazines in accordance with the present invention also relate to latent stabilizing compounds against actinic radiation of the general formulas (I), (III), and (IV), wherein at least one of the hydroxyl groups on an aryl ring ortho to the point of attachment to the triazine or pyrimidine ring is blocked, that is, wherein at least one X is other than hydrogen.
  • latent stabilizing compounds liberate the effective stabilizers by cleavage of the O-X bond, e.g., by heating or by exposure to UV radiation.
  • Latent stabilizing compounds are desirable because they have many favorable properties, i.e., good substrate compatibility, good color properties, a high cleavage rate of the O-X bond and a long shelf life.
  • the use of latent stabilizing compounds is further described in United States Patent Nos. 4,775,707, 5,030,731, 5,563,224 and 5,597,854, which are incorporated herein for all purposes as if fully set forth.
  • Latent stabilizing compounds comprising the benzocycle-substituted pyrimidines and triazines in accordance with the present invention can be prepared from compounds of the general formulas (I), (II) and (IV) through (IX), wherein at least one X is hydrogen, by subjecting said compounds to a further reaction to form latent stabilizing compounds, as described in the immediately preceding incorporated references.
  • blocking groups X may be mentioned one or more of the following groups: allyl, -COR a , -SO 2 R b , -SiR c R d R e , -PR f R ⁇ or -POR f R K , -CONHR ⁇ wherein each R a is independently selected from C,-C 8 alkyl, halogen-substituted C,-C 8 alkyl,
  • the reaction to give the latent stabilizing compounds of the present invention of the general formula (I), (III), and (IV), in which X is allyl, -COR a , -SO 2 R b , -SiR c R d R e , -PR f R 6 or -POR f R B , can be carried out, for example, by reaction of the compounds of the general formula (III) through (X), wherein at least one X is hydrogen with the corresponding halides such as allyl chloride, Cl-COR ⁇ Cl-SO 2 R b , Cl-SiR c R d R e , Cl-PR f R ⁇ , or Cl-POR f R 8 .
  • the reaction to give the latent stabilizing compounds of the present invention of the general formulas (III) through (X) in which X is -CONHR h can be carried out, for example, by reaction of the compounds of the general formulas (III) through (X), wherein at least one X is hydrogen with the corresponding isocyanates.
  • acylated compounds can be obtained by reaction with anhydrides, ketenes or esters, such as lower alkyl esters, as is well known to one skilled in the art.
  • the above-described reagents may be used in approximately equimolar amounts or in excess, for example, from 2 to 20 mol with respect to the hydroxyl groups desired to be made latent in the starting compound of the general formula (I), (III), or (IV).
  • Catalysts customarily used for acylation, sulfonylation, phosphonylation, silylation or urethanation reactions may be used in forming the latent stabilizing benzocycle- substituted pyrimidines and triazines of the present invention.
  • acylation and sulfonylation reaction catalysts such as tertiary or quaternary amines, such as triethylamine, dimethylaminopyridine or tetrabutylammonium salts, may be used for forming these latent stabilizing compounds.
  • the reaction may be carried out in the presence of a solvent, such as relatively inert organics, e.g., hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as carbon tetrachloride or chloroform, or ethers such as tetrahydrofuran or dibutyl ether, or without a solvent.
  • a solvent such as relatively inert organics, e.g., hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as carbon tetrachloride or chloroform, or ethers such as tetrahydrofuran or dibutyl ether, or without a solvent.
  • a solvent such as relatively inert organics, e.g., hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as carbon tetrachloride or chloroform, or ethers such as tetrahydrofuran or dibuty
  • L is selected from the group consisting of hydrogen
  • R 9 and R 10 independently of one another are C C 12 alkyl, C 3 -C 12 alkoxyalkyl, C 4 -C 16 dialkylaminoalkyl, or C 5 -C 12 cycloalkyl, or R 9 and R 10 taken together are
  • R" is C,-C ] g alkyl, C 2 -C ⁇ 8 alkenyl, or phenyl.
  • L may also be an alkyl of 1 - 24 carbon atoms substituted by a hindered amine light stabilizer (HALS) group of the general formula XI.
  • HALS hindered amine light stabilizer
  • Triazines containing tetramethylpiperidine groups are described in U.S. 4,161,592 and 5,376,710, which are hereby incorporated by reference herein as if fully set forth.
  • J is — O— , — NR ⁇ — , — T— (CH2)2— NR 3 ⁇ — wherein T is — O— or — S— , and R 30 is C,-C 12 alkyl or hydrogen;
  • R 31 is hydrogen or C,-C 8 alkyl
  • R 32 is hydrogen, oxygen, C,-C 21 alkoxyalkyl, C 7 -C 8 aralkyl, 2,3-epoxypropyl, and aliphatic acyl group with 1-4 C atoms or one of the groups — CH 2 COOR 33 , — CH — CH(R 34 )— OR 35 , —COOR 36 or —CONHR 36 , wherein R 33 is C,-C 12 alkyl, C 3 -C 6 alkenyl, phenyl, C 7 -C 8 aralkyl or cyclohexyl, R 34 is a hydrogen, methyl or phenyl, R 35 is hydrogen, an aliphatic, aromatic, araliphatic or alicyclic acyl group with 1-8 C atoms, wherein the aromatic part is unsubstituted or is substituted by chlorine, C,C 4 alkyl, C,-C 8 alkoxy or by hydroxyl, and R 36 is C,-C 12 alkyl,
  • R 37 is hydrogen, —OH or one of the groups — O— CO— R 38 or — NR 36 — CO— R 38 , wherein R 38 is C,-C 12 alkyl or phenyl; and K is — O — (C mm H 2mm ) — wherein mm is 1 to 6,
  • Preferred among the sterically hindered amines are members of the group consisting of: bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l,2,2,6,6-pentamethylpiperidin-4- yl)sebacate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino- 2, 6-dichloro- 1,3, 5-triazine; the
  • each L group is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms, or mixtures thereof; an alkyl of 4 to 20 carbon atoms containing one or more oxygen atoms in the chain and optionally substituted with one or more hydroxyl groups, or mixtures thereof.
  • Each R 1 and R 2 is independently selected from hydrogen, chloro, an alkyl of 1 to 8 carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionally containing an oxygen atom in the chain, a hydroxyalkyl of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, a hydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, an acyl group of 2 to 12 carbon atoms and an acyloxy of 2 to 12 carbon atoms.
  • each R' and R 2 is independently selected from hydrogen, chloro, an alkyl of 1 to 4 carbon atoms, and alkoxy of 1 to 4 carbon atoms, and particularly hydrogen, methyl, and methoxy.
  • Each of R 3 and R 4 is independently selected from hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, a hydrocarbyloxy group of 1 to 24 carbon atoms, an acyl group of 2 to 24 carbon atoms and an acyloxy group of 2 to 24 carbon atoms.
  • each R 1 is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain; an alkyloxy of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain; an alkenyl of 2 to 24 carbon atoms optionally containing an oxygen atom in the chain; an alkenyloxy of 2 to 24 carbon atoms optionally containing an oxygen atom in the chain; an acyl group of 2 to 12 carbon atoms; an acyloxy group of 2 to 12 carbon atoms; and optionally substituted benzoyl.
  • each R 1 is independently selected from hydrogen, an alkyl of 1 to 8 carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionally containing an oxygen atom in the chain, a hydroxyalkyl of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, a hydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, an acyl group of 2 to 12 carbon atoms and an acyloxy of 2 to 12 carbon atoms.
  • each of R 3 and R 4 is independently selected from hydrogen, halogen, an acyl of 2 to 24 carbon atoms, benzoyl, alkyl of 1 to 24 carbon atoms, an alkenyl of 2 to 24 carbon atoms, a cycloalkyl of 5 to 24 carbon atoms; and an aralkyl of 7 to 24 carbon atoms.
  • R 3 and R 4 are independently methylene, alkylidene, or benzylidene substituted by a benzophenone UV absorber or a benzotriazole UV absorber.
  • Related triazine - benzotriazole and triazine - benzophenone hybrid UV absorbers are disclosed in U.S. 5,585,422 which is incorporated by reference herein for all purposes fully set forth.
  • R 3 and R 4 are independently methylene, alkylidene, or benzylidene substituted by a second triazine UV absorber.
  • Related triazine dimers (and oligomers) are disclosed in U.S. 5,726,309 and EP 704,437 which are incorporated by reference herein for all purposes fully set forth.
  • Preferred benzotriazoles comprise at least one member of the group consisting of: 2- (2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-2'- hydroxyphenyl)benzotriazole; 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(2'- hydroxy-5'-(l,l,3,3-tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'- hydroxyphenyl)-5-chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5- chloro-benzotriazole; 2-(3 , -sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(2'- hydroxy-4'-octoxyphen
  • Most preferred benzotriazoles are members of the group consisting of: 2-(2'-hydroxy-5'-(l,l,3,3-tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di- tert-amyl-2'-hydroxphenyl)benzotriazole; 2-(3',5'-bis( ⁇ , ⁇ -dimethylbenzyl)-2'- hydroxyphenyl)-benzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-(2- octyloxycarbonylethyl)phenyl)benzotriazole, the transesterification product of 2-[3'-tert- butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300 and mixtures thereof.
  • R' ' is selected from hydrogen and hydrocarbyl of 1 to 24 carbon atoms which may optionally be substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms and/or contain one or more oxygen and/or nitrogen atoms in the chain. More preferably, R" is selected from hydrogen and hydrocarbyl of 1 to 24 carbon atoms which may optionally be substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms.
  • R 12 is selected from hydrogen and an alkyl of 1 to 4 carbon atoms. More preferably, R 12 is selected from hydrogen and a methyl group.
  • R 13 is selected from hydrogen, a hydrocarbyl group of 1 to 8 carbon atoms, or phenyl. More preferably, R 13 is hydrogen or methyl.
  • G is a direct bond
  • m and o are 0, and n is 4.
  • Further preferred embodiments may include any combination of the parameters mentioned above.
  • Lewis acid is intended to include aluminum halides, alkylaluminum halides, boron halides, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium halides, arsenic halide, copper halides, cadmium halides, mercury halides, antimony halides, and the like.
  • Preferred Lewis acids include aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, tin dichloride, tin tetrachloride, or a mixture thereof.
  • step-wise means a reaction sequence wherein a series of reactions are conducted, the first reaction producing compounds of Formulas (XXXII), (XXXV), or (XXXVI) and being carried out to between about 50% to about 100% completion prior to addition of a compound of Formula (XXXIII) to produce compounds of Formulas (I), (IV a/b/c), or (V).
  • the reaction is carried out to between about 70% to about 100% completion prior to addition of compound of Formula (XXXIII), and more preferably to between about 75% to about 100% completion.
  • novel benzocycle-substituted pyrimidines and triazines of the present invention can be prepared through the Friedel-Crafts reaction of a benzocycle moiety (XXX) with a halogen-substituted pyrimidine or triazine compound of Formula (XXXI) or (XXXIV). See Schemes 1, 2, and 3.
  • the relative amounts of the reactants are as follows.
  • the amount of compounds (XXXI) or (XXXIV) should be in sufficient amounts to react with benzocyclic compounds of Formula (XXX) to produce compounds of Formula (XXXII), (XXXV), or (XXXVI).
  • the amount of benzocyclic compound of Formula (XXX) is important to ensure that a sufficient amount of benzocyclic compounds of Formula (XXXII), (XXXV), or (XXXVI) are synthesized without excessive amounts of undesired side products such as trisbenzocyclic triazine or trisbenzocyclic pyrimidine.
  • the amount of benzocyclic compounds (XXX) should be in sufficient amounts to synthesize 2-halo-4,6-bisbenzocyclic- 1 ,3 ,5-triazine, 2,4-dihalo-6-benzocyclic- 1 ,3 ,5-triazine, 2-halo-4,6-bisbenzocyclicpyrimidine, 2,4-dihalo-6-benzocyclicpyrimidine or convert 2-halo- 4,6-bisbenzocyclic- 1,3, 5-triazine into 2,4,6-trisbenzocyclic- 1,3, 5-triazine or convert 2-halo- 4,6-bisbenzocyclicpyrimidine into 2,4,6-trisbenzocyclicpyrimidine.
  • the amount of Lewis acid, Al(Hal) 3 wherein Hal is a halide as defined above, used in the reaction should be in sufficient amounts to transform 2,4,6-trihalo- 1,3, 5-triazine or 2,4,6-trihalo-pyrimidine to the preferred 2-halo-4,6-bisbenzocyclic-l, 3,5-triazine, 2,4,6-trisbenzocyclic- 1,3, 5-triazine, or 2-halo-4,6-bisbenzocyclicpyrimidine, 2,4,6-trisbenzocyclicpyrimidine, respectively.
  • the amount of Lewis acid should be between about 0.5 to about 500 mol equivalents.
  • the amount of Lewis acid should be between about 1 to about 5 mol equivalents.
  • the Lewis acid can be combined with either the benzocyclic compound of Formula (XXX), compounds of Formula (XXXI) or (XXXIV), or both, in any manner.
  • In situ reaction mixture preparation comprises addition of at least one Lewis acid to at least one
  • the reaction should run for a sufficient amount of time, at a sufficient temperature
  • the preferred reaction time for the synthesis of compounds of Formula (XXXII), (XXXV), (XXXVI), i.e., the first step is between about 5 minutes and about 48 hours, more preferred between about 15 minutes and about 24 hours.
  • the preferred reaction time for the synthesis of compounds of Formula (I), (IV a/b/c), (V), i.e., the second step is between about 10 minutes and about
  • reaction pressure is not critical and can be about 1 atm or higher if desired.
  • the reaction is carried out under an inert gas such as nitrogen or argon.
  • an inert gas such as nitrogen or argon.
  • the step-wise process comprises mixing at least one Lewis acid and compounds of Formula (XXXI) or (XXXIV) with one or more of the desired benzocyclic compounds of Formula (XXX), preferably until the reaction is between about 70% to about 100% completed. Thereafter, the product is isolated and purified. The aromatic compound of Formula (XXXIII) is added to the purified product along with Lewis acid to synthesize the compounds of Formula (I), (IV a/b/c), or (V).
  • the step- wise sequence allows for the isolation, purification, and storage of compounds of Formula (XXXII), (XXXV), or (XXXVI) prior to subsequent reaction with aromatic compounds of Formula (XXXIII).
  • the preferred addition time of the aromatic compound of Formula (XXXIII) to the reaction mixture is between about 5 minutes to about 10 hours, more preferred addition time is between about 10 minutes to about 5 hours, and most preferred addition time is between about 15 minutes to about 2 hours.
  • the Lewis acid should be present in amounts sufficient to react with the number of halogens being substituted on compounds of Formula (XXXI) or (XXXIV). A range of between about 1 to about 5 mol equivalents of Lewis acid can be used.
  • the preferred Lewis acid is aluminum chloride.
  • a preferred amount of Lewis acid is between about 2 to about 4 mol equivalents to halo-triazine or halo-pyrimidine.
  • the novel benzocyclic-substituted pyrimidines and triazines of the present invention are particularly useful as ultraviolet light absorber agents for stabilizing a wide variety of materials including, for example, various polymers (both crosslinked and thermoplastic), photographic materials and dye solutions for textile materials, as well as in ultraviolet light screening agents (such as sunscreens).
  • novel benzocyclic-substituted pyrimidines and triazines of the present invention can be incorporated into such material in any one of a variety of conventional manners, including for example, physical mixing or blending, optionally, with chemical bonding to the material (typically to a polymer), as a component in a light stabilizing composition such as a coating or solution, or as a component in a UV screening composition such as a sunscreen composition.
  • the benzocyclic-substituted pyrimidines and triazines of the present invention can be employed to stabilize materials which are subject to degradation by ultraviolet radiation by incorporating the presently claimed compounds into polymeric materials, either chemically or physically.
  • Non-limiting examples of polymeric materials that may be so stabilized are polyolefins, polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, high-impact polystyrenes, polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles, polybutadienes, polystyrenes, ABS, SAN (styrene acrylonitrile), ASA (acrylate styrene acrylonitrile), cellulosic acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylsulfides, PPO, polysulfones, polyethersulfones, polyvinylchlorides, polycarbonates, polyketones, aliphatic polyketones, thermoplastic TPO's, aminoresin crosslinked polyacrylates and polyesters, polyisocyanate crosslinked polyesters and polyacryl
  • the preferred polymeric material is selected from the group consisting of polyolefins; copolymers of one or more monoolefins and/or diolefins with carbon monoxide and/or with other vinyl monomers; hydrocarbon resins (such as C 5 -C 9 ) including hydrogenated modifications thereof and mixtures of polyalkylenes and starch; polyesters; copolyethers esters; polyethers; polyketones; polyamides and copolyamides derived from diamines, dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams; natural and synthetic rubbers and elastomers; polyurethanes; polystyrenes, poly- ⁇ -methylstyrenes and copolymers with other vinyl monomers; graft copolymers of styrene; high impact polystyrenes; polyacrylic acids, polymethacrylics acids, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles
  • polymers which may be stabilized include: 1. Homo- and copolymers of monoolefins and diolefins including but not limited to ethylene, propylene, isobutylene, butene, methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene and cycloolefins such as cyclopentene and norbornene; for example, polyethylenes (which optionally can be crosslinked) such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and branched low density polyethylene (BLDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high mo
  • Copolymers of one or more monoolefins and/or diolefins with carbon monoxide and/or with other vinyl monomers including acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, styrenes, vinyl acetate (such as ethylene/vinyl acetate copolymers), vinyl halides, vinylidene halides, maleic anhydride and allyl monomers such as allyl alcohol, allyl amine ally glycidyl ether and derivatives thereof.
  • Hydrocarbon resins such as C 5 -C 9
  • Hydrocarbon resins including hydrogenated modifications thereof and mixtures of polyalkylenes and starch.
  • Copolymers of one or more styrenes with other vinyl monomers such as olefins and diolefins (e.g., ethylene, isoprene and/or butadiene), acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, vinyl acetate (such as ethylene/vinyl acetate copolymers), vinyl halides, vinylidene halides, maleic anhydride and allyl compounds such as allyl alcohol, allyl amine allyl glycidyl ether and derivatives thereof.
  • vinyl monomers such as olefins and diolefins (e.g., ethylene, isoprene and/or butadiene), acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, vinyl acetate (such as ethylene/vinyl acetate copolymers), vinyl halides,
  • Graft copolymers of styrenes on polybutadienes, polybutadiene/styrene copolymers and polybutadiene/acrylonitrile copolymers styrene (or ⁇ -methylstyrene) and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene copolymers; styrene and acrylonitrile on polyalkyl acrylates or methacrylates; and styrene and acrylonitrile on acrylate/butadiene copolymers.
  • Halogen-containing polymers such as polychloroprene; chlorinated rubbers; chlorinated and brominated isobutylene/isoprene copolymers; chlorinated or sulfochlorinated polyethylene; copolymers of ethylene and chlorinated ethylene; epichlorohydrin polymers and copolymers; and polymers and copolymers of halogen-containing vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride and/or vinylidene fluoride and other vinyl monomers.
  • Homo- and copolymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides and acrylonitriles.
  • Copolymers of the monomers mentioned in (8) with other unsaturated monomers such as olefins and diolefins (e.g., butadiene), styrenes, vinyl halides, maleic anhydride and allyl monomer such as allyl alcohol, allyl amine, allyl glycidyl ether and derivatives thereof.
  • homo- and copolymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof such as vinyl alcohol, vinyl acetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol, allyl amine, allyl glycidyl ether, allyl phthalate and allyl melamine; as well as copolymers of such monomers with other ethylenically unsaturated monomers mentioned above.
  • the present invention further encompasses these polymers as prepared by metallocene catalysts. 10 11.
  • cyclic ethers such as alkylene glycols and alkylene oxides, as well as copolymers with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; and polyoxymethylenes modified with thermoplastic polyurethanes, acrylates and/or MBS. 15 13. Polyphenylene oxides and sulfides.
  • Polyurethanes derived from hydroxy-functional components such as polyhydric alcohols, polyethers, polyesters, polyacrylics and/or polybutadienes on the one hand, and aliphatic and/or aromatic isocyanates on the other, as well as precursors thereof.
  • Polyamides and copolyamides derived from diamines, dicarboxylic acids and/or 20 aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6, polyamide 12/12, polyamide 11 and polyamide 12; aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic and or terephthalic acid and with or
  • poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide block copolymers of the aforementioned polyamides with polyolefins, olefin copolymer, ionomers, chemically bonded or grafted elastomers, or polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides condensed
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids, diols and/or hydroxycarboxylic acids or the corresponding lactones such as polyethylene terephthalate, polybutylene 35 terephthalate, poly- 1 ,4-dimethylcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolycthcr esters derived from hydroxyl- terminated ethers; PETG; PEN; PIT; and also polyesters modified with polycarbonate or MBS.
  • Polysulfoncs, polyether sulfones and polyether ketones are examples of polyethersulfones.
  • Crosslinked polymers derived from aldehydes condensation resins such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds such as bisphenol A and bisphenol F, which are crosslinked with hardeners such as anhydrides or amines.
  • 20 26. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, including cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose, as well as rosins and their derivatives.
  • 27 Polysiloxanes. 25 28.
  • Michael addition polymers of amines or blocked amines e.g., ketimines
  • activated unsaturated and/or methylene compounds such as acrylates and methacrylates, maleates and acetoacetates. 29.
  • PVC/EVA PVC/ABS
  • PVC/MBS PC/ABS
  • PC/ABS PBTP/ABS
  • PC/ASA PC/PBT
  • 30 PVC/CPE PVC/acrylate
  • POM/thermoplastic PUR PC/thermoplastic polyurethane
  • PATENT/HDPE PP/HDPE, PP/LDPE, LDPE/HDPE, LDPE/EVA, LDPE/EAA,
  • PATENT/PP PATENT/PPO
  • PBT/PC/ABS PBT/PET/PC and the like.
  • Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.
  • Epoxymelamine resins such as light-stable epoxy resins cross-linked by an epoxy functional coetherified high solids melamine resin.
  • Other materials which can be stabilized include, for example:
  • Aqueous emulsions of natural or synthetic rubber such as natural latex or lattices of carboxylated styrene/butadiene copolymers.
  • Organic dyes such as azo dyes (diazo, triazo and polyazo), anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethines, styryl dyes, di- and triaryl carbonium dyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitroso dyes, stilbene dyes, formazan dyes, quinacridones, carbazoles and perylene tetracarboxylic diimides.
  • azo dyes diazo, triazo and polyazo
  • anthraquinones such as anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethines, styryl dyes, di- and triaryl carbonium dyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitroso dyes, stilbene dyes, formazan
  • Cosmetic products such as skin lotions, collagen creams, sunscreen, facial make-up, etc., comprising synthetic materials such as antioxidants, preservatives, lipids, solvents, surfactants, colorants, antiperspirants, skin conditioners, moisturizers etc.; as well as natural products such as collagen, proteins, mink oil, olive oil, coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe, etc.
  • synthetic materials such as antioxidants, preservatives, lipids, solvents, surfactants, colorants, antiperspirants, skin conditioners, moisturizers etc.
  • natural products such as collagen, proteins, mink oil, olive oil, coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe, etc.
  • Cellulose-based paper formulations for use e.g., in newsprint, cardboard, posters, packaging, labels, stationery, book and magazine paper, bond typing paper, multipurpose and office paper, computer paper, xerographic paper, laser and ink-jet printer paper, offset paper, currency paper, etc. 38. Photographic film paper.
  • novel benzocyclic-substituted pyrimidines and triazines of the present invention can also be used with aliphatic polyamide polymers.
  • An "Aliphatic polyamide” is 35 a polyamide characterized by the presence of recurring carbonamide groups as an integral part of the polymer chain which are separated from one another by at least two aliphatic carbon atoms.
  • Illustrative of these polyamides are those having recurring monomeric units represented by the general formula:
  • R and R 1 are the same or different and are alkylene groups of at least about two carbon atoms, preferably alkylene having from about 2 to about 12 carbon atoms.
  • exemplary of such polyamides are polyamides formed by the reaction of diamines and diacids such as poly (tetramethylene adipamide)(nylon 4,6); poly(hexamethylene adipamide) (nylon 6,6); poly (hexamethylene azelamide) (nylon 6,9); poly(hexamethylene sebacamide) (nylon 6,10); poly(heptamethylene pimelamide) (nylon 8,8); poly(nonamethylene azelamide) (nylon 9,9); poly(decamethylene azelamide) (nylon 10,9); and the like.
  • useful aliphatic polyamides are those formed by polymerization of amino acids and derivatives thereof, as for example lactams.
  • Illustrative of these useful polyamides are poly(4-aminobutyric acid) (nylon 4); poly(6-aminohexanoic acid) (nylon 6); poly(7-aminoheptanoic acid) (nylon 7); poly(8-aminoocatanoic acid) (nylon 8); poly(9aminononanoic acid) (nylon 9); poly(10-aminodecanoic acid) (nylon 10); poly(l 1- aminoundecanoic acid) (nylon 11); poly(12-aminododecanoic acid) (nylon 12); and the like. Blends of two or more aliphatic polyamides may also be employed.
  • Copolymers formed from any combination of the recurring units of the above referenced aliphatic polyamides can be used.
  • such aliphatic polyamide copolymers include caprolactam/hexamethylene adipamide copolymer (nylon 6/6,6); hexamethylene adipamide/caprolactam copolymer (nylon 6, 6/6); hexamethylene adipamide/hexamethylene-azelamide copolymer (nylon 6,6/6,9); and copolymers formed from recurring units of the above referenced aliphatic polyamides with aliphatic/aromatic polyamide recurring units may also be used.
  • copolyamides examples include nylon 6/6T; nylon 6,6/6, T; nylon 6/1 OT; nylon 6/12T; nylon 6,10/6,T etc.
  • Preferred aliphatic polyamides for use in the practice of this invention are poly(caprolactam); poly(7-aminoheptanic acid); poly(tetramethylene adipamide); poly(hexamethylene adipamide); and mixtures thereof.
  • the particularly preferred aliphatic polyamides are poly(caprolatam); poly(hexamethylene adipamide); poly(tetramethylene adipamide); and mixtures thereof.
  • Aliphatic polyamides useful in the practice of this invention may be obtained from commercial sources or prepared in accordance with known preparatory techniques.
  • polycaprolactam may be obtained from Allied Signal Inc.
  • poly(hexamethylene adipamide) may be obtained from DuPont Co.
  • the number average molecular weight of the aliphatic polyamide may vary widely.
  • the aliphatic polyamide is of film forming molecular weight that is sufficiently high to form a free standing film and sufficiently low to allow melt processing of the blend into a film.
  • Such number average molecular weights are well known to those of skill in the film art and are usually at least about 5,000 as determined by the formic acid viscosity method. In this method, a solution of 9.2 wt. Concentration of aliphatic polyamide in 90% formic acid at 25°C is used.
  • the number average molecular weight of the aliphatic polyamide is from about 5,000 to about 1 ,000,000 and in the particularly preferred embodiments is from about 10,000 to about 100,000. Amongst the particularly preferred embodiments, most preferred are those in which the molecular weight of the aliphatic polyamide is from about 20,000 to about 40,000.
  • Spandex fibers is a PUR elastomer product, which requires very specific UV absorber and hindered amine light stabilizers properties in order to achieve optimum performance.
  • UV absorbers of the triazine class of this invention can be combined with polymeric hindered amine light stabilizers (HALS) to provide outstanding performance in achieving the desired properties for the Spandex fiber applications.
  • HALS polymeric hindered amine light stabilizers
  • HALS provides the following properties in the Spandex fiber application: (1) low color contribution at typical use levels in the 0.5-2.0% range; (2) sufficient MW, thermal stability and low volatility for fiber processing and thermal exposure conditions; (3) high compatibility and permanence; (4) prevent discoloration and loss of elasticity during exposure to UV light energy; (5) low extraction by water and dry cleaning solvents; (6) low color development during exposure to atmospheric pollutants, NO x , SO x , hydrocarbons, etc.;
  • Nylon fibers for Nylon/Spandex fabrics for Nylon/Spandex fabrics.
  • the triazine UV absorber with or without the polymeric HALS provides outstanding stabilization with minimum negative effect on secondary performance properties, such as low color development during NO x exposure and low interaction with copper based antioxidant systems using in Nylon fibers.
  • any of the triazine compounds disclosed herein can be used to impart one or more of the properties described above to Spandex fibers when added thereto in a stabilization effective amount.
  • these triazine compounds are added in combination with polymeric HALS.
  • the polymeric HALS is preferably poly[(6-morpholino-s-triazine-2,4- diyl)[2,2,6,6,-tetramethyl-4-piperidyl)imino]-hexamethylene [(2,2,6,6-tetramethyl-4- piperidyl)imino]].
  • the polymeric HALS is the methylated (M) version of the above HALS, which is sold by Cytec Industries, Inc. as CYASORB®UV-3529 light stabilizer.
  • M methylated
  • Spandex fibers are made from a polyurethane (PUR) prepolymer prepared from a diisocyanate and a glycol.
  • PUR polyurethane
  • the above UV stabilizer alone or in combination with HALS would be suitable for use in any or all four processes.
  • Spandex fibers may contain a processing antioxidant system, such as a phenolic antioxidant, or a phenolic/phosphite antioxidant combination.
  • a processing antioxidant system such as a phenolic antioxidant, or a phenolic/phosphite antioxidant combination.
  • pigments, such as TiO 2 are commonly used in the fiber products.
  • the triazine UV absorber alone or with M-HALS can be dissolved into DMF or DMAC and added to the PUR prepolymer solution prior to solution fiber spinning processes. Also, the combination can be extrusion compounded into the PUR compound used in the melt spinning process.
  • polymeric materials to be stabilized with the novel benzocycle-substituted pyrimidines and triazines of the present invention preference is given to the polycarbonates, polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides, but especially to the polycarbonates.
  • polycarbonates polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides, but especially to the polycarbonates.
  • Those compounds are to be understood as being especially those polymers the constitutional repeating unit of which corresponds to the formula:
  • A is a divalent phenolic radical. Examples of A are given inter alia in U.S. Pat. No. 4,960,863 and
  • A can be derived, for example, from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense of the term, such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers, ketones, sulfones, sulfoxides, ⁇ , ⁇ '-bis(hydroxyphenyl)-diisopropylbenzenes, for example the compounds 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis(3,5- dichloro-4-hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)cyclohexane, or from the compounds of the formulae:
  • the preferred resins are polycarbonates based on dihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,4-bis (4- hydroxyphenyl)-2-methylbutane; 1 , 1 -bis-(4-hydroxyphenyl)-cyclohexane; 2,2-bis-(3-chloro- 4-hydroxyphenyl)propane; 4,4'-sulfonyldiphenol; and l,l-bis-(4-hydroxyphenyl)-3,3,5- trimethy ley cl ohexane .
  • dihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,4-bis (4- hydroxyphenyl)-2-methylbutane; 1 , 1 -bis-(4-hydroxyphenyl)-cyclohexane; 2,2-bis-(3-chloro- 4-hydroxyphenyl)propane; 4,4'-s
  • polycarbonate copolymers incorporating two or more phenols, branched polycarbonates wherein a polyfunctional aromatic compounds is reacted with the dihydric phenol(s) and carbonate precursor, and polymer blends of which polycarbonate comprises a significant portion of the blend.
  • U.S. Patent No. 5,288,788 also describes polycarbonates and polyester carbonates, especially aromatic polycarbonates, for example those based on 2,2-bis(4- hydroxyphenyl)pro ⁇ ane or l,l-bis(4-hydroxyphenyl)cyclohexane.
  • British Patent Application No. 2,290,745 describes a number of methods have been developed to concentrate UV absorbers near or at the surface of polymeric materials. These include surface impregnation (see U.S. Patent Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating a plastic article with solutions containing thermoplastic resins and UV absorbers (see U.S. Patent Nos. 4,668,588 and 4,353,965). Both techniques suffer from drawbacks including requiring additional processing steps (i.e. applying, drying or curing), and encounter difficulties associated with the handling of large processed articles. An additional drawback, particularly relevant to polycarbonate sheet production, is the detrimental effect such post addition treatment would have on the surface of the polymeric substrate.
  • the invention also relates to thermoplastic articles coated with a thermoplastic layer 0.1 to 10 mil (0.00254 mm to 0.254 mm), preferable 0.1 to 5 mil (0.00254 mm to 0.127 mm), thick, in which said layer contains 0.1% to 20% by weight of the benzocyclic-substituted pyrimidines and triazines of the present invention.
  • a thermoplastic layer 0.1 to 10 mil (0.00254 mm to 0.254 mm), preferable 0.1 to 5 mil (0.00254 mm to 0.127 mm), thick, in which said layer contains 0.1% to 20% by weight of the benzocyclic-substituted pyrimidines and triazines of the present invention.
  • Preferred concentrations of are 2% to 15% by weight; most preferred concentrations of 5% to 10% by weight.
  • benzocycle-substituted pyrimidines and triazines of the present invention may be incorporated into the thermoplastics of the surfaces layer by standard methods such as dry mixing the additives with granular resin prior to extruding.
  • the benzocycle-substituted pyrimidine or triazine layer may be applied to one or both sides of the thermoplastic article.
  • Laminated thermoplastic articles which contain additional layers such as a water resistant layer as found in U.S. Pat. No. 4,992,322 are also part of the present invention.
  • the core layer and the coating layer may be the same or different thermoplastic resin including polyesters, polyester carbonates, polyphenylene oxide, polyvinyl chloride, polypropylene, polypropylene, polyethylene, polyacrylates, polymethacrylates and copolymers and blends such as styrene and acrylonitrile on polybutadiene and styrene with maleic anhydride, and mixtures (polyblends) of such polymers with one another or with other polymers, for example with polyolefins, polyacrylates, polydienes or other elastomers in the form of impact strength modifiers.
  • thermoplastic resin including polyesters, polyester carbonates, polyphenylene oxide, polyvinyl chloride, polypropylene, polypropylene, polyethylene, polyacrylates, polymethacrylates and copolymers and blends such as styrene and acrylonitrile on polybutadiene and styrene with maleic anhydride, and mixtures (polyble
  • the benzocycle-substituted pyrimidines and triazines of the present invention can also be chemically bonded to substrates, such as polymers, thereby greatly reducing the migration of such UV absorbers, e.g., out of the substrate or away from the substrate surface.
  • the bonding mechanism of the triazines of the present invention involves the formation of a bond (chemical and/or co-valent) between a functionality attached to the amido or carbamate group, e.g., by a pendant vinyl or hydroxyl group, and the "host" substrate, such as a polymer.
  • Incorporation of the benzocycle-substituted pyrimidines and triazines of the invention can be brought about by copolymerization, copolyaddition, copolycondensation, by reaction with a polymer which carries suitable functional groups, or by grafting, in a manner as disclosed in United States Patent Nos. 3,423,360 and 5,189,084 which are incorporated herein by reference as if fully set forth. Bonding of the benzocycle-substituted pyrimidines and triazines of the invention can occur by polymerization or copolymerization.
  • novel triazines of the present invention comprising pendant vinyl groups
  • polymerization or copolymerization with at least one vinyl monomer e.g., (meth)acrylic acid, esters of (meth)acrylic acid such as methyl acrylate, amides of (meth)acrylic acid, hydroxyethylacrylate, olefins, vinyl chloride, styrene, butadiene, isoprene and acrylonitrile
  • vinyl monomer e.g., (meth)acrylic acid, esters of (meth)acrylic acid such as methyl acrylate, amides of (meth)acrylic acid, hydroxyethylacrylate, olefins, vinyl chloride, styrene, butadiene, isoprene and acrylonitrile
  • Polymerization or copolymerization can be initiated by initiators, such as free radical, anionic and cationic types, or by actinic radiation, such as UV, electron beam, x-rays and gamma irradiation from a Co 60 source, as is well known to those in the polymerization art.
  • initiators such as free radical, anionic and cationic types, or by actinic radiation, such as UV, electron beam, x-rays and gamma irradiation from a Co 60 source, as is well known to those in the polymerization art.
  • Polymerization or copolymerization can be carried out in solution, in an emulsion, in a dispersion, in the melt, or in the solid state as is well known to those in the polymerization art.
  • bonding of the presently claimed benzocycle-substituted pyrimidines and triazines compounds of the present invention can be brought about by copolyaddition or copolycondensation. Such incorporation can be made by addition during the synthesis of an addition polymer or copolymer or by condensation during the synthesis of a condensation polymer or copolymer by methods known to those skilled in the art.
  • compounds of the formula (I), (II), or (IV)-(IX) containing the appropriate functional groups can be incorporated into polyesters, polyamides, polyurethanes, epoxy resins, melamine resins, alkyd resins, phenolic resins, polyurethanes, polycarbonates, polysiloxanes, polyacetals and polyanhydrides, to name but a few.
  • compounds of the formula (I), (II), or (IV)-(IX) can be bonded to a monomeric component which is then incorporated into a polymer or copolymer, e.g., by the free radical initiated addition or copolycondensation methods described above.
  • Analogous methods are disclosed in, for example, United States Patent No. 5,459,222 (incorporated by reference herein for all purposes as if fully set forth) for the bonding of benzotriazole and benzophenone stabilizers to diol precursors which are then incorporated by condensation polymerization into polyurethanes and polyesters to impart UV stabilizing properties to said polymers.
  • the benzocycle-substituted pyrimidines and triazines of the invention may also be bonded to polymers by reaction with an oligomer and/or polymer which carries suitable functional groups.
  • at least one triazine compound comprising a vinyl pendant group can be added, optionally with at least one other vinyl monomer or compound comprising a vinyl group, to unsaturated polyester resins, unsaturated polybutadiene oligomers or unsaturated rubbers and then cured by actinic radiation or by a free radical catalyst.
  • At least one triazine compound comprising a terminal functional group, such as hydroxyl or amido may be reacted with a polymer and/or oligomer such as polyesters, polyurethanes and polydiols with reactive end-groups, partially hydrolyzed polyvinylacetate, epoxy resins, polysiloxanes and polymers comprising maleic anhydride, either in the main chain or as a side-chain, by methods analogous to those well known to those of ordinary skill in the art.
  • a polymer and/or oligomer such as polyesters, polyurethanes and polydiols with reactive end-groups, partially hydrolyzed polyvinylacetate, epoxy resins, polysiloxanes and polymers comprising maleic anhydride, either in the main chain or as a side-chain, by methods analogous to those well known to those of ordinary skill in the art.
  • Grafting is yet another way of bonding of the presently claimed benzocycle- substituted pyrimidines and triazines to polymers and/or oligomers. Grafting may be carried out in solution, in the melt, or in the solid state with the initiators or actinic radiation types discussed above for polymerization when, for example, the novel triazines of the present nn urm .
  • Such benzocycle-substituted pyrimidines and triazines may be grafted to saturated polymers, e.g., polyolefins and their copolymers such as polyethylene, polypropylene and poly(ethylene-vinyl acetate), or to polymers comprising unsaturated moieties, e.g., polybutadiene, polyisoprene, ethylene- propylene-(diene monomer) terpolymers and polystyrene and its copolymers.
  • saturated polymers e.g., polyolefins and their copolymers such as polyethylene, polypropylene and poly(ethylene-vinyl acetate)
  • unsaturated moieties e.g., polybutadiene, polyisoprene, ethylene- propylene-(diene monomer) terpolymers and polystyrene and its copolymers.
  • the benzocycle-substituted pyrimidines and triazines of the present invention may be used in widely varying amounts in such applications depending upon such things as the material to be stabilized and the particular application.
  • the benzocycle-substituted pyrimidines and triazines of the present invention are typically employed in amounts from about 0.01 to about 20% by weight, preferably from about 0.1 to about 10% by weight, and most preferably from about 0.1 to about 5% by weight, based on the weight of the material to be stabilized.
  • the triazines are utilized in the same relative amounts but based on the total weight of the screening agent.
  • novel stabilizers of the present invention may also be employed in a non- bondable capacity, for example, in the stabilization of thermoplastic polymers as set forth in the many of the previously incorporated references.
  • thermoplastic polymers are polyolefins and polymers comprising heteroatoms in the main chain.
  • Preferred polymers are also thermoplastic polymers comprising nitrogen, oxygen and/or sulphur, especially nitrogen or oxygen, in the main chain.
  • compositions in which the polymer is a polyolefin, for example polyethylene or polypropylene.
  • thermoplastic polymers can be carried out by addition of the novel benzocycle-substituted triazine or pyrimidine compound and any further additives by the methods conventional in the art.
  • the incorporation can expediently be made before or during shaping, for example by mixing the pulverulent components or by adding the stabilizer to the melt or solution of the polymer, or by applying the dissolved or dispersed compounds to the polymer, with or without subsequent evaporation of the solvent.
  • Elastomers can also be stabilized as lattices.
  • the novel mixtures can also be added to the polymers to be stabilized in the form of a masterbatch which comprises these compounds, for example, in a concentration of from about 2.5 to about 25%, preferably from about 5 to about 20% by weight of the polymer.
  • novel mixtures can expediently be incorporated into the polymeric material by any number of methods, including those conventionally employed in the art, including by, for example: a) as an emulsion or dispersion (for example to lattices or emulsion polymers); (b) as a dry mix during mixing of additional components or polymer mixtures; (c) by direct addition to the processing equipment (for example extruders, internal mixers, etc.); or (d) as a solution or melt.
  • the stabilized polymer compositions obtained in this way can be converted into shaped articles, for example fibers, films, tapes, sheets, sandwich boards, containers, pipes and other profiles, by any number of conventional methods, for example hot pressing, spinning, extrusion, roto-molding or injection molding. Therefore, the present invention additionally relates to the use of the polymer composition according to the invention for the production of a shaped article.
  • the benzocycle-substituted pyrimidines and triazines of the present invention may be combined with a variety of additives conventionally employed in the UV stabilizing art.
  • additives include but are not limited to: a. Antioxidants
  • Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6- dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2-( ⁇ - methylcyclohexyl)-4,6-dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2,4,6- tricyclohexy lphenol; 2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols which are liner or branched in the side chains such as 2,6-di-nonyl-4-methylphenol; 2,4- dimethyl-6-(l -methy lundec-1 -yl)phenol
  • Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4- methoxyphenol; 2,5-di-tert-butylhydroquinone; 2,5-di-tert-amylhydroquinone; 2,6- diphenyl-4-octadecyloxyphenol; 2,6-di-tert-butylhydroquinone; 2,5-di-tert-butyl-4- hydroxyanisole; 3,5-di-tert-butyl-4-hydroxyanisole; 3, 5-di-tert-buty 1-4- hydroxyphenyl stearate; and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
  • Tocopherols such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methylphenol); 2,2'-thiobis(4-octy lphenol); 4,4'-thiobis(6-tert-butyl-3-methylphenol); 4,4'-thiobis(6-terrorism endeavouring « PCT/US99/1 7
  • Alkylidenebisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol); 2,2'- methylenebis(6-tert-butyl-4-ethylphenol); 2,2'-methylenebis[4-methyl-6-( ⁇ - methylcyclohexyl)phenol]; 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,2'- methylenebis(6-nonyl-4-methylphenol); 2,2'-methylenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(6-tert-butyl-4- isobuty lphenol); 2,2'-methylenebis[6-( ⁇ -methylbenzyl)-4-nony lphenol]; 2,2'- methylenebis[6-( , ⁇ -dimethylbenzyl)
  • O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'- dihydroxydibenzyl ether; octadecyl-4-hydroxy-3 ,5 -dimethy lbenzylmercaptoacetate; tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate; tris(3,5-di-tert-butyl-4- hydroxybenzyl)amine; bis(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)dithioterephthalate; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and isooctyl-3, 5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • Hydroxybenzylate malonates such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonate; dioctadecyl-2-(3-tert-butyl-4-hydroxy-5- methylbenzyl)malonate; didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4- hydroxybenzyl)malonate; and bis[4-(l,l,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di- tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds such as l,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene; l,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- 2,3,5,6-tetramethylbenzene; and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds such as 2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4- hydroxyanilino)-!
  • Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4- hydroxybenzylphosphonate; diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-tert-butyl-
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 , 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 , 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l- phospha-2,6,7-trioxabi
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l- phospha-2,6,7-trio
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol,
  • 1,9-nonanediol ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)-oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l-phospha-2,6,7- trioxabicyclo[2.2.2]octane.
  • esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l -phospha-2,6,7- trioxabicyclo[2.2.2]octane.
  • mono- or polyhydric alcohols such
  • Aminic antioxidants such as N,N'-diisopropyl-p-phenylenediamine; N,N'-di-sec- butyl-p-phenylenediamine; N,N'-bis(l ,4-dimethylpentyl)-p-phenylenediamine; N,N'- bis(l -ethyl-3-methylpentyl)-p-phenylenediamine; N,N'-bis( 1 -methy lheptyl)-p- phenylenediamine; N,N'-dicyclohexyl-p-phenylenediamine; N,N'-diphenyl-p- phenylenediamine; N,N'-bis(2-naphthyl)-p-phenylenediamine; N-isopropyl-N'- phenyl-p-phenylenediamine; N-(l,3-dimethylbutyl
  • UV-absorbers and light stabilizers i) 2-(2'-Hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)- benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(5 '-tert-buty 1- 2'-hydroxyphenyl)benzotriazole; 2-(2'-hydroxy-5'-(l, 1,3,3- tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5- chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro- benzotriazole; 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole;
  • esters of substituted and unsubstituted benzoic acids such as 4-tert-butyl-phenyl salicylate; phenyl salicylate; octylphenyl salicylate; dibenzoyl resorcinol; bis(4-tert- butylbenzoyl) resorcinol; benzoyl resorcinol; 2,4-di-tert-butylphenyl 3,5-di-tert- butyl-4-hydroxybenzoate; hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl 3,5-d
  • Acrylates such as ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate; isooctyl ⁇ -cyano- ⁇ , ⁇ - diphenylacrylate; methyl ⁇ -carbomethoxycinnamate; methyl ⁇ -cyano- ⁇ -methyl-p- methoxy cinnamate; butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate; methyl ⁇ - carbomethoxy-p-methoxycinnamate; and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2- methylindoline.
  • Nickel compounds such as nickel complexes of 2,2'-thio-bis-[4-(l, 1,3,3- tetramethylbutyl)phenol], including the 1 :1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N- cyclohexyldiethano lamine; nickel dibutyldithiocarbamate; nickel salts of monoalkyl esters including the methyl or ethyl ester of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid; nickel complexes of ketoximes including 2-hydroxy-4- methylphenyl undecyl ketoxime; and nickel complexes of l-phenyl-4-lauroyl-5- hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N- cyclohexyldiethano lamine; nickel dibutyldithiocarbamate
  • Sterically hindered amines as well as the N derivatives thereof (e.g., N-alkyl, N- hydroxy, N-alkoxy and N-acyl), such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate; bis(l ,2,2,6,6- pentamethyl ⁇ iperidin-4-yl)sebacate; bis( 1 -octyloxy-2,2,6,6-tetramethylpiperidin-4- yl)sebacate; bis(l,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4- hydroxybenzylmalonate; the condensate of 1 -(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- hydroxypiperidine and succinic acid; the condensate of N-al
  • Oxamides such as 4,4'-dioctyloxyoxanilide; 2,2'-diethoxyoxanilide; 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide; 2,2'-didodecyloxy-5, 5'-di -tert-buty loxanilide; 2-ethoxy-2'- ethyloxanilide; N,N'-bis(3-dimethylaminopropyl)oxamide; 2-ethoxy-5-tert-butyl-2'- ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide; and mixtures of o
  • Metal deactivators such as N,N'-diphenyloxamide; N-salicylal-N'-salicyloyl hydrazine; N,N'-bis(salicyloyl)hydrazine; N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hydrazine; 3-salicyloylamino-l ,2,4-triazole; bis(benzylidene)oxalyl dihydrazide; oxanilide; isophthaloyl dihydrazide; sebacoyl bisphenylhydrazide; N,N'- diacetyladipoyl dihydrazide; N,N'-bis(salicyloyl)oxalyl dihydrazide; and N,N'- bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites such as triphenyl phosphite; diphenyl alkyl phosphites; phenyl dialkyl phosphites; tris(nonylphenyl) phosphite; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphitc; diisodecyl pentaerythritol diphosphite; bis(2,4,-di-tert-butylphenyl)pentaerythritol diphosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite; bis(isodecyloxy)pentaerythritol diphosphite
  • Hydroxylamines such as N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N- dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-ditetradecylhydrcxy lamine; N,N- dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecyl- hydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylamine derived from hydrogenated tallow fatty amines.
  • Nitrones such as N-benzyl-alpha-phenyl nitrone; N-ethyl-alpha-methyl nitrone; N-octyl- alpha-heptyl nitrone; N-lauryl-alpha-undecyl nitrone; N-tetradecyl-alpha-tridecyl nitrone; N- hexadecyl-alpha-pentadecyl nitrone; N-octadecyl-alpha-heptadecyl nitrone; N-hexadecyl- alpha-heptadecyl nitrone; N-octadecyl-alpha-pentadecyl nitrone; N-heptadecyl-alpha- heptadecyl nitrone; N-octadecyl-alpha-hexadecyl nitrone; N
  • Peroxide scavengers such as esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters; mercaptobenzimidazole or the zinc salt of 2- mercaptobenzimidazole; zinc dibutyldithiocarbamate; dioctadecyl disulfide; and pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
  • Polyamide stabilizers such as copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers such as melamine; polyvinylpyrrolidone; dicyandiamide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyamides; polyurethanes; alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate; antimony pyrocatecholate; and tin pyrocatecholate.
  • Nucleating agents including inorganic substances such as talc and metal oxides (e.g.
  • titanium oxide or magnesium oxide and phosphates, carbonates and sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate and sodium benzoate
  • polymeric compounds such as ionic copolymers (e.g., ionomers).
  • Fillers and reinforcing agents such as calcium carbonate; silicates; glass fibers; asbestos; talc; kaolin; mica; barium sulfate; metal oxides and hydroxides; carbon black; graphite; wood flour and flours or fibers from other natural products; and synthetic fibers
  • Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, levelling assistants, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • Benzofuranones and indolinones such as those disclosed in US 4,325,863, US
  • novel benzocycle-substituted pyrimidines and triazines of the present invention can also be employed in multilayer systems.
  • a polymer composition having from about 0.1 to about 20% by weight and preferably a relatively high content of novel stabilizer, for example, about 5-15% by weight, is applied in a thin film (e.g., about 5 - 500 ⁇ m thick and, preferably, about 10 - 100 ⁇ m thick) to a shaped article made from a polymer containing little or no ultraviolet stabilizers.
  • a thin film e.g., about 5 - 500 ⁇ m thick and, preferably, about 10 - 100 ⁇ m thick
  • Such composition may be applied at the same time as the shaping of the base structure, for example by coextrusion in a manner analogous to that described in United States Patent No.
  • the outer layer or layers of the finished article have the function of a UV filter, which protects the interior of the article from UV light.
  • the outer layer preferably contains about 0.1 to about 20%, preferably about 1 to about 15%, and most preferably about 2 to about 10% by weight of the outer layer composition, of at least one of the benzocycle-substituted pyrimidine or triazine compounds of the present invention.
  • the polymers stabilized in this way are notable for high weathering resistance, especially for high resistance to UV light.
  • the novel mixtures comprising compounds of the formula (I), (II), or (IV)-(IX) can be used as stabilizers for coatings, for example for paints such as disclosed in numerous references (see, e.g., US 4,619,956, US 4,740,542, US 4,826,978, US 4,962,142, US 5,106,891, US 5,198,498, US 5,298,067, US 5,322,868, US 5,354,794, US 5,369,140, US 5,420,204, US 5,461,151, US 5,476,937, EP-0434608 and EP-A-0444323).
  • coatings and paints for the automobile industry The invention therefore also relates to those compositions which are film-forming binders for coatings.
  • Such novel coating compositions comprise about 0.01 to about 20%, preferably about 0.01 to about 10%, and more preferably about 0.02 to about 5% by weight of the binder of the coating composition of the presently claimed benzocycle-substituted pyrimidines and triazines of the present invention.
  • Multilayer systems are possible here as well (such as electrocoat/basecoat/clearcoat systems), where the concentration of the novel stabilizer in one or more of the layers, and typically the outer layer such as the clearcoat, can be relatively high, for example from about 0.01 to about 20%, preferably about 0.01 to about 10%, and more preferably about 0.02 to about 5% by weight of binder.
  • novel stabilizer in coatings is accompanied by the additional advantage that it prevents delamination, i.e. the flaking-off of the coating from the substrate.
  • This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates, and particularly epoxy e-coated metallic substrates.
  • the binder can in principle be any binder which is customary in industry, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991 which is incorporated herein by reference. In general, it is a film-forming binder based on a thermoplastic or curable resin, predominantly on a curable resin.
  • thermoplastic binders include acrylics, polyesters, polyurethanes and PVC plastisols.
  • curable binders include functional alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.
  • Such curable binders can be an ambient curable or a thermosetting binder.
  • binders include those which comprise a functional acrylate resin and a crosslinking agent.
  • binders may be employed in such coating systems.
  • suitable coating compositions containing specific binders include but are not limited to:
  • thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;
  • the coating composition according to the invention preferably further comprise one or more additional ultraviolet light absorbers, including but not limited to those specifically listed above in section b.
  • the additional UV absorbers may be, for example, another tris-aryl- 1,3, 5-triazine, a 2-hydroxyphenyl-2H-benzotriazole, a 2-hydroxybenzophenone, an ester of an unsubstituted benzoic acid, an acrylate, an oxamide (oxanilide), or any combination of the above.
  • the additional UV absorber is a 2-hydroxyphenyl-2H-benzotriazole and the weight ratio of benzotriazole to triazine is 4:1 to 1 :4. More preferably, the weight ratio is 2: 1 to 1 :2.
  • the invention therefore also relates to a coating composition which, in addition to the binder, the novel benzocycle-substituted pyrimidines and triazines and, optionally, additional UV absorbers, comprises a light stabilizer of the sterically hindered amine type.
  • the sterically hindered amine is employed in an amount of about 0.01 to 5% by weight based on the weight of the solid binder, preferably about 0.02 to 2% by weight.
  • a sterically hindered amine is a 2,2,6,6- tetramethyl piperazinone containing at least one group of the formula:
  • the stabilizer is a 2,2,6,6-tetraalkylpiperidine derivative containing at least one group of the formula:
  • J is, for example, hydrogen, hydroxyl, alkyl (such as methyl), alkoxy (such as methoxy) or acyl.
  • alkyl such as methyl
  • alkoxy such as methoxy
  • acyl examples of tetraalkylpiperidine derivatives which can be used in combination with the present trisaryl-1, 3, 5-triazine compounds are given in United States Patent Nos. 4,314,933, 4,344,876, 4,426,471, 4,426,472, 4,619,956, 5,004,770, 5,006,577, 5,064,883, 5,1 12,890, 5,124,378, 5,106,891, 5,204,473, and 5,461,151 , which are incorporated by reference herein for all purposes as if fully set forth.
  • tetraalkylpiperidine derivatives as well as their N-alkyl, N-acyl, N-hydroxyl and N-alkoxy analogs (where not already included in the following list): bis(2,2,6,6-tetramethylpiperid-4-yl) succinate, bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate, bis(l ,2,2,6,6-pentamethylpiperid-4-yl) sebacate, di(l ,2,2,6,6-pentamethylpiperid-4-yl) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis( 1 -octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate, tetra(2,2,6,6-tetramethylpiperid-4- yl) butane-l, 2,3, 4-tetracarboxylate, tetra(l,
  • tetraalkylpipieridine derivatives include SANDUVOR® 3050, 3052, 3055, 3056, 3058, PR-31 and PR-32 (Clariant Corp.); TINUVIN® 079L, 123, 144, 292, 440L and 622LD (Ciba Specialty Chemicals); CHIMASORB® 1 19 and 944 (Ciba Specialty Chemicals); and CYASORB® UV-3346, UV 3529, UV-3853, UV-500 and UV-516 (Cytec Industries Inc.).
  • the coating composition can also comprise further components, examples being solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts and/or leveling agents.
  • solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts and/or leveling agents examples are those described in many of the previously incorporated references as well as Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. Al 8,
  • Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, acids, amino-containing resins and/or phosphines.
  • acid catalysts are mineral acids, aliphatic and aromatic sulfonic acids (e.g. p-toluene sulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid), oxalic acid, maleic acid, hexamic acid, phosphoric acid, alkyl phosphate esters, phthalic acid and acrylic acid copolymers.
  • organometallic compounds are metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially those of the metal Al, It or Zr, or organometallic compounds such as organotin compounds, for example.
  • metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates.
  • metal chelates are the aluminum, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate and the alkoxides of these metals.
  • organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.
  • amine drying or curing catalysts are, in particular, tertiary amines, for example tributylamine, triethanolamine, N-methyldiethanolamine, N- dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane
  • ammonium salts for example trimethylbenzylammonium chloride.
  • Amino-containing resins are simultaneously binder and curing catalyst. Examples thereof are amino-containing acrylate copolymers.
  • the curing catalyst used can also be a phosphine, for example triphenylphosphine.
  • curing catalyst is a peroxide which can be used, for example, to cure a gel coating for a fiberglass article.
  • the novel coating compositions can also be radiation-curable coating compositions.
  • the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which after application are cured by actinic radiation, i.e. converted into a crosslinked, high molecular weight form.
  • the system is UV-curing, it generally contains a photoinitiator as well.
  • novel stabilizers can also be employed without the addition of sterically hindered amines.
  • novel coating compositions according to the invention can be applied to any desired substrates, for example to metal, wood, plastic, fiberglass or ceramic materials.
  • the coating compositions can be pigmented mono-coats or multi-layer
  • the novel coating composition can be used for either the base coat, or clear coat, or for both layers. If the topcoat of an automotive finish comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be
  • novel coating compositions can be applied to the substrates by the customary methods, for example by brushing, spraying, pouring, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 491-
  • the coatings can be cured at room temperature or by heating.
  • Thermosetting coatings are preferably cured at 50 - 150°C and, in the case of powder coatings, even at higher temperatures.
  • the invention therefore also relates to a coating, in particular a paint, which has been stabilized against the damaging effects of light, oxygen and heat by a content of the
  • the paint can be a pigmented mono-coat which comprises a film-forming binder and an organic pigment or dye, an inorganic pigment, a metallic pigment, or a mixture thereof.
  • the paint may also be a composition which comprises a primer in adhesion to a metal or plastic substrate; a pigmented basecoat that is in adhesion to the primer and which comprises a film-forming
  • a paint which is a clear topcoat for automobile original equipment manufacture (OEM) and/or refinish applications.
  • the invention furthermore relates to a process for stabilizing a coating based on polymers against damage by light, oxygen and/or heat, which comprises mixing with the coating composition a mixture comprising a compound of a benzocycle-substituted pyrimidine or triazine and to the use of mixtures comprising benzocycle-substituted pyrimidine or triazine compound in coating compositions as stabilizers against damage by light, oxygen and/or heat.
  • the coating compositions can comprise an organic solvent or solvent mixture in which the binder is soluble.
  • the coating composition can otherwise be an aqueous solution or dispersion.
  • the vehicle can also be a mixture of organic solvent and water.
  • the coating composition maybe a high-solids paint or can be solvent-free (e.g. a powder coating material).
  • the pigments can be inorganic, organic or metallic pigments.
  • the novel coating compositions preferably contain no pigments and are used as a clearcoat.
  • the coating composition as a topcoat for applications in the automobile industry, especially as a pigmented or unpigmented topcoat of the paint finish. Its use for underlying coats, however, is also possible.
  • the benzocycle-substituted pyrimidine or triazines of this invention may be applied topically by polishing a surface with a composition comprising the benzocycle- substituted pyrimidine or triazines and an inert carrier such as solvent, petroleum jelly, silicone oil in water emulsions, or automotive paint wax, e.g. Carnauba wax.
  • an inert carrier such as solvent, petroleum jelly, silicone oil in water emulsions, or automotive paint wax, e.g. Carnauba wax.
  • These topical treatment compositions may be used to stabilize coating films, fabrics, leather, vinyl and other plastics and wood.
  • the invention therefore also relates to a photographic material comprising an benzocycle-substituted pyrimidine or triazine compound.
  • the compounds according to the invention can be used for photosensitive materials of all kinds.
  • they can be employed for color paper, color reversal paper, direct-positive color material, color negative film, color positive film, color reversal film and other materials. They are preferably used, inter alia, for photosensitive color material which comprises a reversal substrate or which forms positives.
  • novel compounds can be combined with other UV absorbers, especially those which are dispersible in aqueous gelatin, for example with hydroxyphenylbenzotriazoles (cf. for example United States Patent Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701), benzophenones, oxanilides, cyanoacrylates, salicylates, or acrylonitriles or thiazolines.
  • hydroxyphenylbenzotriazoles cf. for example United States Patent Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701
  • benzophenones oxanilides
  • cyanoacrylates cyanoacrylates
  • salicylates or acrylonitriles or thiazolines.
  • oil-dissolved UV absorbers in the photographic material in layers other than those comprising the novel UV absorbers.
  • the present invention also encompasses compositions containing one or more binders.
  • the binder may comprise an alkyd, acrylic, polyester, phenolic, melamine, epoxy or polyurethane resin, or blends thereof.
  • binders include, but are not limited to:
  • the invention therefore additionally relates to a photographic material comprising, on support, a blue-sensitive, a green-sensitive and/or a red-sensitive silver- halide emulsion layer and, if desired, a protective layer, with a layer comprising a UV absorber being arranged above the uppermost silver-halide emulsion layer, wherein the UV absorber is a benzocycle-substituted pyrimidine or triazine compound.
  • photographic materials which have a layer comprising a compound of the formula (I), (II), or (IV)-(IX) above the uppermost silver- halide emulsion layer and/or between the green- and red-sensitive silver-halide emulsion layers.
  • the said layers which can comprise a UV absorber may have a UV absorber mixture and/or a further UV absorber which is dispersible in aqueous gelatin, but a compound of the formula (I), (II), or (IV)-(IX) must be present at least in one layer.
  • the novel material preferably has gelatin interlayers between the silver- halide emulsion layers.
  • silver halide in the blue-sensitive, green-sensitive and/or red-sensitive layer is silver chloride bromide comprising at least 90 mol % of silver chloride.
  • the compounds of the formula (I), (II), or (IV)-(IX), which are used in accordance with the invention, can be incorporated, alone or together with the color coupler and, if used, further additives, into the color photographic materials by dissolving the compounds beforehand in high-boiling organic solvents. It is preferred to use solvents which boil at higher than 160°C. Typical examples of such solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids, or alkylamides and phenols.
  • Preferred color couplers for use in the compositions of the invention examples of such compounds, further additives such as color cast inhibitors, DIR couplers and further light stabilizers, such as UV absorbers, phenols, phosphorus (III) compounds, organometallic complexes, hydroquinones and hydroquinone ethers, and more precise details on the structure of various photographic materials, can be found, for example, in the publications EP-A-0531258 and EP-A-0520938 and in the literature cited therein.
  • the invention also relates to a process for the stabilization of polyolefin or polyolefin copolymer films for agricultural applications, especially greenhouse applications, this polyolefin or polyolefin copolymer film having improved light stability and pesticide resistance, comprising incorporation of at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention, sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium into the polyolefin or polyolefin copolymer.
  • a further subject of the invention is a greenhouse, characterized in that it is covered by a polyolefin or polyolefin copolymer film having improved light stability and pesticide resistance and stabilized with a at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention, sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium.
  • Another subject of the invention is a process for stabilizing a polyolefin or polyolefin copolymer greenhouse film against detrimental effects of pesticides and light, oxygen and/or heat, which process comprises incorporation of at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention, sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium into said greenhouse film.
  • a polyolefin copolymer film stabilized with at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium for the stabilization of polyolefin or polyolefin copolymer films in contact with pesticides against photodegradation and damage by pesticides.
  • a film die such as a flat film die or a circular blown film die, and forming a film therefrom.
  • the films may be unoriented, or may be subjected to a conventional operation to impart a degree of orientation on the film.
  • Such a film may be oriented in one direction, such as in the machine direction, such as in the "machine direction” and/or the “transverse direction", or may be oriented in both directions, or "biaxially" oriented.
  • the present invention is also suitable for sheet applications.
  • the benzocycle-substituted pyrimidine or triazine compounds of the formula (I), (II), or (IV)-(IX) are suitable for the photochemical stabilization of undyed, dyed or printed fiber materials comprising for example, silk, leather, wool, polyamide or polyurethanes and especially cellulose-containing fiber materials of all kinds.
  • fiber materials are the natural cellulose fibers, such as cotton, linen, jute and hemp and also viscose staple fiber and regenerated cellulose.
  • Preferred textile fiber materials are those of cotton.
  • the triazine and pyrimidine compounds of the present invention are also suitable for the photochemical stabilization of hydroxyl-containing fibers in blend fabrics, for example blends of cotton with polyester fibers or polyamide fibers.
  • a further preferred area of application relates to the blocking or reduction of the UV radiation which passes through the above-mentioned textile materials (UV cutting) and the heightened sun protection which textile materials finished with a novel compound offer to the human skin.
  • one or a number of different compounds of the formula (I), (II), or (IV)-(IX) are applied to the textile fiber material by one of the customary dyeing methods, advantageously in a quantity of 0.01 to 5% by weight, preferably 0.1 to 3% by weight and, in particular, from 0.25 to 2% by weight, based on the weight of the fiber material.
  • the benzocycle-substituted pyrimidine or triazine compounds can be applied to the fiber material in various ways and fixed on the fiber, especially in the form of aqueous dispersions or printing pastes.
  • (I), (II), or (IV)-(IX) possess improved protection against photochemical breakdown of the fiber and yellowing phenomena and, in the case of dyed fibre material, are of enhanced (hot) light fastness.
  • Particular emphasis should be drawn to the greatly improved photoprotective effect of the treated textile fiber material and, in particular, the good protective effect with respect to short-wave UV-B rays. This is manifested by the fact that the textile fiber material finished with an benzocycle-substituted pyrimidine or triazine compound has, relative to untreated fabric, a greatly increased sun protection factor (SPF).
  • SPF sun protection factor
  • the sun protection factor is defined as the quotient of the dose of UV radiation which damages protected skin to that which damages unprotected skin. Accordingly, a sun protection factor is also a measure of the extent to which untreated fiber materials and fiber materials treated with a novel compound of the formula (I), (II), or (IV)-(IX) are permeable to UV radiation.
  • the determination of the sun protection factor of textile fiber materials is explained, for example, in WO94/04515 or in J. Soc. Cosmet. Chem. 40, 127-133 (1989) and can be carried out analogously thereto.
  • Yet another use of the UV absorbers according to the invention is in the stabilization of intra-ocular and contact lenses.
  • the inventive UV absorbers are suitable as photoprotective agents in cosmetic preparations.
  • the invention additionally relates, therefore, to a cosmetic preparation comprising at least one benzocycle-substituted pyrimidine or triazine compound and cosmetically acceptable carriers or auxiliaries.
  • the novel cosmetic composition contains from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the overall weight of the composition, of a benzocycle-substituted pyrimidine or triazine UV absorber and a cosmetically acceptable auxiliary.
  • the cosmetic composition can be prepared by physically mixing the novel UV absorber with the auxiliary by means of customary methods, for example by simply stirring together the two materials.
  • the cosmetic preparation according to the invention can be formulated as a water-in-oil or oil-in-water emulsion, as an oil-in-oil alcohol lotion, as a vesicular dispersion of an ionic or nonionic amphiphilic lipid, as a gel, solid stick or as an aerosol formulation.
  • the cosmetically acceptable auxiliary preferably contains from 5 to 50% of an oily phase, from 5 to 20% of an emulsifier and from 30 to 90% water.
  • the oil phase can comprise any oil which is suitable for cosmetic formulations, e.g., one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol.
  • Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
  • any conventionally employed emulsifier e.g., one or more ethoxylated esters of naturally occurring derivatives, i.e., polyethoxylated esters of hydrogenated castor oil; or a silicone oil emulsifier such as silicone polyol; an unmodified or ethoxylated fatty acid soap; an ethoxylated fatty alcohol; an unmodified or ethoxylated sorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride.
  • emulsifier e.g., one or more ethoxylated esters of naturally occurring derivatives, i.e., polyethoxylated esters of hydrogenated castor oil
  • silicone oil emulsifier such as silicone polyol
  • an unmodified or ethoxylated fatty acid soap an ethoxylated fatty alcohol
  • an unmodified or ethoxylated sorbitan ester an e
  • the cosmetic formulation can also comprise further components, for example emollients, emulsion stabilizers, skin moisteners, tanning accelerators, thickeners such as xanthan, moisture retention agents such as glycerol, preservatives, or fragrances and colorants.
  • emollients for example emollients, emulsion stabilizers, skin moisteners, tanning accelerators, thickeners such as xanthan, moisture retention agents such as glycerol, preservatives, or fragrances and colorants.
  • novel cosmetic formulations are notable for good protection of human skin against the damaging effect of sunlight while at the same time providing for reliable tanning of the skin.
  • the invention will now be illustrated by the following examples. The examples are not intended to be limiting of the scope of the present invention. In conjunction with the general and detailed descriptions above, the examples provide further understanding of the present invention.
  • Example 4 Monotetralin-bisresorcinol-triazine (Compound G .
  • the solid was dissolved in 50 mL of hot toluene. The slurry was warmed in a water bath until all of the solid dissolved. Methanol (300 mL) was added to the mixture maintained at reflux temperature. The solution was then cooled to room temperature. The resulting solid was filtered, washed with several portions of methanol, and dried in vacuo to give 20.25 g of the title compound as a pale yellow solid.
  • tetralin triazine UV absorbers Compound E and Compound J have lower color than Tinuvin 1577, a current art triazine UV absorber.
  • Thermogravimetric analysis was carried out. Duplicate specimens were heated in a Perkin-Elmer 7 Series thermobalance from 30 - 500°C at 10°C/ min in both air. The purge gas flow rate was ⁇ 25 mL/min. Compound E was compared against the major current art stabilizers for polycarbonate. As can be seen from Table II, Compound E is significantly less volatile than Tinuvin 1577, a current art stabilizer. (T-10% and T-20% are the temperatures at which 10% and 20%, respectively, of weight loss occurs during the above heating protocol.)
  • Polycarbonate plaques were prepared as follows. GE Lexan 105 barefoot natural flake polycarbonate resin (melt temperature 310 - 333 °C) was dry blended with
  • the blended compositions were j melt-mixed and extruded in a Haake torque rheometer equipped with a a 0.75-inch 25 : 1 single mixing screw extruder.
  • the zone temperatures were 246, 265, 295, and 304 °C.
  • the extruded polycarbonate was pulled through a water bath, dried, pelletized, and redried at 120°C for 4 - 48 hr in a forced air oven.
  • the pellets were injection molded at 340 °C with a 40 second dwell time using an Arburg "Allrounder" hydraulic injection molder to form 2 x
  • Stabilized polycarbonate plaques were prepared as in Example 3 with the 35 exception that the injection molding temperatures were lower. The temperatures were: nozzle - 305 °C; nozzle side - 310°C; middle - 300°C; and feed - 290°C. The plaques were subjected to 18 days of oven aging at 100°C. As can be seen from Table IV, Compound E inhibits thermal yellowing of polycarbonate and has performance equal or better than current art triazine UV absorbers Tinuvin 1577 and UV-1164.
  • Stabilized polycarbonate plaques were prepared as in Example 4. They were exposed in a xenon-arc WeatherOmeter following ASTM G-26 using Test Method B (Miami, Fla. conditions). The conditions were an irradiance of 0.35 W/m 2 at 340 nm, alternating cycles of light and darkness, intermittent water spray, and a black panel temperature of 63 ⁇ 3 °C. Delta E (total color change) was measured after 400 hr. of exposure. The results, summarized in Table V show that Compound E is more effective in reducing total color change than current art stabilizers Tinuvin 1577 and Tinuvin 234.
  • Stabilized clear acrylic melamine compositions were prepared and coated onto steel panels for accelerated weathering testing as follows.
  • Compound E (2% based on total resin solids) was pre-dissolved in xylenes, alone and in combination with Sanduvor ® 3058 HALS (0.67% or 1.0% based on total resin solids), and added to the clear acrylic melamine formulation given in Table VI.
  • Steel panels pre-coated with ED5050A E-coat, 764204 primer, and 542DF716 white base-coat and measuring 4" x 12" were obtained from ACT Laboratories, Inc. (Hillsdale, Michigan).
  • the panels were coated with the clear coat formulations using the draw-down technique (WC-52 Wire-CatorsTM obtained from Leneta Co., Ho-Ho-Kus, N.J.).
  • the clear coats were allowed to flash for 10 min. at ambient temperature and cured for 30 min. at 135°C.
  • Accelerated weathering is carried out with a QUV following ASTM G53 (GM cycle), which is weathering under alternate cycles of (i) UV light at 70 C for 8 hours and (ii) condensation with no UV light at 50 C for 4 hr. Specular properties (gloss and distinctness of image, or DOI) are measured as a function of weathering time.
  • Compositions containing either Compound E or Compound J both have improved gloss and DOI retention relative to the unstabilized control.
  • Compositions containing HALS S-3058 in addition to Compound E or Compound J also exhibit improved gloss and DOI retention.

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Abstract

This invention relates generally to benzocycle-substituted pyrimidines and triazines and the use thereof to protect against degradation by environmental forces, inclusive of ultraviolet light, actinic radiation, oxidation, moisture, atmospheric pollutants and combinations thereof. The new class of benzocycle-substituted pyrimidines and triazines comprises a benzocycle attached to the triazine or pyrimidine ring, and preferably an additional aryl ring containing a hydroxyl group, either free or blocked to form a latent stabilizer, ortho- to the point of attachment to the triazine or pyrimidine ring. These materials may, under the appropriate circumstances, be bonded to formulations comprising coatings, polymers, resins, organic compounds and the like via reaction of the bondable functionality with the materials of the formulation. A method for stabilizing a material by incorporating such benzocycle-substituted pyrimidines and triazines is also disclosed.

Description

BENZOCYCLE-SUBSTITUTED TRIAZINE AND PYRIMIDINE ULTRAVIOLET LIGHT ABSORBERS
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates generally to novel benzocycle-substituted pyrimidines and triazines and their use as protectants against degradation by environmental forces, including ultraviolet light, actinic radiation, oxygen, moisture, atmospheric pollutants and combinations thereof.
Description of Related Art
Exposure to sunlight and other sources of ultraviolet radiation is known to cause degradation of a variety of materials, especially polymeric materials. For example, polymeric materials such as plastics often discolor and may become brittle as a result of exposure to ultraviolet light. Accordingly, a large body of art has been developed directed towards materials such as ultraviolet light absorbers and stabilizers which are capable of inhibiting such degradation. A class of materials known to be ultraviolet light absorbers are o- hydroxyphenyltriazines, in which at least one substituent on the 1 , 3 or 5 carbon on the triazine ring is a phenyl group with a hydroxyl group ortho to the point of attachment to the triazine ring. In general this class of materials is well known in the art.
For example, United States Patent No. 3,843,371 discloses hydroxyphenyltriazines for use in photographic materials. The triazines in this patent, however, show poor solubilities and poor stabilities.
United States Patent No. 3,896,125 discloses hydroxyphenyl triazines, but these, too are poorly soluble and discolor with time.
The use of hydroxyphenyltriazines alone or in combination with other light stabilizers such as hydroxyphenylbenzotriazoles, benzophenones, oxanilides, cyanoacrylates, salicylates, and hindered amine light stabilizers (HALS), for the stabilization of polymers is also well known. For example, United States Patent Nos. 4,853,471 , 4,921,966, and 4,973,701, 4,973,702 disclose such combinations.
Typically, the aforementioned aryl ring with the hydroxyl group ortho to the point of attachment to the triazine ring is based on resorcinol and, consequently, this aryl ring also « ««, ,, * PCT/US99/
WO 99/67225
contains a second substituent (either a hydroxyl group or a derivative thereof) para- to the point of attachment to the triazine ring. For example, United states Patents No. 3,1 18,837 and 3,244,708 disclose /?-alkoxy-ø-hydroxyphenyl triazines with improved UV protection, but many embodiments of such triazines exhibit poor compatibility and solubility, and poor yellowing performance.
This para- substituent can be "non-reactive," as in the case of an alkyloxy group, or "reactive" as in the case of a hydroxyalkyloxy (active hydrogen reactive site) or (meth)acryloyl (ethylenic unsaturation reactive site) group. For the purposes of the present invention, the former are referred to as "non-bondable" benzocycle-substituted pyrimidines and triazines and the latter are referred to as "bondable" benzocycle-substituted pyrimidines and triazines.
Low volatility is an important characteristic of stabilizers used in any applications where high temperatures are encountered. High temperatures are used in the processing of thermoplastics and in the curing of thermoset resins and coatings. High temperatures are also often present in the end-use applications for the stabilized material. Low volatility will prevent loss of the stabilizer during processing, curing, and high temperature end-uses. Besides reducing losses of stabilizer during processing or curing, low volatility will minimize processing problems such as die lip build-up and plate-out.
Many polymer additives (such as ultraviolet light stabilizers) migrate out of the polymer substrate to be protected, or are adsorbed (chemically or physically) by one or more systems components (such as pigments), thereby diminishing their effectiveness. Such migration and adsorption problems are examples of the general problems of lack of solubility and compatibility found for many commercial polymer additives.
Bondable triazines are well known in the art. For example, United States Patent Nos. 3,423,360, 4,962,142 and 5,189,084 disclose various bondable and the incorporation of these compounds into polymers by chemical bonding. Bondable stabilizers have a potential advantage in this respect in that, depending on the bondable functionality and the particular polymer system to be stabilized, they can be chemically incorporated into a polymer structure via reaction of the bondable functionality either during polymer formation (such as in the case of polymerizing monomers or a crosslinking polymer system) or subsequently with a preformed polymer having appropriate reactive functionality. Accordingly, due to such bonding, migration of these UV absorbers between layers of multi-layer coatings and into polymer substrates is greatly reduced. SUMMARY OF THE INVENTION The present invenlion provides a new class ol' benzocycle-substiluted pyrimidines and triazines depicted below, in which a substituent attached to the triazine or pyrimidine ring is a fused benzocyclic group:
Figure imgf000005_0001
wherein X signifies hydrogen or a blocking group, A can be a nitrogen or optionally substituted methine, and the fused ring designated by S is a non-aromatic 4 to 12 membered ring, optionally containing one or more heteroatoms; any of the three rings may bear one or more additional substituents. These fused benzocyclic-substituted triazines and pyrimidines have the advantage of being highly soluble in and compatible; of having extremely low volatility, and therefore low losses during high temperature processing or curing; of being highly effective in inhibiting yellowing; and of being highly effective in preventing degradation of polymers and coatings due to the action of actinic radiation, heat, oxygen, and moisture. The benzocyclic substituted triazine and pyrimidine UV absorbers of the present invention possess exceptionally low volatility, lower than most current art UV absorbers. Furthermore these benzocyclic triazine UV absorbers, impart improved weatherability and yellowing resistance to polymers compared to current art UV absorbers. None of the previously available triazine UV stabilizers and absorbers combine the unexpected low volatility along with the weatherability, yellowing resistance, solubility, and compatibility of the benzocyclic substituted triazine and pyrimidine absorbers and stabilizers of the present invention.
More specifically, the new benzocycle-substituted pyrimidines and triazines of the present invention have general formula (I):
Figure imgf000006_0001
(I) wherein each A is independently nitrogen or methine optionally substituted with R2, and at least two A are nitrogen; each of T and T' is independently a direct bond, carbon, oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or functional groups containing these elements. X is independently selected from hydrogen and a blocking group; each of R1 and R2 is independently a hydrocarbyl group, a functional hydrocarbyl group, hydroxy, alkoxy, hydrogen, halogen, cyano, or isocyano; each of Y, Z, R3 and R4 are independently a hydrogen, hydrocarbyl group, a functional hydrocarbyl group, halogen, hydroxyl, cyano, -O(hydrocarbyl), -O(functional hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl), -N(hydrocarbyl)(functional hydrocarbyl), -S(hydrocarbyl),
-S(functional hydrocarbyl), -SO2(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -SO3(functional hydrocarbyl), -COO(hydrocarbyl), -COO(functional hydrocarbyl), -CO(hydrocarbyl), -CO(functional hydrocarbyl, -OCO(hydrocarbyl), -OCO(functional hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -CONH2, -CONH(hyrdocarbyl), -CONH(functional hyrdocarbyl),
-CON(hydrocarbyl)(hyrdocarbyl), -CON(hydrocarbyl)(functional hyrdocarbyl), -CON(functional hydrocarbyl)(functional hyrdocarbyl), -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups; each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous, boron, silicon, selenium, tellurium, or functional groups containing these elements; each of m, n, and o is independently an integer between 0 and 4, provided that when both G are direct bonds, the sum of m, n and o is between 2 and 10, and that when one G is a direct bond, the sum of m, n and o is between 1 and 9, and when neither G is a direct bond, the sum of m, n and o is between 0 and 8; p is an integer between 0 and 3; and q is an integer between 0 and 20.
Preferably, T' is an oxygen atom and Y is a group L, to give a mono-resorcinol derived benzocycle-substituted pyrimidine or triazine of formula (II):
Figure imgf000007_0001
(II) wherein L is defined as Y, Z, R3 and R4 as defined above; and substituents A, G, T, X, Y, Z, R1 to R4, and subscripts m, n, o, p, and q, are defined as above for general formula (I).
More preferably, TZ in formula (II) is a resorcinol derivative of formula (Ilia) or (Illb):
Figure imgf000008_0001
( Ilia) ( Illb)
to give a mono benzocycle bis-resorcinol derived triazine of formulas (IVa) and (IVb):
Figure imgf000008_0002
More Preferably, each L in formulas III and IV are independently selected from the group consisting of : hydrogen; an alkyl of 1 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; an aralkyl of 7 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, chloro, cyano, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; a polyoxyalkylene radical of the formula XII
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-D, (XII) wherein D, is hydrogen,
-CH2-CH2— CH2
-CH2-CH(OH)-CH2-OH, V or R25; a polyoxyalkylene radical of the formula XIII
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D2 (XIII) wherein D2 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula VIII
-YY-O-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D3 (XIV) wherein D3 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula XV
-(CH2)kk-CH(R21)-CO-BI-(CnnH2nn-0-)mm-CnnH2nn-B1-D4 (XV) wherein D4 is hydrogen of R25; a polyoxyalkylene radical of the formula XVI
-CO-CH2-CH2-NH-(CnnH2„„-0-)mm-CnnH2nn-D5 (XVI) wherein D5 is -NH2, -NH-(CH2)2-COO-R23 or -O-R25; a polyoxyalkylene radical of the formula XVII
-YY-O-CO-CH2-CH2-NH-(CnnH2nn-O-)mm-CnnH2nn-D5 (XVII) wherein D5 is as defined under formula (XVI); a polyoxyalkylene radical of the formula XVIII
"(CnnH2nn-O-)mm-CnnH2nn-D6 (XVIII) wherein D6 is -NH-CO-R24, -OR25, OH or H; a polyoxyalkylene radical of the formula XIX
-CH-CH2-(OCH— CH2)m-D7
Figure imgf000009_0001
wherein D7 is -OR25, -NHCOR24 or -OCH2CH2OR25; R21 is hydrogen or C,-C16 alkyl; R22 is halogen or -O-R23;
R23 is hydrogen, C,-C6 alkyl, C3-C6 alkenyl, aryl, or aryl-C,-C4-alkyl; R24 is hydrogen, C,-C12 alkyl or aryl; R25 is C,-C16 alkyl, C5-C12 cycloalkyl, C3-C6 alkenyl,
C,-C12 alkylaryl or aryl-C,-C4 alkyl; R26 is hydrogen or C,-C4 alkyl; R27 is hydrogen, C,-C18 alkyl, C3-C6 alkenyl, C,-C18 alkoxy, halogen or aryl-C,-C4- alkyl; R28 and R29 independently of one another are hydrogen,
C,-Clg alkyl, C3-C6 alkenyl, C,-C,8 alkoxy, or halogen; R30 is hydrogen, C,-C4 alkyl or CN; YY is unsubstituted or substituted C2-C20 alkyl; kk is zero or an integer from 1-16; B, is O or NH; mm is an integer from 2 to 60; nn is an integer from 2 to 6; u is an integer from 1 to 4.
Preferred in the present invention are compounds of formula (IV) wherein both G are direct bonds, m = 4, n, o, p and q are 0, and all A are nitrogen of formula (IVc):
Figure imgf000010_0001
(IVc)
Even more preferred in the present invention are bis-benzocycle-substituted pyrimidines and triazines of formula (V):
Figure imgf000011_0001
(V) wherein all substituents are as defined above for general formulas (I) to (IV). Most preferred in the present invention are compounds of formula 5 wherein all G are direct bonds; m = 4; n, o, p, and q are 0; and all A are nitrogen, said compound having formula:
Figure imgf000011_0002
wherein
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms;
X is independently selected from hydrogen and a blocking group; and
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano. The benzocycle-substituted pyrimidines and triazines of the present invention further comprise oligomeric species of formulas (VI) and (VII):
Figure imgf000012_0001
(VI) wherein
A, T, T', Y, Z, R1 - R4, G, m-q, and X, are as defined above; r is an integer between 2 and 4;
D when r is 2, is selected from the group consisting of C2-C16 alkyl, C4-C12 alkenyl, xylylene, C3-C20 alkyl which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20 alkyl which is interrupted by one or more oxygen atoms, — CH2CH(OH)CH2O— R15— OCH2CH(OH)CH2,
— CO— R16— CO— , —CO— NH— R17— NH— CO— ,
— (CH2) — COO— R18— OCO— (CH2) — a polyoxyalkylene bridge member of the formula XX
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-CH2-CH(OH)-CH2- (XX), a polyoxyalkylene bridge member of the formula XXI
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-(CII2)u-CO- (XXI), a polyoxyalkylene bridge member of the formula XXII
-YY-O-CO(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-COO-YY- (XXII), a polyoxyalkylene bridge member of the formula XXIII -(CIl2)u-ClI(R2l)-CO-B1^(CnnH2nn-O-)mmCnnlI2nn-BI-CO-CH(R2,)-
(CH2)kk- (XXIII), a polyoxyalkylene bridge member of the formula XXIV ( XXIV) ;
Figure imgf000013_0001
a polyoxyalkylene bridge member of the formula XXV
-YY-O-CO-(CH2)2-NH-(CnnH2nn-O-)mm-CnnH2nn-NH-
(CH2)2COO-YY- (XXV), a polyoxyalkylene bridge member of the formula XXVI
-(CnnH2nn-O-)mm-CnnH2nn- (XXVI), and a polyoxyalkylene bridge member of the formula XXVII
-CH(CH3)-CH2-(O-CH(CH3)-CH2)a-(O-CH2-CH2)b-(O-CH2- CH(CH3)C- (XXVII), wherein a + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0, R2' is hydrogen or C,-C,6 alkyl, R22 is halogen or -O-R23,
R23 is hydrogen, C,-C6 alkyl, C3-C6 alkenyl, aryl, or aryl-C,-C4-alkyl, R24 is hydrogen, C,-C12 alkyl or aryl, R25 is C,-C16 alkyl, C5-C12 cycloalkyl, C3-C6 alkenyl,
C,-C12 alkylaryl or aryl-C,-C4 alkyl, R26 is hydrogen or C,-C4 alkyl, R27 is hydrogen, C,-C,g alkyl, C3-C6 alkenyl, C,-C)g alkoxy, halogen or aryl-C,-C4 alkyl, R28 and R29 independently of one another are hydrogen, C,-C,8 alkyl, C3-C6 alkenyl, or C,-C18 alkoxy, or halogen; R30 is hydrogen, C,-C4 alkyl or CN, YY is unsubstituted or substituted C2-C20 alkyl, kk is zero or an integer from 1-16, B, is O or NH, mm is an integer from 2 to 60, nn is an integer from 2 to 6, u is an integer from 1 to 4; when r is 3, D is
(CH2)s-COO- R 19
and when r is 4, D is
(CH2)s-COO- R 20
wherein R19 is C3-C10 alkanetriyl and R20 is C4-C10 alkanetetryl; and s is 1-6;
R15 is C2-Cl0 alkyl, C2-C10 oxaalkyl or C2-C10 dithiaalkyl, phenyl, naphthyl, diphenyl, or C2-C6 alkenyl, or phenylene-XX-phenylene wherein XX is — O— , — S— , — SO2— , — CH2— , or — C(CH3)2— ; R'6 is C2-C!0 alkyl, C2-C10 oxaalkyl or C2-C,0 dithiaalkyl, phenyl, naphthyl, diphenyl, or C2-C6 alkenyl provided that when r is 3 the alkenyl has at least 3 carbons; R'7 is C2-C10 alkyl, phenyl, naphthyl, diphenyl, or C2-C6 alkenyl, methylenediphenylene, or C4-C,5 alkylphenyl; and R18 is C2-C]0 alkyl, or C4-C20 alkyl interrupted by one or more oxygen atoms; and
Figure imgf000014_0001
(VII) wherein A, T, T', Y, Z, R1 - R4, G, m-q, and X, are as defined above; r is 2 or 3; X', when r is
2, is —CO— R16— CO— , — CO2— R16— CO2— — SO2— R16— SO2— ,
— CO— NH— R'7— NH— CO— , a polyoxyalkylene bridge member of formula -CO-(CH2)u-
O-(CH2-(CH2)u-O-)mm-(CH2)u-CO-, or (XXIV) ;
Figure imgf000015_0001
when r = 3, X' is:
-(-CO2-R16)R19, -(-CONH-R16)R19, -(-SO2-Rl6)R19 wherein R16, R17, R18, and R19 are as defined above.
The benzocycle-substituted pyrimidines and triazines of the present invention also comprise oligomeric species of the formulas (VIII) and (IX):
Figure imgf000015_0002
(VIII)
wherein A, T, , Y, Z, R1 through R3, G, m through q, and X, are as defined above;
R4 is selected from the group consisting of straight chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkyl substituted by phenylene, alkyl interrupted by phenylene,
Figure imgf000015_0003
67225 wherein E is selected from the group consisting of alkyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by cyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8 to 12 carbon atoms; and r is an integer between 2 and 4.
Figure imgf000016_0001
(IX) wherein each A is independently nitrogen or methine optionally substituted with R2, and at least two A are nitrogen; each of T and T' is independently a direct bond, carbon, oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or a functional group containing these elements; each of Y, Z, R1, and R2 is independently a hydrocarbyl group, a functional hydrocarbyl group, hydrogen, halogen, cyano, or isocyano; each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous, boron, silicon, selenium, tellurium, or functional groups containing these elements; each of m, n, and o is independently an integer between 0 and 4, provided that when both G are direct bonds, the sum of m, n and o is between 2 and 10, and that when one G is a direct bond, the sum of m, n and o is between 1 and 9, and when neither G is a direct bond, the sum of m, n and o is between 0 and 8; p is an integer between 0 and 3; q is an integer between 0 and 12; X is independently hydrogen or a blocking group; 67225
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano; r is an integer between 2 and 4; D, when r is 2, is selected from the group consisting of C2-C]6alkylene,
C4-C12alkenylene, xylylene, C3-C20alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20alkylene which is interrupted by one or more oxygen atoms, — OOCR14COO — , — CH2CH(OH)CH2O— R15— OCH2CH(OH)CH2, — CO— R16— CO— , — CO— NH— R17— NH— CO— , and — (CH2) — COO— R18— OCO— (CH2). — ; and when r is 3, D is
19
(CH2)s-COO- ■ R1
and when r is 4, D is
-(CH2)s-COO- R 20
wherein
R19 is C3-C10alkanetriyl and R20 is C4-C10alkanetetryl; s is 1-6; r is an integer between 2 and 4;
D, when r is 2, is selected from the group consisting of C2-C16alkylene, C4-C12alkenylene, xylylene, C3-C20alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20alkylene which is interrupted by one or more oxygen atoms, — CH2CH(OH)CH2O— R15— OCH2CH(OH)CH2, — CO— R16— CO— , —CO— NH— R17— NH— CO— , and — (CH2) — COO— R18— OCO— (CH2) — ; and when r is 3, D is
r-(CH2)s-COO- -R 19
and when r is 4, D is
(CH2)s-COO- R 20
wherein R19 is C3-Cι0alkanetriyl and R20 is C4-C,0alkanetetryl; s is 1-6;
R8 is C,-C18 alkyl, C3-C18 alkenyl, C3-C20 alkyl, which is interrupted by O, N, or S, and/or substituted by OH, C,-C4 alkyl which is substituted by — P(O)(OR14)2, — N(R9) (R10), or — OCOR", and/or OH, or is glycidyl, cyclohexyl or C7-C„ pheny lalkyl; R9 and R10 are each independently of the other, C,-Cl2 alkyl, C3-C12 alkoxyalkyl, C4-
CI6 dialkylaminoalkyl or C5-C,2 cycloalkyl, or R9 and R10, when taken together, are C3-C9 alkylene or C3-C9 oxaalkylene of C3-C9 azaalkylene; R" is C,-C18 alkyl, C2-C18 alkenyl or phenyl;
R12 is C,-C,8 alkyl, C2-C18 alkenyl, phenyl, C,-C)2 alkoxy, phenoxy, C,-C,2 alkylamino; phenylamino, tolylamino or naphthylamino;
R13 is C,-C12 alkyl, phenyl, naphthyl or C7-C14 alkylphenyl; R14 is C,-C12 alkyl or phenyl;
R'5 is C2-C10 alkylene phenylene or a phenylene-x-phenylene- group, wherein X is — O— , — S— , — SO2— , — CH2— , or — C(CH3)2— ; R16 is C2-C10 alkylene, C2-C,0 oxaalkylene or C2-CI0 dithiaalkylene, phenylene, naphthylene, diphenylene or C2-C6 alkenylene; R17 is C2-C10 alkylene, phenylene, naphthylene, methylenediphenylene or C7-C)5 alkylphenylene, and R18 is C2-CI0 alkylene or C4-C20 alkylene which is interrupted by one or more oxygen atoms.
The benzocycle-substituted pyrimidines and triazines of the present invention may optionally have the added benefit of being capable of being chemically bonded to appropriate polymer systems via functionality attached to the benzocycle, pyrimidine and triazine groups (e.g., by a hydroxyl, ethylenic unsaturated and/or activated unsaturated group in one or more of R1, R2, Y or Z). These benzocycle-substituted pyrimidines and triazines may in general be prepared via a number of procedures well known in the art, for example, those described in Brunetti, H; Luethi, C; Helv. ChemicaActa, 55 (1972) pp. 1566-1595; Tanimoto, S.; Yamagata, M. Senryo to Yakahin, 40 (1995) pp 339ff; United States Patent Nos. 5,106,972, 5,288,868, 5,438,138, and 5,478,935; EP 395,938; EP 577,559; EP 649,841; EP 779,280; WO
9,628,431 ; GB 884,802; and Japanese Patent Kokai Tokkyo Koho 9,059,263 all of which are incorporated herein by reference for all purposes as if fully set forth.
The novel benzocycle-substituted pyrimidines and triazines of the present invention are particularly useful as ultraviolet light absorber agents for stabilizing a wide variety of materials including, for example, organic compounds, oils, fats, waxes, cosmetics, dyes and biocides, and particularly various organic polymers (both crosslinked and non-crosslinked) used in applications such as photographic materials, plastics, fibers or dyed fibers, rubbers, paints and other coatings, and adhesives. The present invention, consequently, also relates to (1) a method of stabilizing a material which is subject to degradation by actinic radiation (e.g., an organic material such as an organic polymer in the form of a film, fiber, shaped article or coating) by incorporating into said material an amount of an actinic radiation stabilizer composition effective to stabilize the material against the effects of actinic radiation, wherein the actinic radiation stabilizer composition comprises the inventive benzocycle-substituted 1,3, 5 -triazine or pyrimidine; and (2) the material so stabilized. The novel benzocycle-substituted pyrimidines and triazines of the present invention are also effective as ultraviolet light screening agents in applications such as sunscreens and other cosmetic preparations, capstock layers for extruded polymers, dyed fibers and laminated UV-screening window films, among others. The present invention, consequently, also relates (1) to a method of protecting a substrate against degradation by actinic radiation by applying to the substrate an actinic radiation screening layer (e.g., a coating film or capstock layer) containing an actinic radiation screening composition in an amount effective to reduce the amount of actinic radiation impinging on the substrate, wherein the actinic radiation screening composition comprises the inventive benzocycle-substituted pyrimidines and triazines; and (2) the substrate so protected. The novel benzocycle-substituted pyrimidines and triazines of the present invention may also be employed to form light stabilizing compositions. Such light stabilizing compositions may include a variety of other components known in the art including other ultraviolet light absorbers of the triazine class, other ultraviolet light absorbers of different classes (e.g. benzotriazoles, benzophenones), hindered amine light stabilizers, radical scavengers, antioxidants and the like. PO7US99/1370 WO 99/67225
These and other features and advantages of the present invention will be more readily understood by those of ordinary skill in the art from a reading of the following detailed description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The Benzocycle-substituted pyrimidines and triazines
As used herein, the term "benzocycle-substituted pyrimidines and triazines" broadly refers to any compound of formulas (I) through (IX), above.
As used herein, the term "benzocycle" broadly refers to any compound or substituent of general formula (X):
Figure imgf000020_0001
(X) Wherein substituents G, R1, R2, and subscripts m, n, o, p, and q, are defined as above for general formulas (I), (II), (III), and (IV);
The term "hydrocarbyl" in the context of the present invention, and in the above formulas, broadly refers to a monovalent hydrocarbon group in which the valency is derived by abstraction of a hydrogen from a carbon atom. Hydrocarbyl includes, for example, aliphatics (straight and branched chain), cycloaliphatics, aromatics and mixed character groups (e.g., aralkyl and alkaryl). Hydrocarbyl also includes such groups with internal unsaturation and activated unsaturation. More specifically, hydrocarbyl includes (but is not limited to) such groups as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl and alkynyl, preferably having up to 24 carbon atoms. A hydrocarbyl may optionally contain a carbonyl group or groups (which is/are included in the carbon count) and/or a heteroatom or heteroatoms (such as at least one oxygen, sulfur, nitrogen or silicon), in the chain or ring.
The term "functional hydrocarbyl" in the context of the present invention, and in the above formulas, broadly refers to a hydrocarbyl possessing pendant and/or terminal reactive and/or latent reactive functionality and/or leaving groups. "Reactive" functionality refers to functionality which is reactive with common monomer/polymer functionality under normal conditions well understood by those persons of ordinary skill in the relevant art. As non- limiting examples of reactive functionality may be mentioned active hydrogen-containing groups such as hydroxyl, amino, carboxyl, thio, amido, carbamoyl and activated methylene; isocyanato; cyano; epoxy; ethylenically unsaturated groups such as allyl and methallyl; and activated unsaturated groups such acryloyl and methacryloyl, and maleate and maleimido (including the Diels-Alder adducts thereof with dienes such as butadiene). "Latent reactive" functionality within the meaning of the present invention and, as would clearly be understood by those persons of ordinary skill in the art, refers to reactive functionality which is blocked or masked to prevent premature reaction. As examples of latent reactive functionality may be mentioned ketimines and aldimines (amines blocked, respectively, with ketones and aldehydes); amine-carboxylate salts; and blocked isocyanates such as alcohol (carbamates), oxime and caprolactam blocked variations. A "leaving" group within the meaning of the present invention, as would clearly be understood by those persons of ordinary skill in the relevant art, is a substituent attached to the hydrocarbyl chain or ring which during reaction is dislodged or displaced to create a valency on a carbon or heteroatom in the hydrocarbyl chain or ring, said valency being filled by a nucleophile. As examples of leaving groups may be mentioned halogen atoms such as chlorine, bromine and iodine; hydroxyl groups (protonated and unprotonated); quaternary ammonium salts (NT4 +); sulfonium salts (ST3 +); and sulfonates (-OSO3T); where T is, e.g., methyl or para-tolyl. Of all these classes of reactive functionality, the preferred functionality includes hydroxyl, -COOR5, -CR6=CH2, -CO-CR6=CH2, Cl, an isocyanate group, a blocked isocyanate group and -NHR5, wherein
R5 is selected from hydrogen and a hydrocarbyl (preferably of up to 24 carbon atoms); and R6 is selected from hydrogen and an alkyl of 1 to 4 carbon atoms (preferably hydrogen and methyl).
The term "hydrocarbylene" in the context of the present invention is a divalent hydrocarbon group in which both valencies derive by abstraction of hydrogens from carbon atoms. Included within the definition of hydrocarbylene are the same groups as indicated above for hydrocarbyl and functional hydrocarbyl with, of course, the extra valency (for example, alkylene, alkenylene, arylene, alkylaryl, etc.).
The term "functional hydrocarbylene" in the context of the present invention refers to a species of hydrocarbylene possessing pendant reactive functionality, latent reactive functionality and/or leaving groups. The term "non-functional hydrocarbylene" in the context of the present invention refers generally to a hydrocarbylene other than a functional hydrocarbylene. The benzocycle-substituted pyrimidines and triazines in accordance with the present invention also relate to latent stabilizing compounds against actinic radiation of the general formulas (I), (III), and (IV), wherein at least one of the hydroxyl groups on an aryl ring ortho to the point of attachment to the triazine or pyrimidine ring is blocked, that is, wherein at least one X is other than hydrogen. Such latent stabilizing compounds liberate the effective stabilizers by cleavage of the O-X bond, e.g., by heating or by exposure to UV radiation. Latent stabilizing compounds are desirable because they have many favorable properties, i.e., good substrate compatibility, good color properties, a high cleavage rate of the O-X bond and a long shelf life. The use of latent stabilizing compounds is further described in United States Patent Nos. 4,775,707, 5,030,731, 5,563,224 and 5,597,854, which are incorporated herein for all purposes as if fully set forth.
Latent stabilizing compounds comprising the benzocycle-substituted pyrimidines and triazines in accordance with the present invention can be prepared from compounds of the general formulas (I), (II) and (IV) through (IX), wherein at least one X is hydrogen, by subjecting said compounds to a further reaction to form latent stabilizing compounds, as described in the immediately preceding incorporated references.
As preferred examples of blocking groups X may be mentioned one or more of the following groups: allyl, -CORa, -SO2Rb, -SiRcRdRe, -PRfRε or -PORfRK, -CONHR\ wherein each Ra is independently selected from C,-C8 alkyl, halogen-substituted C,-C8 alkyl,
C5-CI2 cycloalkyl, C2-C8 alkenyl, -CH2-CO-CH3, CrC12 alkoxy, and phenyl or phenoxy which is unsubstituted or substituted by C C12 alkyl, C,-C4 alkoxy, halogen and/or benzyl; each Rb is independently selected from C,-CI2 alkyl, C6-C10 aryl and C7-C18 alkylaryl; each Rc, Rd and Re is independently selected from C,-C]8 alkyl, cyclohexyl, phenyl and C,-C18 alkoxy; each Rf and Rg is independently selected from C,-C,2 alkoxy, C,-C12 alkyl, C5-C!2 cycloalkyl, and phenyl or phenoxy which is unsubstituted or substituted by C,-Cl2 alkyl, C,-C4 alkoxy, halogen and/or benzyl; and each Rh is independently selected from C,-C8 alkyl, C5-C12 cycloalkyl, C2-C8 alkenyl, -CH2-CO-CH3, and phenyl which is unsubstituted or substituted by C,-C12 alkyl, C2-C8 alkenyl, C,-C4 alkoxy, halogen and/or benzyl. The reaction to give the latent stabilizing compounds of the present invention of the general formula (I), (III), and (IV), in which X is allyl, -CORa, -SO2Rb, -SiRcRdRe, -PRfR6 or -PORfRB, can be carried out, for example, by reaction of the compounds of the general formula (III) through (X), wherein at least one X is hydrogen with the corresponding halides such as allyl chloride, Cl-COR\ Cl-SO2Rb, Cl-SiRcRdRe, Cl-PRfRε, or Cl-PORfR8. The reaction to give the latent stabilizing compounds of the present invention of the general formulas (III) through (X) in which X is -CONHRh can be carried out, for example, by reaction of the compounds of the general formulas (III) through (X), wherein at least one X is hydrogen with the corresponding isocyanates. Furthermore, acylated compounds can be obtained by reaction with anhydrides, ketenes or esters, such as lower alkyl esters, as is well known to one skilled in the art. The above-described reagents may be used in approximately equimolar amounts or in excess, for example, from 2 to 20 mol with respect to the hydroxyl groups desired to be made latent in the starting compound of the general formula (I), (III), or (IV).
Catalysts customarily used for acylation, sulfonylation, phosphonylation, silylation or urethanation reactions may be used in forming the latent stabilizing benzocycle- substituted pyrimidines and triazines of the present invention. For example, acylation and sulfonylation reaction catalysts such as tertiary or quaternary amines, such as triethylamine, dimethylaminopyridine or tetrabutylammonium salts, may be used for forming these latent stabilizing compounds.
The reaction may be carried out in the presence of a solvent, such as relatively inert organics, e.g., hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as carbon tetrachloride or chloroform, or ethers such as tetrahydrofuran or dibutyl ether, or without a solvent. Alternatively, the reagent(s) may be employed as the solvent. The reaction temperature is usually between room temperature and about 150°C, for example, up to the boiling point of the solvent when a solvent is used. In preferred embodiments, each X is hydrogen.
In preferred embodiments, L is selected from the group consisting of hydrogen,
C,-C24 alkyl or mixtures thereof; C,-C24 branched alkyl or mixtures thereof; C3-C6 alkenyl; -COR12; -COOR12; -CONHR12; -SO2R13; C,-C18 alkyl which is substituted with one or more of the groups: hydroxy, C,-C18 alkoxy, C3-C18 alkenoxy, halogen, phenoxy, C,-C,8 alkyl-substituted phenoxy, C,-Cl8 alkoxy-substituted phenoxy, halogen-substituted phenoxy, -COOH, -COOR8, -CONH2, -CONHR9, -CON(R9)(R10), -NH2, -NHR9, -N(R9)(R10), -NHCOR", -N(R9)COR", -NHCOOR", -N(R9)COOR", -CN, -OCOR", -OC(O)NHR9, -OC(O)NHR9, -OC(O)N(R9)(R'°); C2-C50 alkyl which is interrupted by one or more oxygen atoms or carbonyl groups and optionally substituted by one or more substituents selected from the group consisting of hydroxy, C,-C|2 alkoxy, and glycidyloxy; glycidyl; and cyclohexyl optionally substituted with hydroxyl or -OCOR". R9 and R10 independently of one another are C C12 alkyl, C3-C12 alkoxyalkyl, C4-C16 dialkylaminoalkyl, or C5-C12 cycloalkyl, or R9 and R10 taken together are
C3-C9 alkylene or C3-C9 oxoaalkylene or C3-C9 azaalkylene. R" is C,-C] g alkyl, C2-Cι8 alkenyl, or phenyl.
Some of these groups as well as others are described in U.S. 5,106,891, U.S. 5,189,084, U.S. 5,356,995, U.S. 5,637,706, U.S. 5,726,309, EP 434,608, EP 704,437, WO 96/28431 , and GB 2,293,823 which are incorporated herein by reference for all purposes as if fully set forth.
L may also be an alkyl of 1 - 24 carbon atoms substituted by a hindered amine light stabilizer (HALS) group of the general formula XI. Triazines containing tetramethylpiperidine groups are described in U.S. 4,161,592 and 5,376,710, which are hereby incorporated by reference herein as if fully set forth.
Figure imgf000024_0001
wherein
J is — O— , — NR υ— , — T— (CH2)2— NR3ϋ— wherein T is — O— or — S— , and R30 is C,-C12 alkyl or hydrogen;
R31 is hydrogen or C,-C8 alkyl;
R32 is hydrogen, oxygen, C,-C21 alkoxyalkyl, C7-C8 aralkyl, 2,3-epoxypropyl, and aliphatic acyl group with 1-4 C atoms or one of the groups — CH2COOR33, — CH — CH(R34)— OR35, —COOR36 or —CONHR36, wherein R33 is C,-C 12 alkyl, C3-C6 alkenyl, phenyl, C7-C8 aralkyl or cyclohexyl, R34 is a hydrogen, methyl or phenyl, R35 is hydrogen, an aliphatic, aromatic, araliphatic or alicyclic acyl group with 1-8 C atoms, wherein the aromatic part is unsubstituted or is substituted by chlorine, C,C4 alkyl, C,-C8 alkoxy or by hydroxyl, and R36 is C,-C12 alkyl, cyclohexyl, phenyl or benzyl; nn„„^ PCT/US99/13
WO 99/67225
R37 is hydrogen, —OH or one of the groups — O— CO— R38 or — NR36— CO— R38, wherein R38 is C,-C12 alkyl or phenyl; and K is — O — (CmmH2mm) — wherein mm is 1 to 6, Preferred among the sterically hindered amines are members of the group consisting of: bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l,2,2,6,6-pentamethylpiperidin-4- yl)sebacate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino- 2, 6-dichloro- 1,3, 5-triazine; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4- yl)hexamethylenediamine and 4-morpholino-2,6-dichloro- 1 ,3, 5-triazine; 3-dodecyl-l- (2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-l-(l-acetyl-2,2,6,6- tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; a mixture of 4-hexadecyloxy- and 4- stearyloxy-2,2,6,6-tetramethylpiperidine, and mixtures thereof.
Most preferably, each L group is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms, or mixtures thereof; an alkyl of 4 to 20 carbon atoms containing one or more oxygen atoms in the chain and optionally substituted with one or more hydroxyl groups, or mixtures thereof.
Each R1 and R2 is independently selected from hydrogen, chloro, an alkyl of 1 to 8 carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionally containing an oxygen atom in the chain, a hydroxyalkyl of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, a hydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, an acyl group of 2 to 12 carbon atoms and an acyloxy of 2 to 12 carbon atoms. Especially preferred is when each R' and R2 is independently selected from hydrogen, chloro, an alkyl of 1 to 4 carbon atoms, and alkoxy of 1 to 4 carbon atoms, and particularly hydrogen, methyl, and methoxy. Each of R3 and R4 is independently selected from hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, a hydrocarbyloxy group of 1 to 24 carbon atoms, an acyl group of 2 to 24 carbon atoms and an acyloxy group of 2 to 24 carbon atoms. More preferably, each R1 is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain; an alkyloxy of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain; an alkenyl of 2 to 24 carbon atoms optionally containing an oxygen atom in the chain; an alkenyloxy of 2 to 24 carbon atoms optionally containing an oxygen atom in the chain; an acyl group of 2 to 12 carbon atoms; an acyloxy group of 2 to 12 carbon atoms; and optionally substituted benzoyl. Still more preferably, each R1 is independently selected from hydrogen, an alkyl of 1 to 8 carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionally containing an oxygen atom in the chain, a hydroxyalkyl of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, a hydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, an acyl group of 2 to 12 carbon atoms and an acyloxy of 2 to 12 carbon atoms. Some of these groups as well as others are described in U.S. 5,189,084, U.S. 5,354,794, U.S. 5,543,518, U.S. 5,637,706, EP 434,608, EP 704,437, and WO 96/28431 , which are incorporated herein by reference for all purposes as if fully set forth.
In preferred embodiments, each of R3 and R4 is independently selected from hydrogen, halogen, an acyl of 2 to 24 carbon atoms, benzoyl, alkyl of 1 to 24 carbon atoms, an alkenyl of 2 to 24 carbon atoms, a cycloalkyl of 5 to 24 carbon atoms; and an aralkyl of 7 to 24 carbon atoms.
In another preferred embodiment, R3 and R4 are independently methylene, alkylidene, or benzylidene substituted by a benzophenone UV absorber or a benzotriazole UV absorber. Related triazine - benzotriazole and triazine - benzophenone hybrid UV absorbers are disclosed in U.S. 5,585,422 which is incorporated by reference herein for all purposes fully set forth. In a related preferred embodiment, R3 and R4 are independently methylene, alkylidene, or benzylidene substituted by a second triazine UV absorber. Related triazine dimers (and oligomers) are disclosed in U.S. 5,726,309 and EP 704,437 which are incorporated by reference herein for all purposes fully set forth.
Preferred benzotriazoles comprise at least one member of the group consisting of: 2- (2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-2'- hydroxyphenyl)benzotriazole; 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(2'- hydroxy-5'-(l,l,3,3-tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'- hydroxyphenyl)-5-chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5- chloro-benzotriazole; 2-(3,-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(2'- hydroxy-4'-octoxyphenyl)benzotriazole; 2-(3',5,-di-tert-arnyl-2,-hydroxphenyl)benzotriazole; 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole; a mixture of 2-(3'-tert- butyl-2'-hydroxy-5,-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert- butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2- (3'-tert-butyl-2,-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'- tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'- hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2- ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecy]-2'-hydroxy-5'- methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2- isooctyloxycarbonylethyl)phenylbenzotriazole; 2,2-methylenebis[4-(l , 1 ,3,3- tetramethylbutyl)-6-benzotriazol-2-y lphenol]; the transesterification product of 2-[3'-tert- butyl-5'-(2-methoxycarbonylethyl)-2,-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [R-CH2CH-COO(CH2)3]2 - where R=3,-tert-butyl-4'-hydroxy-5,-2H-benzotriazol-2- ylphenyl; and derivatives thereof. Most preferred benzotriazoles are members of the group consisting of: 2-(2'-hydroxy-5'-(l,l,3,3-tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di- tert-amyl-2'-hydroxphenyl)benzotriazole; 2-(3',5'-bis(α,α-dimethylbenzyl)-2'- hydroxyphenyl)-benzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-(2- octyloxycarbonylethyl)phenyl)benzotriazole, the transesterification product of 2-[3'-tert- butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300 and mixtures thereof. In preferred embodiments, R' ' is selected from hydrogen and hydrocarbyl of 1 to 24 carbon atoms which may optionally be substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms and/or contain one or more oxygen and/or nitrogen atoms in the chain. More preferably, R" is selected from hydrogen and hydrocarbyl of 1 to 24 carbon atoms which may optionally be substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms. In preferred embodiments, R12 is selected from hydrogen and an alkyl of 1 to 4 carbon atoms. More preferably, R12 is selected from hydrogen and a methyl group.
In preferred embodiments, R13 is selected from hydrogen, a hydrocarbyl group of 1 to 8 carbon atoms, or phenyl. More preferably, R13 is hydrogen or methyl.
In preferred embodiments, G is a direct bond, m and o are 0, and n is 4. Further preferred embodiments may include any combination of the parameters mentioned above.
Methods of Preparation
The term "Lewis acid" is intended to include aluminum halides, alkylaluminum halides, boron halides, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium halides, arsenic halide, copper halides, cadmium halides, mercury halides, antimony halides, and the like. Preferred Lewis acids include aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, tin dichloride, tin tetrachloride, or a mixture thereof. As used herein, the term "step-wise" means a reaction sequence wherein a series of reactions are conducted, the first reaction producing compounds of Formulas (XXXII), (XXXV), or (XXXVI) and being carried out to between about 50% to about 100% completion prior to addition of a compound of Formula (XXXIII) to produce compounds of Formulas (I), (IV a/b/c), or (V). Preferably the reaction is carried out to between about 70% to about 100% completion prior to addition of compound of Formula (XXXIII), and more preferably to between about 75% to about 100% completion.
The novel benzocycle-substituted pyrimidines and triazines of the present invention can be prepared through the Friedel-Crafts reaction of a benzocycle moiety (XXX) with a halogen-substituted pyrimidine or triazine compound of Formula (XXXI) or (XXXIV). See Schemes 1, 2, and 3.
Figure imgf000028_0001
Scheme 1 wherein Hal is bromine, chlorine, or iodine. Compound (XXX) is defined as a protonated compound of Formula (X), as defined above. In compounds (XXXI) and (XXXIV) Hal, is a halogen, preferably bromine, chlorine, or iodine, and A, T, and Z are as defined above. In compound (XXXIII) L, X, T', Y, R3, and R4 are as defined above.
The relative amounts of the reactants are as follows. The amount of compounds (XXXI) or (XXXIV) should be in sufficient amounts to react with benzocyclic compounds of Formula (XXX) to produce compounds of Formula (XXXII), (XXXV), or (XXXVI). The amount of benzocyclic compound of Formula (XXX) is important to ensure that a sufficient amount of benzocyclic compounds of Formula (XXXII), (XXXV), or (XXXVI) are synthesized without excessive amounts of undesired side products such as trisbenzocyclic triazine or trisbenzocyclic pyrimidine. Moreover, excess amounts of benzocyclic compounds can lead to undesired product distributions enriched in mono- and tris- benzocyclic triazines, or mono- and tris-benzocyclic pyrimidines thus, making product separation and purification difficult and resource consuming.
(CH2)n
AI(Hal)3
Figure imgf000029_0001
(XXX) (XXXIV)
Figure imgf000029_0002
Scheme 2
The amount of benzocyclic compounds (XXX) should be in sufficient amounts to synthesize 2-halo-4,6-bisbenzocyclic- 1 ,3 ,5-triazine, 2,4-dihalo-6-benzocyclic- 1 ,3 ,5-triazine, 2-halo-4,6-bisbenzocyclicpyrimidine, 2,4-dihalo-6-benzocyclicpyrimidine or convert 2-halo- 4,6-bisbenzocyclic- 1,3, 5-triazine into 2,4,6-trisbenzocyclic- 1,3, 5-triazine or convert 2-halo- 4,6-bisbenzocyclicpyrimidine into 2,4,6-trisbenzocyclicpyrimidine. Preferably, there should be between about 1 to about 5 mol equivalents of benzocyclic compound of Formula (XXX) to compound of Formula (XXXI) or (XXXIV). The amount of aromatic compound of Formula (XXXIII) should be between about 0.5 to about 2.5 mol equivalents of aromatic compound of Formula (XXXIII) to compounds of Formula (XXXII), (XXXV), or (XXXVI). The amount of Lewis acid, Al(Hal)3 wherein Hal is a halide as defined above, used in the reaction should be in sufficient amounts to transform 2,4,6-trihalo- 1,3, 5-triazine or 2,4,6-trihalo-pyrimidine to the preferred 2-halo-4,6-bisbenzocyclic-l, 3,5-triazine, 2,4,6-trisbenzocyclic- 1,3, 5-triazine, or 2-halo-4,6-bisbenzocyclicpyrimidine, 2,4,6-trisbenzocyclicpyrimidine, respectively. The amount of Lewis acid should be between about 0.5 to about 500 mol equivalents. Preferably, the amount of Lewis acid should be between about 1 to about 5 mol equivalents. (
Figure imgf000030_0001
(XXX) (XXXIV)
Figure imgf000030_0002
15
Scheme 3
The Lewis acid can be combined with either the benzocyclic compound of Formula (XXX), compounds of Formula (XXXI) or (XXXIV), or both, in any manner. In situ reaction mixture preparation comprises addition of at least one Lewis acid to at least one
20 compound of Formula (XXXI) or (XXXIV), at least one benzocyclic compound of Formula (XXX), and optionally solvent, without regard to addition order. As used herein, one or more Lewis acids may be used, the first step and the second step Lewis acid may be the same or different.
The reaction should run for a sufficient amount of time, at a sufficient temperature
25 and pressure to synthesize the desired triazine or pyrimidine compound. The preferred reaction time for the synthesis of compounds of Formula (XXXII), (XXXV), (XXXVI), i.e., the first step, is between about 5 minutes and about 48 hours, more preferred between about 15 minutes and about 24 hours. The preferred reaction time for the synthesis of compounds of Formula (I), (IV a/b/c), (V), i.e., the second step, is between about 10 minutes and about
30 24 hours, more preferably time is between about 30 minutes and about 12 hours. The reaction pressure is not critical and can be about 1 atm or higher if desired. Preferably, the reaction is carried out under an inert gas such as nitrogen or argon. One of ordinary skill in the art with little or no experimentation can determine the reaction temperature necessary to obtain the desired product.
35 ^.. ^ε PCT/US99/1370
WO 99/67225
The step-wise process comprises mixing at least one Lewis acid and compounds of Formula (XXXI) or (XXXIV) with one or more of the desired benzocyclic compounds of Formula (XXX), preferably until the reaction is between about 70% to about 100% completed. Thereafter, the product is isolated and purified. The aromatic compound of Formula (XXXIII) is added to the purified product along with Lewis acid to synthesize the compounds of Formula (I), (IV a/b/c), or (V). The step- wise sequence allows for the isolation, purification, and storage of compounds of Formula (XXXII), (XXXV), or (XXXVI) prior to subsequent reaction with aromatic compounds of Formula (XXXIII).
To synthesize compounds of Formula (I), (IV a/b/c), (V), the preferred addition time of the aromatic compound of Formula (XXXIII) to the reaction mixture is between about 5 minutes to about 10 hours, more preferred addition time is between about 10 minutes to about 5 hours, and most preferred addition time is between about 15 minutes to about 2 hours.
The Lewis acid should be present in amounts sufficient to react with the number of halogens being substituted on compounds of Formula (XXXI) or (XXXIV). A range of between about 1 to about 5 mol equivalents of Lewis acid can be used. The preferred Lewis acid is aluminum chloride. A preferred amount of Lewis acid is between about 2 to about 4 mol equivalents to halo-triazine or halo-pyrimidine.
The synthesis of compounds of Formula (VI), (VII), VIII), or (IX) can be performed by methods commonly known in the art. One of ordinary skill in the art with little or no experimentation can determine the appropriate conditions to obtain the polymer product desired.
Uses of the benzocycle-substituted pyrimidines and triazines As indicated earlier, the novel benzocyclic-substituted pyrimidines and triazines of the present invention are particularly useful as ultraviolet light absorber agents for stabilizing a wide variety of materials including, for example, various polymers (both crosslinked and thermoplastic), photographic materials and dye solutions for textile materials, as well as in ultraviolet light screening agents (such as sunscreens). The novel benzocyclic-substituted pyrimidines and triazines of the present invention can be incorporated into such material in any one of a variety of conventional manners, including for example, physical mixing or blending, optionally, with chemical bonding to the material (typically to a polymer), as a component in a light stabilizing composition such as a coating or solution, or as a component in a UV screening composition such as a sunscreen composition. In one embodiment of the present invention, the benzocyclic-substituted pyrimidines and triazines of the present invention can be employed to stabilize materials which are subject to degradation by ultraviolet radiation by incorporating the presently claimed compounds into polymeric materials, either chemically or physically. Non-limiting examples of polymeric materials that may be so stabilized are polyolefins, polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, high-impact polystyrenes, polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles, polybutadienes, polystyrenes, ABS, SAN (styrene acrylonitrile), ASA (acrylate styrene acrylonitrile), cellulosic acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylsulfides, PPO, polysulfones, polyethersulfones, polyvinylchlorides, polycarbonates, polyketones, aliphatic polyketones, thermoplastic TPO's, aminoresin crosslinked polyacrylates and polyesters, polyisocyanate crosslinked polyesters and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins, drying and non-drying alkyd resins, alkyd resins, polyester resins, acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins, cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds, which are cross-linked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines, blocked amines with activated unsaturated and methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacetate resins, polyketimines in combination with unsaturated acrylic resins, radiation curable compositions, epoxymelamine resins, organic dyes, cosmetic products, cellulose-based paper formulations, photographic film paper, ink, and blends thereof. The preferred polymeric material is selected from the group consisting of polyolefins; copolymers of one or more monoolefins and/or diolefins with carbon monoxide and/or with other vinyl monomers; hydrocarbon resins (such as C5-C9) including hydrogenated modifications thereof and mixtures of polyalkylenes and starch; polyesters; copolyethers esters; polyethers; polyketones; polyamides and copolyamides derived from diamines, dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams; natural and synthetic rubbers and elastomers; polyurethanes; polystyrenes, poly-α-methylstyrenes and copolymers with other vinyl monomers; graft copolymers of styrene; high impact polystyrenes; polyacrylic acids, polymethacrylics acids, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles; homo- and copolymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof such as poly vinyl Λn„ tvt. PCT/US9
WO 99/67225
alcohol, poly vinyl acetate, polyacetals, and polybutyrals; homo- and copolymers of cyclic ethers such as alkylene glycols and alkylene oxides, as well as copolymers with bisglycidyl ethers; poly butadienes; polystyrenes; ABS (acrylonitrile butadiene styrene); SAN (styrene acrylonitrile); ASA (acrylate styrene acrylonitrile); cellulosic acetate butyrate; cellulosic polymers; polyureas; polyimides; polyamides-imides; polyester-imides; polyether-imides; polyhydantoins; polybenzimidazoles; polyphenylsulfide; PPO (polypropylene oxide); polysulfones; polyether sulfones; polyether ketones; halogen-containing polymers; polyvinylchlorides; polycarbonates; polyester carbonates; thermoplastic TPO's; amino resin cross-linked polyacrylates and polyesters; polyisocyante cross-linked polyesters and polyacrylates; phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins; saturated and unsaturated polyester resins; cross-linkable acrylic resins derived from substituted acrylates such as epoxy acrylates, hydroxy acrylates, isocyanato acrylates, urethane acrylates or polyester acrylates; alkyd resins, polyester resins, and acrylate resins cross-linked with melamine resins, urea resins, isocyantes, isocyanurates, carbamates, or epoxy resins; cross-linked epoxy resins derived from aliphatic cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds which are cross-linked with anhydrides or amines; polysiloxanes; Michael addition polymers of amines or blocked amines (e.g., ketimines) with activated unsaturated and/or methylene compounds; of ketimines with activated unsaturated and/or methylene compounds such as acrylates and methacrylates, maleates, and acetoacetates; polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins; radiation curable compositions; epoxymelamine resins; natural polymers such as cellulose, rubber, gelatin, and chemically modified derivatives thereof; organic dyes and pigments; any mixture or blends of the above; cosmetic products; cellulose-based paper formulations; photographic film; paper; ink; and intraocular lenses. Further non-limiting examples of specific polymers which may be stabilized include: 1. Homo- and copolymers of monoolefins and diolefins including but not limited to ethylene, propylene, isobutylene, butene, methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene and cycloolefins such as cyclopentene and norbornene; for example, polyethylenes (which optionally can be crosslinked) such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and branched low density polyethylene (BLDPE). 2. Copolymers of one or more monoolefins and/or diolefins with carbon monoxide and/or with other vinyl monomers, including acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, styrenes, vinyl acetate (such as ethylene/vinyl acetate copolymers), vinyl halides, vinylidene halides, maleic anhydride and allyl monomers such as allyl alcohol, allyl amine ally glycidyl ether and derivatives thereof.
3. Hydrocarbon resins (such as C5-C9) including hydrogenated modifications thereof and mixtures of polyalkylenes and starch.
4. Homo- and copolymers of styrenes such as styrene, p-methylstyrene and α — methylstyrene.
5. Copolymers of one or more styrenes with other vinyl monomers such as olefins and diolefins (e.g., ethylene, isoprene and/or butadiene), acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, vinyl acetate (such as ethylene/vinyl acetate copolymers), vinyl halides, vinylidene halides, maleic anhydride and allyl compounds such as allyl alcohol, allyl amine allyl glycidyl ether and derivatives thereof.
6. Graft copolymers of styrenes on polybutadienes, polybutadiene/styrene copolymers and polybutadiene/acrylonitrile copolymers; styrene (or α-methylstyrene) and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene copolymers; styrene and acrylonitrile on polyalkyl acrylates or methacrylates; and styrene and acrylonitrile on acrylate/butadiene copolymers.
7. Halogen-containing polymers such as polychloroprene; chlorinated rubbers; chlorinated and brominated isobutylene/isoprene copolymers; chlorinated or sulfochlorinated polyethylene; copolymers of ethylene and chlorinated ethylene; epichlorohydrin polymers and copolymers; and polymers and copolymers of halogen-containing vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride and/or vinylidene fluoride and other vinyl monomers. 8. Homo- and copolymers derived from α,β-unsaturated acids and derivatives thereof such as acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides and acrylonitriles. 9. Copolymers of the monomers mentioned in (8) with other unsaturated monomers such as olefins and diolefins (e.g., butadiene), styrenes, vinyl halides, maleic anhydride and allyl monomer such as allyl alcohol, allyl amine, allyl glycidyl ether and derivatives thereof. 10. Homo- and copolymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, such as vinyl alcohol, vinyl acetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol, allyl amine, allyl glycidyl ether, allyl phthalate and allyl melamine; as well as copolymers of such monomers with other ethylenically unsaturated monomers mentioned above. For the preceding groups 1-10 of polymers, the present invention further encompasses these polymers as prepared by metallocene catalysts. 10 11. Homo- and copolymers of cyclic ethers such as alkylene glycols and alkylene oxides, as well as copolymers with bisglycidyl ethers. 12. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; and polyoxymethylenes modified with thermoplastic polyurethanes, acrylates and/or MBS. 15 13. Polyphenylene oxides and sulfides.
14. Polyurethanes derived from hydroxy-functional components such as polyhydric alcohols, polyethers, polyesters, polyacrylics and/or polybutadienes on the one hand, and aliphatic and/or aromatic isocyanates on the other, as well as precursors thereof.
15. Polyamides and copolyamides derived from diamines, dicarboxylic acids and/or 20 aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6, polyamide 12/12, polyamide 11 and polyamide 12; aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic and or terephthalic acid and with or
25 without an elastomer as a modifier, for example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; block copolymers of the aforementioned polyamides with polyolefins, olefin copolymer, ionomers, chemically bonded or grafted elastomers, or polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides condensed
30 during processing (RIM polyamide systems).
16. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
17. Polyesters derived from dicarboxylic acids, diols and/or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene 35 terephthalate, poly- 1 ,4-dimethylcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolycthcr esters derived from hydroxyl- terminated ethers; PETG; PEN; PIT; and also polyesters modified with polycarbonate or MBS. 18. Polycarbonates and polyester carbonates. 19. Polysulfoncs, polyether sulfones and polyether ketones.
20. Crosslinked polymers derived from aldehydes condensation resins such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
21. Drying and non-drying alkyd resins.
10 22. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and also halogen-containing modifications thereof. 23. Crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylates, hydroxy acrylates, isocyanato acrylates, urethane acrylates or polyester acrylates. 15 24. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates or epoxy resins. 25. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds such as bisphenol A and bisphenol F, which are crosslinked with hardeners such as anhydrides or amines. 20 26. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, including cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose, as well as rosins and their derivatives. 27. Polysiloxanes. 25 28. Michael addition polymers of amines or blocked amines (e.g., ketimines) with activated unsaturated and/or methylene compounds such as acrylates and methacrylates, maleates and acetoacetates. 29. Mixtures or blends of any of the above, such as PP/EPDM, polyamide/EPDM or ABS,
PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, 30 PVC/CPE, PVC/acrylate, POM/thermoplastic PUR, PC/thermoplastic polyurethane,
POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and copolymers,
PATENT/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE, LDPE/EVA, LDPE/EAA,
PATENT/PP, PATENT/PPO, PBT/PC/ABS, PBT/PET/PC and the like.
35 „nv„,t P
WO 99/67225
30. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins including urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and acrylated melamines.
31. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.
32. Epoxymelamine resins such as light-stable epoxy resins cross-linked by an epoxy functional coetherified high solids melamine resin. Other materials which can be stabilized include, for example:
33. Naturally occurring and synthetic organic materials which may be mixtures of
10 compounds, including mineral oils, animal and vegetable fats, oils and waxes, or oils, fats or waxes based on synthetic esters (e.g., phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any ratio.
34. Aqueous emulsions of natural or synthetic rubber such as natural latex or lattices of carboxylated styrene/butadiene copolymers.
15 35. Organic dyes such as azo dyes (diazo, triazo and polyazo), anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethines, styryl dyes, di- and triaryl carbonium dyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitroso dyes, stilbene dyes, formazan dyes, quinacridones, carbazoles and perylene tetracarboxylic diimides.
20 36. Cosmetic products, such as skin lotions, collagen creams, sunscreen, facial make-up, etc., comprising synthetic materials such as antioxidants, preservatives, lipids, solvents, surfactants, colorants, antiperspirants, skin conditioners, moisturizers etc.; as well as natural products such as collagen, proteins, mink oil, olive oil, coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe, etc.
25 37. Cellulose-based paper formulations for use, e.g., in newsprint, cardboard, posters, packaging, labels, stationery, book and magazine paper, bond typing paper, multipurpose and office paper, computer paper, xerographic paper, laser and ink-jet printer paper, offset paper, currency paper, etc. 38. Photographic film paper.
30 39. Ink.
ALIPHATIC POLYAMIDE
The novel benzocyclic-substituted pyrimidines and triazines of the present invention can also be used with aliphatic polyamide polymers. An "Aliphatic polyamide" is 35 a polyamide characterized by the presence of recurring carbonamide groups as an integral part of the polymer chain which are separated from one another by at least two aliphatic carbon atoms. Illustrative of these polyamides are those having recurring monomeric units represented by the general formula:
-NHC(O)RC(O)NHR ' - or -NH-R-C(O)-
or a combination hereof in which R and R1 are the same or different and are alkylene groups of at least about two carbon atoms, preferably alkylene having from about 2 to about 12 carbon atoms. Exemplary of such polyamides are polyamides formed by the reaction of diamines and diacids such as poly (tetramethylene adipamide)(nylon 4,6); poly(hexamethylene adipamide) (nylon 6,6); poly (hexamethylene azelamide) (nylon 6,9); poly(hexamethylene sebacamide) (nylon 6,10); poly(heptamethylene pimelamide) (nylon 8,8); poly(nonamethylene azelamide) (nylon 9,9); poly(decamethylene azelamide) (nylon 10,9); and the like. Also illustrative of useful aliphatic polyamides are those formed by polymerization of amino acids and derivatives thereof, as for example lactams. Illustrative of these useful polyamides are poly(4-aminobutyric acid) (nylon 4); poly(6-aminohexanoic acid) (nylon 6); poly(7-aminoheptanoic acid) (nylon 7); poly(8-aminoocatanoic acid) (nylon 8); poly(9aminononanoic acid) (nylon 9); poly(10-aminodecanoic acid) (nylon 10); poly(l 1- aminoundecanoic acid) (nylon 11); poly(12-aminododecanoic acid) (nylon 12); and the like. Blends of two or more aliphatic polyamides may also be employed.
Copolymers formed from any combination of the recurring units of the above referenced aliphatic polyamides can be used. By way of illustration and not limitation, such aliphatic polyamide copolymers include caprolactam/hexamethylene adipamide copolymer (nylon 6/6,6); hexamethylene adipamide/caprolactam copolymer (nylon 6, 6/6); hexamethylene adipamide/hexamethylene-azelamide copolymer (nylon 6,6/6,9); and copolymers formed from recurring units of the above referenced aliphatic polyamides with aliphatic/aromatic polyamide recurring units may also be used. Examples of such copolyamides are nylon 6/6T; nylon 6,6/6, T; nylon 6/1 OT; nylon 6/12T; nylon 6,10/6,T etc. Preferred aliphatic polyamides for use in the practice of this invention are poly(caprolactam); poly(7-aminoheptanic acid); poly(tetramethylene adipamide); poly(hexamethylene adipamide); and mixtures thereof. The particularly preferred aliphatic polyamides are poly(caprolatam); poly(hexamethylene adipamide); poly(tetramethylene adipamide); and mixtures thereof.
Aliphatic polyamides useful in the practice of this invention may be obtained from commercial sources or prepared in accordance with known preparatory techniques. For example, polycaprolactam may be obtained from Allied Signal Inc. and poly(hexamethylene adipamide) may be obtained from DuPont Co.
The number average molecular weight of the aliphatic polyamide may vary widely. Usually, the aliphatic polyamide is of film forming molecular weight that is sufficiently high to form a free standing film and sufficiently low to allow melt processing of the blend into a film. Such number average molecular weights are well known to those of skill in the film art and are usually at least about 5,000 as determined by the formic acid viscosity method. In this method, a solution of 9.2 wt. Concentration of aliphatic polyamide in 90% formic acid at 25°C is used. In the preferred embodiments of the invention, the number average molecular weight of the aliphatic polyamide is from about 5,000 to about 1 ,000,000 and in the particularly preferred embodiments is from about 10,000 to about 100,000. Amongst the particularly preferred embodiments, most preferred are those in which the molecular weight of the aliphatic polyamide is from about 20,000 to about 40,000.
POLYURETHANE
Polyurethane (PUR) elastomer products ("spandex") can be stabilized against discoloration and loss of elasticity during UV light exposure with combinations of UV absorbers according to the invention and hindered amine light stabilizers. Spandex fibers is a PUR elastomer product, which requires very specific UV absorber and hindered amine light stabilizers properties in order to achieve optimum performance. UV absorbers of the triazine class of this invention can be combined with polymeric hindered amine light stabilizers (HALS) to provide outstanding performance in achieving the desired properties for the Spandex fiber applications. The triazine UV absorber of the invention, used alone or in combination with
HALS provides the following properties in the Spandex fiber application: (1) low color contribution at typical use levels in the 0.5-2.0% range; (2) sufficient MW, thermal stability and low volatility for fiber processing and thermal exposure conditions; (3) high compatibility and permanence; (4) prevent discoloration and loss of elasticity during exposure to UV light energy; (5) low extraction by water and dry cleaning solvents; (6) low color development during exposure to atmospheric pollutants, NOx, SOx, hydrocarbons, etc.;
(7) low interaction with sea water and pool chemicals; (8) low interaction and color development with typical phenolic antioxidants used for the thermal stabilization of
Spandex fibers; and (9) low interaction with copper based antioxidant systems used in
Nylon fibers for Nylon/Spandex fabrics. The triazine UV absorber with or without the polymeric HALS provides outstanding stabilization with minimum negative effect on secondary performance properties, such as low color development during NOx exposure and low interaction with copper based antioxidant systems using in Nylon fibers. As noted above, any of the triazine compounds disclosed herein can be used to impart one or more of the properties described above to Spandex fibers when added thereto in a stabilization effective amount.
Preferably, these triazine compounds are added in combination with polymeric HALS. The polymeric HALS is preferably poly[(6-morpholino-s-triazine-2,4- diyl)[2,2,6,6,-tetramethyl-4-piperidyl)imino]-hexamethylene [(2,2,6,6-tetramethyl-4- piperidyl)imino]]. Most preferably, the polymeric HALS is the methylated (M) version of the above HALS, which is sold by Cytec Industries, Inc. as CYASORB®UV-3529 light stabilizer. Other polymeric HALS disclosed in US Patent 4,331,586 are also suitable.
Spandex fibers are made from a polyurethane (PUR) prepolymer prepared from a diisocyanate and a glycol. There are four basic processes used to convert the PUR prepolymer into the fiber product. These processes are Solution Dry Spinning, Solution Wet Spinning, Melt Extrusion, and Reaction Spinning. The above UV stabilizer alone or in combination with HALS would be suitable for use in any or all four processes.
Spandex fibers may contain a processing antioxidant system, such as a phenolic antioxidant, or a phenolic/phosphite antioxidant combination. In addition, pigments, such as TiO2 are commonly used in the fiber products.
The triazine UV absorber alone or with M-HALS can be dissolved into DMF or DMAC and added to the PUR prepolymer solution prior to solution fiber spinning processes. Also, the combination can be extrusion compounded into the PUR compound used in the melt spinning process.
POLYCARBONATES
Among polymeric materials to be stabilized with the novel benzocycle-substituted pyrimidines and triazines of the present invention, preference is given to the polycarbonates, polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides, but especially to the polycarbonates. Those compounds are to be understood as being especially those polymers the constitutional repeating unit of which corresponds to the formula:
Figure imgf000041_0001
wherein A is a divalent phenolic radical. Examples of A are given inter alia in U.S. Pat. No. 4,960,863 and
DE-A-3 922,496. A can be derived, for example, from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense of the term, such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers, ketones, sulfones, sulfoxides, α,α'-bis(hydroxyphenyl)-diisopropylbenzenes, for example the compounds 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis(3,5- dichloro-4-hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)cyclohexane, or from the compounds of the formulae:
Figure imgf000041_0002
Figure imgf000041_0003
Figure imgf000041_0004
Figure imgf000042_0001
Figure imgf000042_0002
25
Figure imgf000042_0003
35
Figure imgf000043_0001
Figure imgf000043_0002
In one embodiment, the preferred resins are polycarbonates based on dihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,4-bis (4- hydroxyphenyl)-2-methylbutane; 1 , 1 -bis-(4-hydroxyphenyl)-cyclohexane; 2,2-bis-(3-chloro- 4-hydroxyphenyl)propane; 4,4'-sulfonyldiphenol; and l,l-bis-(4-hydroxyphenyl)-3,3,5- trimethy ley cl ohexane .
Also preferred are polycarbonate copolymers incorporating two or more phenols, branched polycarbonates wherein a polyfunctional aromatic compounds is reacted with the dihydric phenol(s) and carbonate precursor, and polymer blends of which polycarbonate comprises a significant portion of the blend.
The most preferred resins for both layers are polycarbonates based on bisphenol A. ~ „„.,„„, PCT/US99/137
WO 99/67225
U.S. Patent No. 5,288,788 also describes polycarbonates and polyester carbonates, especially aromatic polycarbonates, for example those based on 2,2-bis(4- hydroxyphenyl)proρane or l,l-bis(4-hydroxyphenyl)cyclohexane.
MULTILAYER SYSTEMS
British Patent Application No. 2,290,745 describes a number of methods have been developed to concentrate UV absorbers near or at the surface of polymeric materials. These include surface impregnation (see U.S. Patent Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating a plastic article with solutions containing thermoplastic resins and UV absorbers (see U.S. Patent Nos. 4,668,588 and 4,353,965). Both techniques suffer from drawbacks including requiring additional processing steps (i.e. applying, drying or curing), and encounter difficulties associated with the handling of large processed articles. An additional drawback, particularly relevant to polycarbonate sheet production, is the detrimental effect such post addition treatment would have on the surface of the polymeric substrate.
As described in the U.S. Pat. No. 5,445,872, application of surface layers via coextrusion takes place in a known manner in known coextrusion equipment as taught in U.S. Pat. Nos. 3,487,505 and 3,557,265. Coextrusion is a well recognized method of producing laminated thermoplastic materials by simultaneously extruding various numbers of layers which form a single composite material. U.S. Patent No. 4,540,623 describes coextruded materials of at least forty layers. Other methods produce as few as two or three different layers.
In one embodiment, the invention also relates to thermoplastic articles coated with a thermoplastic layer 0.1 to 10 mil (0.00254 mm to 0.254 mm), preferable 0.1 to 5 mil (0.00254 mm to 0.127 mm), thick, in which said layer contains 0.1% to 20% by weight of the benzocyclic-substituted pyrimidines and triazines of the present invention. Preferred concentrations of are 2% to 15% by weight; most preferred concentrations of 5% to 10% by weight.
The benzocycle-substituted pyrimidines and triazines of the present invention may be incorporated into the thermoplastics of the surfaces layer by standard methods such as dry mixing the additives with granular resin prior to extruding.
The benzocycle-substituted pyrimidine or triazine layer may be applied to one or both sides of the thermoplastic article. Laminated thermoplastic articles which contain additional layers such as a water resistant layer as found in U.S. Pat. No. 4,992,322 are also part of the present invention.
The core layer and the coating layer may be the same or different thermoplastic resin including polyesters, polyester carbonates, polyphenylene oxide, polyvinyl chloride, polypropylene, polypropylene, polyethylene, polyacrylates, polymethacrylates and copolymers and blends such as styrene and acrylonitrile on polybutadiene and styrene with maleic anhydride, and mixtures (polyblends) of such polymers with one another or with other polymers, for example with polyolefins, polyacrylates, polydienes or other elastomers in the form of impact strength modifiers.
BONDABLE STABILIZERS
The benzocycle-substituted pyrimidines and triazines of the present invention can also be chemically bonded to substrates, such as polymers, thereby greatly reducing the migration of such UV absorbers, e.g., out of the substrate or away from the substrate surface. The bonding mechanism of the triazines of the present invention involves the formation of a bond (chemical and/or co-valent) between a functionality attached to the amido or carbamate group, e.g., by a pendant vinyl or hydroxyl group, and the "host" substrate, such as a polymer. Incorporation of the benzocycle-substituted pyrimidines and triazines of the invention can be brought about by copolymerization, copolyaddition, copolycondensation, by reaction with a polymer which carries suitable functional groups, or by grafting, in a manner as disclosed in United States Patent Nos. 3,423,360 and 5,189,084 which are incorporated herein by reference as if fully set forth. Bonding of the benzocycle-substituted pyrimidines and triazines of the invention can occur by polymerization or copolymerization. In the case of the novel triazines of the present invention comprising pendant vinyl groups, polymerization or copolymerization with at least one vinyl monomer, e.g., (meth)acrylic acid, esters of (meth)acrylic acid such as methyl acrylate, amides of (meth)acrylic acid, hydroxyethylacrylate, olefins, vinyl chloride, styrene, butadiene, isoprene and acrylonitrile can be carried out to form homopolymers or copolymers in which the vinyl group is incorporated into the backbone of the polymer. Polymerization or copolymerization can be initiated by initiators, such as free radical, anionic and cationic types, or by actinic radiation, such as UV, electron beam, x-rays and gamma irradiation from a Co60 source, as is well known to those in the polymerization art. Polymerization or copolymerization can be carried out in solution, in an emulsion, in a dispersion, in the melt, or in the solid state as is well known to those in the polymerization art.
Also, bonding of the presently claimed benzocycle-substituted pyrimidines and triazines compounds of the present invention can be brought about by copolyaddition or copolycondensation. Such incorporation can be made by addition during the synthesis of an addition polymer or copolymer or by condensation during the synthesis of a condensation polymer or copolymer by methods known to those skilled in the art. For example, compounds of the formula (I), (II), or (IV)-(IX) containing the appropriate functional groups can be incorporated into polyesters, polyamides, polyurethanes, epoxy resins, melamine resins, alkyd resins, phenolic resins, polyurethanes, polycarbonates, polysiloxanes, polyacetals and polyanhydrides, to name but a few.
In addition, compounds of the formula (I), (II), or (IV)-(IX) can be bonded to a monomeric component which is then incorporated into a polymer or copolymer, e.g., by the free radical initiated addition or copolycondensation methods described above. Analogous methods are disclosed in, for example, United States Patent No. 5,459,222 (incorporated by reference herein for all purposes as if fully set forth) for the bonding of benzotriazole and benzophenone stabilizers to diol precursors which are then incorporated by condensation polymerization into polyurethanes and polyesters to impart UV stabilizing properties to said polymers. Alternately, the benzocycle-substituted pyrimidines and triazines of the invention may also be bonded to polymers by reaction with an oligomer and/or polymer which carries suitable functional groups. For example, at least one triazine compound comprising a vinyl pendant group can be added, optionally with at least one other vinyl monomer or compound comprising a vinyl group, to unsaturated polyester resins, unsaturated polybutadiene oligomers or unsaturated rubbers and then cured by actinic radiation or by a free radical catalyst. Or, at least one triazine compound comprising a terminal functional group, such as hydroxyl or amido, may be reacted with a polymer and/or oligomer such as polyesters, polyurethanes and polydiols with reactive end-groups, partially hydrolyzed polyvinylacetate, epoxy resins, polysiloxanes and polymers comprising maleic anhydride, either in the main chain or as a side-chain, by methods analogous to those well known to those of ordinary skill in the art.
Grafting is yet another way of bonding of the presently claimed benzocycle- substituted pyrimidines and triazines to polymers and/or oligomers. Grafting may be carried out in solution, in the melt, or in the solid state with the initiators or actinic radiation types discussed above for polymerization when, for example, the novel triazines of the present nn urm.B PCT/US99/13
WO 99/67225
invention comprising pendant vinyl groups are used. Such benzocycle-substituted pyrimidines and triazines may be grafted to saturated polymers, e.g., polyolefins and their copolymers such as polyethylene, polypropylene and poly(ethylene-vinyl acetate), or to polymers comprising unsaturated moieties, e.g., polybutadiene, polyisoprene, ethylene- propylene-(diene monomer) terpolymers and polystyrene and its copolymers.
The benzocycle-substituted pyrimidines and triazines of the present invention may be used in widely varying amounts in such applications depending upon such things as the material to be stabilized and the particular application. However, when employed as a stabilizing additive for materials such as organic polymers, the benzocycle-substituted pyrimidines and triazines of the present invention are typically employed in amounts from about 0.01 to about 20% by weight, preferably from about 0.1 to about 10% by weight, and most preferably from about 0.1 to about 5% by weight, based on the weight of the material to be stabilized. In screening applications such as sunscreening compositions, the triazines are utilized in the same relative amounts but based on the total weight of the screening agent.
The novel stabilizers of the present invention may also be employed in a non- bondable capacity, for example, in the stabilization of thermoplastic polymers as set forth in the many of the previously incorporated references. Examples of preferred thermoplastic polymers are polyolefins and polymers comprising heteroatoms in the main chain. Preferred polymers are also thermoplastic polymers comprising nitrogen, oxygen and/or sulphur, especially nitrogen or oxygen, in the main chain. Also of interest are compositions in which the polymer is a polyolefin, for example polyethylene or polypropylene.
Incorporation into the thermoplastic polymers can be carried out by addition of the novel benzocycle-substituted triazine or pyrimidine compound and any further additives by the methods conventional in the art. The incorporation can expediently be made before or during shaping, for example by mixing the pulverulent components or by adding the stabilizer to the melt or solution of the polymer, or by applying the dissolved or dispersed compounds to the polymer, with or without subsequent evaporation of the solvent. Elastomers can also be stabilized as lattices. The novel mixtures can also be added to the polymers to be stabilized in the form of a masterbatch which comprises these compounds, for example, in a concentration of from about 2.5 to about 25%, preferably from about 5 to about 20% by weight of the polymer.
The novel mixtures can expediently be incorporated into the polymeric material by any number of methods, including those conventionally employed in the art, including by, for example: a) as an emulsion or dispersion (for example to lattices or emulsion polymers); (b) as a dry mix during mixing of additional components or polymer mixtures; (c) by direct addition to the processing equipment (for example extruders, internal mixers, etc.); or (d) as a solution or melt. The stabilized polymer compositions obtained in this way can be converted into shaped articles, for example fibers, films, tapes, sheets, sandwich boards, containers, pipes and other profiles, by any number of conventional methods, for example hot pressing, spinning, extrusion, roto-molding or injection molding. Therefore, the present invention additionally relates to the use of the polymer composition according to the invention for the production of a shaped article.
Depending upon their ultimate end use, the benzocycle-substituted pyrimidines and triazines of the present invention may be combined with a variety of additives conventionally employed in the UV stabilizing art. Examples of such additives include but are not limited to: a. Antioxidants
(i) Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6- dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2-(α- methylcyclohexyl)-4,6-dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2,4,6- tricyclohexy lphenol; 2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols which are liner or branched in the side chains such as 2,6-di-nonyl-4-methylphenol; 2,4- dimethyl-6-(l -methy lundec-1 -yl)phenol; 2,4-dimethyl-6-(l -methylheptadec- 1 - yl)phenol; 2,4-dimethyl-6-(l-methyltridec-l-yl)phenol; and mixtures thereof, (ii) Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol; 2,4- dioctylthiomethyl-6-methylphenol; 2,4-dioctylthiomethyl-6-ethylphenol; and 2,6-di- dodecylthiomethyl-4-nonylphenol. (iii) Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4- methoxyphenol; 2,5-di-tert-butylhydroquinone; 2,5-di-tert-amylhydroquinone; 2,6- diphenyl-4-octadecyloxyphenol; 2,6-di-tert-butylhydroquinone; 2,5-di-tert-butyl-4- hydroxyanisole; 3,5-di-tert-butyl-4-hydroxyanisole; 3, 5-di-tert-buty 1-4- hydroxyphenyl stearate; and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate. (iv) Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof (vitamin E). (v) Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methylphenol); 2,2'-thiobis(4-octy lphenol); 4,4'-thiobis(6-tert-butyl-3-methylphenol); 4,4'-thiobis(6- „„„„« PCT/US99/1 7
WO 99/67225 tert-butyl-2-methylphenol); 4,4'-thiobis(3,6-di-sec-amylphenol); and 4,4'-bis(2,6- dimethyl-4-hydroxyphenyl)disulfide. (vi) Alkylidenebisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol); 2,2'- methylenebis(6-tert-butyl-4-ethylphenol); 2,2'-methylenebis[4-methyl-6-(α- methylcyclohexyl)phenol]; 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,2'- methylenebis(6-nonyl-4-methylphenol); 2,2'-methylenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(6-tert-butyl-4- isobuty lphenol); 2,2'-methylenebis[6-(α-methylbenzyl)-4-nony lphenol]; 2,2'- methylenebis[6-( ,α-dimethylbenzyl)-4-nonylphenol]; 4,4'-methylenebis(2,6-di-tert- butylphenol); 4,4'-methylenebis(6-tert-butyl-2-methylphenol); l,l-bis(5 -tert-buty 1-4- hydroxy-2-methylphenyl)butane; 2,6-bis(3-tert-butyl-5-methyl-2-hydroxylbenzyl)-4- methylphenol; 1 , 1 ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 1 , 1 -bis(5- tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane; ethylene glycol bis [3 ,3 -bis(3 '-tert-buty l-4'-hy droxypheny l)butyrate] , bis(3 -tert-buty l-4-hydroxy-5- methylphenyl)dicycloρentadiene; bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6- tert-buty l-4-methylphenyl]terephthalate; 1 , 1 -bis(3,5-dimethyl-2- hydroxyphenyl)butane; 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane; 2,2-bis(5- tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane; and 1,1,5,5- tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane. (vii) O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'- dihydroxydibenzyl ether; octadecyl-4-hydroxy-3 ,5 -dimethy lbenzylmercaptoacetate; tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate; tris(3,5-di-tert-butyl-4- hydroxybenzyl)amine; bis(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)dithioterephthalate; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and isooctyl-3, 5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
(viii) Hydroxybenzylate malonates such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonate; dioctadecyl-2-(3-tert-butyl-4-hydroxy-5- methylbenzyl)malonate; didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4- hydroxybenzyl)malonate; and bis[4-(l,l,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di- tert-butyl-4-hydroxybenzyl)malonate.
(ix) Aromatic hydroxybenzyl compounds such as l,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene; l,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- 2,3,5,6-tetramethylbenzene; and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol. (x) Triazine compounds such as 2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4- hydroxyanilino)-! , 3,5-triazine; 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-l, 3,5-triazine; 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-l,3,5-triazine; 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1 ,3, 5-triazine; 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate; 1 ,3,5-tris(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; 2,4,6-tris(3,5-di-tert-butyl-4- hydroxyphenylethyl)- 1 ,3, 5-triazine; 1 ,3,5-tris(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)-hexahydro- 1,3, 5-triazine; and l,3,5-tris(3,5-dicyclohexyl- 4-hydroxybenzyl)isocyanurate. (xi) Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4- hydroxybenzylphosphonate; diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-tert-butyl-
4-hydroxy-3-methylbenzylphosphonate; and the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, (xii) Acylaminophenols such as 4-hydroxylauranilide; 4-hydroxystearanilide; and octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate. (xϋi) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 , 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 , 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l- phospha-2,6,7-trioxabicyclo[2.2.2]octane. (xiv) Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l- phospha-2,6,7-trioxabicyclo[2.2.2]octane. (xv) Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)-oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l-phospha-2,6,7- trioxabicyclo[2.2.2]octane. (xvi) Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l -phospha-2,6,7- trioxabicyclo[2.2.2]octane. (xvii) Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid such as N,N'-bis(3,5- di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine; N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hydrazine. (xviii) Ascorbic acid (Vitamin C). (xix) Aminic antioxidants such as N,N'-diisopropyl-p-phenylenediamine; N,N'-di-sec- butyl-p-phenylenediamine; N,N'-bis(l ,4-dimethylpentyl)-p-phenylenediamine; N,N'- bis(l -ethyl-3-methylpentyl)-p-phenylenediamine; N,N'-bis( 1 -methy lheptyl)-p- phenylenediamine; N,N'-dicyclohexyl-p-phenylenediamine; N,N'-diphenyl-p- phenylenediamine; N,N'-bis(2-naphthyl)-p-phenylenediamine; N-isopropyl-N'- phenyl-p-phenylenediamine; N-(l,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine; N-( 1 -methylheptyl)-N'-phenyl-p-phenylenediamine; N-cyclohexyl-N'-phenyl-p- phenylenediamine; 4-(p-toluenesulfonamoyl)diphenylamine; N,N'-dimethyl-N,N'-di- sec-butyl-p-phenylenediamine; diphenylamine; allyldiphenylamine; 4- isopropoxydiphenylamine; -phenyl- 1 -naphthy lamine; N-(4-tert-octylphenyl)- 1 - naphthylamine; N-phenyl-2-naphthylamine; octylated diphenylamine such as p,p'-di- tert-octyldiphenylamine; 4-n-butylaminophenol; 4-butyrylaminophenol; 4- nonanoylaminophenol; 4-dodecanoylaminophenol; 4-octadecanoylaminophenol; bis(4-methoxyphenyl)amine; 2,6-di-tert-butyl-4-dimethylaminomethylphenol; 2,4'- diaminophenylmethane; 4,4'-diaminodiphenylmethane; N,N,N',N'-tetramethyl-4,4'- dia inodiphenylmethane; l,2-bis[(2-methylphenyl)amino]ethane; 1,2- bis(ρhenylamino)propane; (o-tolyl)biguanide; bis[4-(l',3'- dimethylbutyl)phenyl]amine; tert-octylated N-phenyl-1 -naphthylamine; a mixture of mono- and dialkylated tert-butyl/tert-octyldipheny lamines, a mixture of mono- and dialkylated nonyldiphenylamines; a mixture of mono- and dialkylated dodecyldiphenylamines; a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert- butyldiphenylamines; 2,3-dihydro-3,3-dimethyl-4H- 1 ,4-benzothiazine; phenothiazine; a mixture of mono- and dialkylated tert-butyl/tert-octyl phenothiazines; a mixture of mono- and dialkylated tert-octylphenothiazines; N- allylphenothiazine; N,N,N',N'-tetraphenyl-l ,4-diaminobut-2-ene; N,N-bis(2,2,6,6- tetramethylpiperid-4-yl)hexamethylenediamine; bis(2,2,6,6-tetramethylpiperid-4- yl)sebacate; 2,2,6,6-tetramethylpiperidin-4-one; and 2,2,6,6-tetramethylpiperidin-4- ol. b. UV-absorbers and light stabilizers (i) 2-(2'-Hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)- benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(5 '-tert-buty 1- 2'-hydroxyphenyl)benzotriazole; 2-(2'-hydroxy-5'-(l, 1,3,3- tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5- chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro- benzotriazole; 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(2'- hydroxy-4'-octoxyphenyl)benzotriazole; 2-(3',5'-di-tert-amyl-2'- hydroxphenyl)benzotriazole; 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)- benzotriazole; a mixture of 2-(3'-tert-butyl-2'-hydroxy-5,-(2- octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2- ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert- butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'- tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert- butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3 '-tert-buty 1- 5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'- dodecyl-2,-hydroxy-5,-methylphenyl)benzotriazole and 2-(3l-tert-butyl-2'-hydroxy-5'- (2-isooctyloxycarbonylethyl)phenylbenzotriazole; 2,2-methylenebis[4-(l, 1,3,3- tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product of 2-[3'- tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300; and [R-CH2CH-COO(CH2)3]2 B where R = 3'-tert-butyl-4'- hydroxy-5'-2H-benzotriazol-2-ylphenyl. (ii) 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4- decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'- dimethoxy derivative, (iii) Esters of substituted and unsubstituted benzoic acids such as 4-tert-butyl-phenyl salicylate; phenyl salicylate; octylphenyl salicylate; dibenzoyl resorcinol; bis(4-tert- butylbenzoyl) resorcinol; benzoyl resorcinol; 2,4-di-tert-butylphenyl 3,5-di-tert- butyl-4-hydroxybenzoate; hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate; and 2-methyl-4,6-di-tert-butylphenyl 3,5-di- tert-butyl-4-hydroxybenzoate. (iv) Acrylates such as ethyl α-cyano-β,β-diphenylacrylate; isooctyl α-cyano-β,β- diphenylacrylate; methyl α-carbomethoxycinnamate; methyl α-cyano-β-methyl-p- methoxy cinnamate; butyl α-cyano-β-methyl-p-methoxycinnamate; methyl α- carbomethoxy-p-methoxycinnamate; and N-(β-carbomethoxy-β-cyanovinyl)-2- methylindoline. (v) Nickel compounds such as nickel complexes of 2,2'-thio-bis-[4-(l, 1,3,3- tetramethylbutyl)phenol], including the 1 :1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N- cyclohexyldiethano lamine; nickel dibutyldithiocarbamate; nickel salts of monoalkyl esters including the methyl or ethyl ester of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid; nickel complexes of ketoximes including 2-hydroxy-4- methylphenyl undecyl ketoxime; and nickel complexes of l-phenyl-4-lauroyl-5- hydroxypyrazole, with or without additional ligands.
(vi) Sterically hindered amines as well as the N derivatives thereof (e.g., N-alkyl, N- hydroxy, N-alkoxy and N-acyl), such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate; bis(l ,2,2,6,6- pentamethylρiperidin-4-yl)sebacate; bis( 1 -octyloxy-2,2,6,6-tetramethylpiperidin-4- yl)sebacate; bis(l,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4- hydroxybenzylmalonate; the condensate of 1 -(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- hydroxypiperidine and succinic acid; the condensate of N,N'-bis(2,2,6,6- tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6- dichloro-1 ,3, 5-triazine; tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)- 1,2,3,4-butanetetracarboxylate; 1,1'-(1,2- ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-2,2,6,6- tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis(l ,2,2,6,6- pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate; 3-n- octyl-7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decan-2,4-dione; bis(l-octyloxy- 2,2,6, 6-tetramethylpiperidyl)sebacate; bis(l-octyloxy-2,2,6,6- tetramethylpiperidyl)succinate; the condensate of N,N'-bis(2,2,6,6- tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro- 1, 3,5-triazine; the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6- tetramethylpiperidyl)-l, 3,5-triazine and l,2-bis(3-aminopropylamino)ethane; the condensate of 2-chloro-4,6-bis(4-n-butylamino- 1 ,2,2,6,6-pentamethylpiperidyl)- WO 99/67225 P fC^Ti//UuS^99y//1u3708
1, 3,5-triazine and l,2-bis-(3- aminopropylamino)ethane; 8-acetyl-3-dodecyl-7,7,9,9- tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione; 3-dodecyl-l -(2,2,6,6- tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-l -(1 -ethanoyl-2,2,6,6- tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-l -(1,2,2,6,6- pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine; the condensate of N,N'-bis(2,2,6,6- tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6- dichloro-1, 3,5-triazine; the condensate of l,2-bis(3-aminoρropylamino)ethane, 2,4,6- trichloro- 1 ,3, 5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); 2-undecyl-7,7,9,9-tetramethyl-l-oxa-3,8-diaza-4- oxosρiro[4.5]decane; oxo-piperanzinyl-triazines or so-called PIP-T HALS, e.g., GOODRITE® 3034, 3150 and 3159 and similar materials disclosed in US5071981; photobondable HALS such as SANDUVOR® PR-31 and PR-32 (Clariant Corp.) and similar materials disclosed in GB-A-2269819; and the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l -oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin. See also generally US4619956, US5106891, GB-A-2269819, EP- A-0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608. (vii) Oxamides such as 4,4'-dioctyloxyoxanilide; 2,2'-diethoxyoxanilide; 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide; 2,2'-didodecyloxy-5, 5'-di -tert-buty loxanilide; 2-ethoxy-2'- ethyloxanilide; N,N'-bis(3-dimethylaminopropyl)oxamide; 2-ethoxy-5-tert-butyl-2'- ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide; and mixtures of o- and p-methoxy disubstituted oxanilides and mixtures of o- and p- ethoxy disubstituted oxanilides. (viii) 2-(2-Hydroxyphenyl)- 1,3, 5-triazines disclosed in the previously incorporated references, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-l , 3,5-triazine; 2-(2- hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine; 2-(2- hydroxy-4-(mixed iso-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine; 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethy lphenyl)- 1 ,3,5-triazine; 2,4-bis(2- hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine; 2-(2-hydroxy-4- octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine; 2-(2-hydroxy-4- dodecyloxypheny l)-4,6-bis(2,4-dimethy lphenyl)- 1,3, 5-triazine; 2-(2-hydroxy-4- tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine; 2-[2-hydroxy-4-(2- hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine; 2- [2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4- dimethylphenyl)- 1 ,3,5-triazine; 2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2- hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-l, 3,5-triazine; 2-[2-hydroxy-4-(2- hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-l, 3,5-triazine; 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl- 1 ,3,5-triazine; 2-(2-hydroxy-4- methoxyphenyl)-4,6-diphenyl- 1 ,3,5-triazine; 2,4,6-tris[2-hydroxy-4-(3-butoxy-2- hydroxypropoxy)phenyl]- 1,3, 5-triazine; and 2-(2-hydroxyphenyl)-4-(4- methoxyphenyl)-6-pheny 1-1, 3, 5-triazine.
(c) Metal deactivators such as N,N'-diphenyloxamide; N-salicylal-N'-salicyloyl hydrazine; N,N'-bis(salicyloyl)hydrazine; N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hydrazine; 3-salicyloylamino-l ,2,4-triazole; bis(benzylidene)oxalyl dihydrazide; oxanilide; isophthaloyl dihydrazide; sebacoyl bisphenylhydrazide; N,N'- diacetyladipoyl dihydrazide; N,N'-bis(salicyloyl)oxalyl dihydrazide; and N,N'- bis(salicyloyl)thiopropionyl dihydrazide.
(d) Phosphites and phosphonites, such as triphenyl phosphite; diphenyl alkyl phosphites; phenyl dialkyl phosphites; tris(nonylphenyl) phosphite; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphitc; diisodecyl pentaerythritol diphosphite; bis(2,4,-di-tert-butylphenyl)pentaerythritol diphosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite; bis(isodecyloxy)pentaerythritol diphosphite; bis(2,4-di-tert-butyl-6- methylphenyl)pentaerythritol diphosphite; bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite; tristearyl sorbitol triphosphite; tetrakis(2,4-di-tert-butylphenyl)-4,4'- biphenylene diphosphonite; 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-l,3,2- dioxaphosphocin; 6-fluoro-2,4,8, 10-tetra-tert-butyl- 12-methyl-dibenzo[d,g]- 1 ,3,2- dioxaphosphocin; bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite; and bis(2,4-di-tert- butyl-6-methylphenyl)ethylphosphite. (e) Hydroxylamines such as N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N- dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-ditetradecylhydrcxy lamine; N,N- dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecyl- hydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylamine derived from hydrogenated tallow fatty amines. (f) Nitrones such as N-benzyl-alpha-phenyl nitrone; N-ethyl-alpha-methyl nitrone; N-octyl- alpha-heptyl nitrone; N-lauryl-alpha-undecyl nitrone; N-tetradecyl-alpha-tridecyl nitrone; N- hexadecyl-alpha-pentadecyl nitrone; N-octadecyl-alpha-heptadecyl nitrone; N-hexadecyl- alpha-heptadecyl nitrone; N-octadecyl-alpha-pentadecyl nitrone; N-heptadecyl-alpha- heptadecyl nitrone; N-octadecyl-alpha-hexadecyl nitrone; and nitrones derived from N,N- dialkylhydroxylamines prepared from hydrogenated tallow fatty amines. „„, ,„„ PCT/US99/1370
WO 99/67225
(g) Thiosyncrgists such as dilauryl thiodipropionate and dislcaryl thiodipropionate. (h) Peroxide scavengers such as esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters; mercaptobenzimidazole or the zinc salt of 2- mercaptobenzimidazole; zinc dibutyldithiocarbamate; dioctadecyl disulfide; and pentaerythritol tetrakis(β-dodecylmercapto)propionate.
(i) Polyamide stabilizers such as copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
(j) Basic co-stabilizers such as melamine; polyvinylpyrrolidone; dicyandiamide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyamides; polyurethanes; alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate; antimony pyrocatecholate; and tin pyrocatecholate. (k) Nucleating agents including inorganic substances such as talc and metal oxides (e.g. titanium oxide or magnesium oxide) and phosphates, carbonates and sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate and sodium benzoate; and polymeric compounds such as ionic copolymers (e.g., ionomers). (1) Fillers and reinforcing agents such as calcium carbonate; silicates; glass fibers; asbestos; talc; kaolin; mica; barium sulfate; metal oxides and hydroxides; carbon black; graphite; wood flour and flours or fibers from other natural products; and synthetic fibers, (m) Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, levelling assistants, optical brighteners, flameproofing agents, antistatic agents and blowing agents. (n) Benzofuranones and indolinones such as those disclosed in US 4,325,863, US
4,338,244, US 5,175,312, US 5,216,052, US 5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 and EP-A-0591102; 3-[4-(2-acetoxy-ethoxy)phenyl]-5,7-di- tert-butyl-benzofuran-2-one; 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)- ρhenyl]benzofuran-2-one; 3,3'-bis[5,7-di-tert-butyl-3-(4-[2- hydroxyethoxy]phenyI)benzofuran-2-one]; 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran- 2-one; 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one; 3-(3,5- dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one; and 5,7-di-tert-butyl-3- (3 ,4-dimethylphenyl)-3 H-benzofuran-2-one.
The novel benzocycle-substituted pyrimidines and triazines of the present invention can also be employed in multilayer systems. In such systems, a polymer composition having from about 0.1 to about 20% by weight and preferably a relatively high content of novel stabilizer, for example, about 5-15% by weight, is applied in a thin film (e.g., about 5 - 500 μm thick and, preferably, about 10 - 100 μm thick) to a shaped article made from a polymer containing little or no ultraviolet stabilizers. Such composition may be applied at the same time as the shaping of the base structure, for example by coextrusion in a manner analogous to that described in United States Patent No. 4,948,666 (incorporated by reference herein for all purposes as if fully set forth). Alternatively, application can also be made to the ready-formed base structure, for example by lamination with a film or by coating with a solution. The outer layer or layers of the finished article have the function of a UV filter, which protects the interior of the article from UV light. The outer layer preferably contains about 0.1 to about 20%, preferably about 1 to about 15%, and most preferably about 2 to about 10% by weight of the outer layer composition, of at least one of the benzocycle-substituted pyrimidine or triazine compounds of the present invention. The polymers stabilized in this way are notable for high weathering resistance, especially for high resistance to UV light. This enables them to retain their mechanical properties, and their color surface properties such as gloss and distinctness of image, for a long time even when used outside. Moreover, due to the bondable nature of the presently claimed triazine compounds, migration of these UV absorbers between the layers of the multi-layer coatings can, under the appropriate circumstances, be minimized. In another embodiment of the present invention, the novel mixtures comprising compounds of the formula (I), (II), or (IV)-(IX) can be used as stabilizers for coatings, for example for paints such as disclosed in numerous references (see, e.g., US 4,619,956, US 4,740,542, US 4,826,978, US 4,962,142, US 5,106,891, US 5,198,498, US 5,298,067, US 5,322,868, US 5,354,794, US 5,369,140, US 5,420,204, US 5,461,151, US 5,476,937, EP-0434608 and EP-A-0444323). Of particular interest are coatings and paints for the automobile industry. The invention therefore also relates to those compositions which are film-forming binders for coatings.
Such novel coating compositions comprise about 0.01 to about 20%, preferably about 0.01 to about 10%, and more preferably about 0.02 to about 5% by weight of the binder of the coating composition of the presently claimed benzocycle-substituted pyrimidines and triazines of the present invention.
Multilayer systems are possible here as well (such as electrocoat/basecoat/clearcoat systems), where the concentration of the novel stabilizer in one or more of the layers, and typically the outer layer such as the clearcoat, can be relatively high, for example from about 0.01 to about 20%, preferably about 0.01 to about 10%, and more preferably about 0.02 to about 5% by weight of binder.
The use of the novel stabilizer in coatings is accompanied by the additional advantage that it prevents delamination, i.e. the flaking-off of the coating from the substrate. This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates, and particularly epoxy e-coated metallic substrates.
The binder can in principle be any binder which is customary in industry, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991 which is incorporated herein by reference. In general, it is a film-forming binder based on a thermoplastic or curable resin, predominantly on a curable resin. Examples of thermoplastic binders include acrylics, polyesters, polyurethanes and PVC plastisols. Examples of curable binders include functional alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof. Such curable binders can be an ambient curable or a thermosetting binder.
Further, in some systems it may be advantageous to add a curing catalyst to such systems. Suitable catalysts which accelerate curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim 1991. Preferred binders include those which comprise a functional acrylate resin and a crosslinking agent.
A wide variety of binders may be employed in such coating systems. Examples of suitable coating compositions containing specific binders include but are not limited to:
1. paints based on ambient curable or thermosetting alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, if desired with addition of a curing catalyst;
2. two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
3. one-component polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking; 4. two-component paints based on (poly)ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
5. two-component paints based on (ρoly)ketimines and an unsa irated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;
6. two-component paints based on carboxyl- or amino-containing polyacrylates and polyepoxides; 7. two-component paints based on acrylate resins containing anhydride groups and on a polyhydroxy or polyamino component;
8. two-component paints based on (poly)oxazolines and acrylate resins containing anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
9. two-component paints based on unsaturated polyacrylates and polymalonates;
10. thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;
1 1. paint systems based on siloxane-modified or fluorine-modified acrylate resins. In addition to the binder and novel benzocycle-substituted pyrimidines and triazines of the present invention, the coating composition according to the invention preferably further comprise one or more additional ultraviolet light absorbers, including but not limited to those specifically listed above in section b. The additional UV absorbers may be, for example, another tris-aryl- 1,3, 5-triazine, a 2-hydroxyphenyl-2H-benzotriazole, a 2-hydroxybenzophenone, an ester of an unsubstituted benzoic acid, an acrylate, an oxamide (oxanilide), or any combination of the above. Preferably, the additional UV absorber is a 2-hydroxyphenyl-2H-benzotriazole and the weight ratio of benzotriazole to triazine is 4:1 to 1 :4. More preferably, the weight ratio is 2: 1 to 1 :2.
To achieve maximum light stability, it is of particular interest to add sterically hindered amines, examples of which are set out in the above-mentioned section b(vi). The invention therefore also relates to a coating composition which, in addition to the binder, the novel benzocycle-substituted pyrimidines and triazines and, optionally, additional UV absorbers, comprises a light stabilizer of the sterically hindered amine type. The sterically hindered amine is employed in an amount of about 0.01 to 5% by weight based on the weight of the solid binder, preferably about 0.02 to 2% by weight.
One specific example of such a sterically hindered amine is a 2,2,6,6- tetramethyl piperazinone containing at least one group of the formula:
—
Figure imgf000059_0001
in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl), alkoxy (such as methoxy) or acyl. More preferably the stabilizer is a 2,2,6,6-tetraalkylpiperidine derivative containing at least one group of the formula:
Figure imgf000060_0001
in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl), alkoxy (such as methoxy) or acyl. Examples of tetraalkylpiperidine derivatives which can be used in combination with the present trisaryl-1, 3, 5-triazine compounds are given in United States Patent Nos. 4,314,933, 4,344,876, 4,426,471, 4,426,472, 4,619,956, 5,004,770, 5,006,577, 5,064,883, 5,1 12,890, 5,124,378, 5,106,891, 5,204,473, and 5,461,151 , which are incorporated by reference herein for all purposes as if fully set forth. It is particularly expedient to employ the following tetraalkylpiperidine derivatives, as well as their N-alkyl, N-acyl, N-hydroxyl and N-alkoxy analogs (where not already included in the following list): bis(2,2,6,6-tetramethylpiperid-4-yl) succinate, bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate, bis(l ,2,2,6,6-pentamethylpiperid-4-yl) sebacate, di(l ,2,2,6,6-pentamethylpiperid-4-yl) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis( 1 -octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate, tetra(2,2,6,6-tetramethylpiperid-4- yl) butane-l, 2,3, 4-tetracarboxylate, tetra(l,2,2,6,6-pentamethylpiperid-4-yl) butane- 1,2, 3,4- tetracarboxylate, 2,2,4 ,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.1 1.2]heneicosane, and 8-acetyl-3-dodecyl-l,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione. Commercially available examples of these and other tetraalkylpipieridine derivatives include SANDUVOR® 3050, 3052, 3055, 3056, 3058, PR-31 and PR-32 (Clariant Corp.); TINUVIN® 079L, 123, 144, 292, 440L and 622LD (Ciba Specialty Chemicals); CHIMASORB® 1 19 and 944 (Ciba Specialty Chemicals); and CYASORB® UV-3346, UV 3529, UV-3853, UV-500 and UV-516 (Cytec Industries Inc.). Apart from the binder, the benzocycle-substituted pyrimidine or triazine, and, if used, the additional ultraviolet light absorber or stabilizer, the coating composition can also comprise further components, examples being solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts and/or leveling agents. Examples of possible components are those described in many of the previously incorporated references as well as Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. Al 8, pp. 429-471, VCH, „« «,,-« PCT/US99/13708
WO 99/67225
Weinheim 1991; and Calbo, Leonard J., ed., Handbook of Coatings Additives, New York.Marcel Dekkcr (1987).
Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, acids, amino-containing resins and/or phosphines. Examples of acid catalysts are mineral acids, aliphatic and aromatic sulfonic acids (e.g. p-toluene sulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid), oxalic acid, maleic acid, hexamic acid, phosphoric acid, alkyl phosphate esters, phthalic acid and acrylic acid copolymers.
Examples of organometallic compounds are metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially those of the metal Al, It or Zr, or organometallic compounds such as organotin compounds, for example. Examples of metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates. Examples of metal chelates are the aluminum, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate and the alkoxides of these metals. Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.
Examples of amine drying or curing catalysts are, in particular, tertiary amines, for example tributylamine, triethanolamine, N-methyldiethanolamine, N- dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane
(triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride. Amino-containing resins are simultaneously binder and curing catalyst. Examples thereof are amino-containing acrylate copolymers. The curing catalyst used can also be a phosphine, for example triphenylphosphine.
Another type of curing catalyst is a peroxide which can be used, for example, to cure a gel coating for a fiberglass article.
The novel coating compositions can also be radiation-curable coating compositions. In this case, the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which after application are cured by actinic radiation, i.e. converted into a crosslinked, high molecular weight form. Where the system is UV-curing, it generally contains a photoinitiator as well. Corresponding systems are described in the above-mentioned publication Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 18, pages 451-453. In radiation-curable coating Λ.„„* PCT/US99/13708
WO 99/67225
compositions, the novel stabilizers can also be employed without the addition of sterically hindered amines.
The novel coating compositions according to the invention can be applied to any desired substrates, for example to metal, wood, plastic, fiberglass or ceramic materials. The coating compositions can be pigmented mono-coats or multi-layer
(primer/basecoat/clearcoat) systems typical of automotive finishes. In the latter case, the novel coating composition can be used for either the base coat, or clear coat, or for both layers. If the topcoat of an automotive finish comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be
10 used for either the upper or the lower layer or for both layers, but preferably for the upper topcoat layer.
The novel coating compositions can be applied to the substrates by the customary methods, for example by brushing, spraying, pouring, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 491-
15 500.
Depending on the binder system, the coatings can be cured at room temperature or by heating. Thermosetting coatings are preferably cured at 50 - 150°C and, in the case of powder coatings, even at higher temperatures.
The coatings obtained in accordance with the invention have excellent
20 resistance to the damaging effects of light, oxygen and heat; particular mention should be made of the good light stability and weathering resistance of the coatings thus obtained, for example paints.
The invention therefore also relates to a coating, in particular a paint, which has been stabilized against the damaging effects of light, oxygen and heat by a content of the
25 compound of the formula (I), (II), or (IV)-(IX), according to the invention. The paint can be a pigmented mono-coat which comprises a film-forming binder and an organic pigment or dye, an inorganic pigment, a metallic pigment, or a mixture thereof. The paint may also be a composition which comprises a primer in adhesion to a metal or plastic substrate; a pigmented basecoat that is in adhesion to the primer and which comprises a film-forming
30 binder and an organic pigment or dye, an inorganic pigment, a metallic pigment, or a mixture thereof; and a clear coat that is in adhesion to the base coat and which comprises a film-forming binder and optionally a transparent pigment. One especially preferred use is a paint which is a clear topcoat for automobile original equipment manufacture (OEM) and/or refinish applications.
35 The invention furthermore relates to a process for stabilizing a coating based on polymers against damage by light, oxygen and/or heat, which comprises mixing with the coating composition a mixture comprising a compound of a benzocycle-substituted pyrimidine or triazine and to the use of mixtures comprising benzocycle-substituted pyrimidine or triazine compound in coating compositions as stabilizers against damage by light, oxygen and/or heat.
The coating compositions can comprise an organic solvent or solvent mixture in which the binder is soluble. The coating composition can otherwise be an aqueous solution or dispersion. The vehicle can also be a mixture of organic solvent and water. The coating composition maybe a high-solids paint or can be solvent-free (e.g. a powder coating material).
The pigments can be inorganic, organic or metallic pigments. The novel coating compositions preferably contain no pigments and are used as a clearcoat.
Likewise preferred is the use of the coating composition as a topcoat for applications in the automobile industry, especially as a pigmented or unpigmented topcoat of the paint finish. Its use for underlying coats, however, is also possible.
The benzocycle-substituted pyrimidine or triazines of this invention may be applied topically by polishing a surface with a composition comprising the benzocycle- substituted pyrimidine or triazines and an inert carrier such as solvent, petroleum jelly, silicone oil in water emulsions, or automotive paint wax, e.g. Carnauba wax. These topical treatment compositions may be used to stabilize coating films, fabrics, leather, vinyl and other plastics and wood.
Preference is also given to the use of the novel benzocycle-substituted pyrimidine or triazine compounds in photographic materials as stabilizer against damage by light, especially by UV light. The invention therefore also relates to a photographic material comprising an benzocycle-substituted pyrimidine or triazine compound.
The compounds according to the invention can be used for photosensitive materials of all kinds. For example, they can be employed for color paper, color reversal paper, direct-positive color material, color negative film, color positive film, color reversal film and other materials. They are preferably used, inter alia, for photosensitive color material which comprises a reversal substrate or which forms positives.
Furthermore, the novel compounds can be combined with other UV absorbers, especially those which are dispersible in aqueous gelatin, for example with hydroxyphenylbenzotriazoles (cf. for example United States Patent Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701), benzophenones, oxanilides, cyanoacrylates, salicylates, or acrylonitriles or thiazolines. In this context it is advantageous to employ these further, oil-dissolved UV absorbers in the photographic material in layers other than those comprising the novel UV absorbers.
The present invention also encompasses compositions containing one or more binders. In particular, the binder may comprise an alkyd, acrylic, polyester, phenolic, melamine, epoxy or polyurethane resin, or blends thereof. Examples of such binders include, but are not limited to:
(a) cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins; (b) a two-component polyurethane system comprising hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; (c) a one-component polyurethane system comprising blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking; (d) a two-component system comprising (poly)ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; (e) a two-component system comprising (poly)ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester; (f) a two-component system comprising carboxyl- or amino-containing polyacrylates and polyepoxides; (g) a two-component system comprising acrylate resins containing anhydride groups and on a polyhydroxy or polyamino component; (h) a two-component system comprising (poly)oxazolines and acrylate resins containing anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; (i) a two-component system comprising unsaturated polyacrylates and polymalonates; (j) a thermoplastic polyacrylate system comprising thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins; and (k) a system comprising siloxane-modified or fluorine-modified acrylate resins. Such binder-containing compositions may further comprise a curing catalyst, or an organic solvent, and may be radiation-curable. In particular, such compositions may serve as coating compositions. Λ ,mWB PCT/US99/137
WO 99/67225
In particular, it is possible successfully to stabilize photographic materials similar to those described in United States Patent No. 4,518,686.
The invention therefore additionally relates to a photographic material comprising, on support, a blue-sensitive, a green-sensitive and/or a red-sensitive silver- halide emulsion layer and, if desired, a protective layer, with a layer comprising a UV absorber being arranged above the uppermost silver-halide emulsion layer, wherein the UV absorber is a benzocycle-substituted pyrimidine or triazine compound.
Preference is additionally given to photographic materials which have a layer comprising a compound of the formula (I), (II), or (IV)-(IX) above the uppermost silver- halide emulsion layer and/or between the green- and red-sensitive silver-halide emulsion layers.
Furthermore, it may be advantageous for all or some of the said layers which can comprise a UV absorber to have a UV absorber mixture and/or a further UV absorber which is dispersible in aqueous gelatin, but a compound of the formula (I), (II), or (IV)-(IX) must be present at least in one layer.
The novel material preferably has gelatin interlayers between the silver- halide emulsion layers.
Preference is given to photographic materials in which the silver halide in the blue-sensitive, green-sensitive and/or red-sensitive layer is silver chloride bromide comprising at least 90 mol % of silver chloride.
The compounds of the formula (I), (II), or (IV)-(IX), which are used in accordance with the invention, can be incorporated, alone or together with the color coupler and, if used, further additives, into the color photographic materials by dissolving the compounds beforehand in high-boiling organic solvents. It is preferred to use solvents which boil at higher than 160°C. Typical examples of such solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids, or alkylamides and phenols.
Preferred color couplers for use in the compositions of the invention, examples of such compounds, further additives such as color cast inhibitors, DIR couplers and further light stabilizers, such as UV absorbers, phenols, phosphorus (III) compounds, organometallic complexes, hydroquinones and hydroquinone ethers, and more precise details on the structure of various photographic materials, can be found, for example, in the publications EP-A-0531258 and EP-A-0520938 and in the literature cited therein.
FILM The invention also relates to a process for the stabilization of polyolefin or polyolefin copolymer films for agricultural applications, especially greenhouse applications, this polyolefin or polyolefin copolymer film having improved light stability and pesticide resistance, comprising incorporation of at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention, sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium into the polyolefin or polyolefin copolymer.
A further subject of the invention is a greenhouse, characterized in that it is covered by a polyolefin or polyolefin copolymer film having improved light stability and pesticide resistance and stabilized with a at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention, sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium.
Another subject of the invention is a process for stabilizing a polyolefin or polyolefin copolymer greenhouse film against detrimental effects of pesticides and light, oxygen and/or heat, which process comprises incorporation of at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention, sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium into said greenhouse film.
Further subjects of the invention are the use of a polyolefin copolymer film stabilized with at least one benzocycle-substituted pyrimidine or triazine UV absorbers of the present invention, sterically hindered amines and metal oxides of hydroxides selected from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium for the stabilization of polyolefin or polyolefin copolymer films in contact with pesticides against photodegradation and damage by pesticides.
To form a film, forcing a quantity of the said melted composition through a film die, such as a flat film die or a circular blown film die, and forming a film therefrom. In the case where the composition is used to form a film therefrom, it is contemplated that the films may be unoriented, or may be subjected to a conventional operation to impart a degree of orientation on the film. Such a film may be oriented in one direction, such as in the machine direction, such as in the "machine direction" and/or the "transverse direction", or may be oriented in both directions, or "biaxially" oriented.
The present invention is also suitable for sheet applications. „„„-w PCT/US9
WO 99/67225
The benzocycle-substituted pyrimidine or triazine compounds of the formula (I), (II), or (IV)-(IX) are suitable for the photochemical stabilization of undyed, dyed or printed fiber materials comprising for example, silk, leather, wool, polyamide or polyurethanes and especially cellulose-containing fiber materials of all kinds. Examples of such fiber materials are the natural cellulose fibers, such as cotton, linen, jute and hemp and also viscose staple fiber and regenerated cellulose. Preferred textile fiber materials are those of cotton. The triazine and pyrimidine compounds of the present invention are also suitable for the photochemical stabilization of hydroxyl-containing fibers in blend fabrics, for example blends of cotton with polyester fibers or polyamide fibers. A further preferred area of application relates to the blocking or reduction of the UV radiation which passes through the above-mentioned textile materials (UV cutting) and the heightened sun protection which textile materials finished with a novel compound offer to the human skin.
To this end, one or a number of different compounds of the formula (I), (II), or (IV)-(IX) are applied to the textile fiber material by one of the customary dyeing methods, advantageously in a quantity of 0.01 to 5% by weight, preferably 0.1 to 3% by weight and, in particular, from 0.25 to 2% by weight, based on the weight of the fiber material.
The benzocycle-substituted pyrimidine or triazine compounds can be applied to the fiber material in various ways and fixed on the fiber, especially in the form of aqueous dispersions or printing pastes. The textile fiber materials finished with the novel compounds of the formula
(I), (II), or (IV)-(IX) possess improved protection against photochemical breakdown of the fiber and yellowing phenomena and, in the case of dyed fibre material, are of enhanced (hot) light fastness. Particular emphasis should be drawn to the greatly improved photoprotective effect of the treated textile fiber material and, in particular, the good protective effect with respect to short-wave UV-B rays. This is manifested by the fact that the textile fiber material finished with an benzocycle-substituted pyrimidine or triazine compound has, relative to untreated fabric, a greatly increased sun protection factor (SPF).
The sun protection factor is defined as the quotient of the dose of UV radiation which damages protected skin to that which damages unprotected skin. Accordingly, a sun protection factor is also a measure of the extent to which untreated fiber materials and fiber materials treated with a novel compound of the formula (I), (II), or (IV)-(IX) are permeable to UV radiation. The determination of the sun protection factor of textile fiber materials is explained, for example, in WO94/04515 or in J. Soc. Cosmet. Chem. 40, 127-133 (1989) and can be carried out analogously thereto. Yet another use of the UV absorbers according to the invention is in the stabilization of intra-ocular and contact lenses.
The inventive UV absorbers are suitable as photoprotective agents in cosmetic preparations. The invention additionally relates, therefore, to a cosmetic preparation comprising at least one benzocycle-substituted pyrimidine or triazine compound and cosmetically acceptable carriers or auxiliaries.
The novel cosmetic composition contains from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the overall weight of the composition, of a benzocycle-substituted pyrimidine or triazine UV absorber and a cosmetically acceptable auxiliary.
The cosmetic composition can be prepared by physically mixing the novel UV absorber with the auxiliary by means of customary methods, for example by simply stirring together the two materials.
The cosmetic preparation according to the invention can be formulated as a water-in-oil or oil-in-water emulsion, as an oil-in-oil alcohol lotion, as a vesicular dispersion of an ionic or nonionic amphiphilic lipid, as a gel, solid stick or as an aerosol formulation.
As a water-in-oil or oil-in-water emulsion, the cosmetically acceptable auxiliary preferably contains from 5 to 50% of an oily phase, from 5 to 20% of an emulsifier and from 30 to 90% water. The oil phase can comprise any oil which is suitable for cosmetic formulations, e.g., one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
For these cosmetic formulations, it is possible to use any conventionally employed emulsifier, e.g., one or more ethoxylated esters of naturally occurring derivatives, i.e., polyethoxylated esters of hydrogenated castor oil; or a silicone oil emulsifier such as silicone polyol; an unmodified or ethoxylated fatty acid soap; an ethoxylated fatty alcohol; an unmodified or ethoxylated sorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride.
The cosmetic formulation can also comprise further components, for example emollients, emulsion stabilizers, skin moisteners, tanning accelerators, thickeners such as xanthan, moisture retention agents such as glycerol, preservatives, or fragrances and colorants.
The novel cosmetic formulations are notable for good protection of human skin against the damaging effect of sunlight while at the same time providing for reliable tanning of the skin. The invention will now be illustrated by the following examples. The examples are not intended to be limiting of the scope of the present invention. In conjunction with the general and detailed descriptions above, the examples provide further understanding of the present invention.
EXAMPLES
Examples and reaction schemes for producing specific examples of benzocycle substituted triazines in accordance with the invention are provided below. While the following examples illustrate preparations with one or more tetralin benzocylcs, one of ordinary skill will understand that these reactions may also be carried out with any of a variety of other benzocycles, where when necessary, reactive substituents on such other benzocycles are protected in accordance with procedures and reagents well known and understood by those of ordinary skill.
PREPARATIVE EXAMPLES
Example 1 : Reaction of Cyanuric Chloride with Tetralin; Use of Tetralin as Solvent
Figure imgf000069_0001
AlCla
Figure imgf000069_0002
B
To a reaction flask equipped with a reflux condenser, an argon inlet, a magnetic stirring bar and a glass stopper was added 100 mL of tetralin and 9.2 g of cyanuric chloride. To the resulting solution was added 10 g of anhydrous A1C13 over a period of 10 minutes at 0°C. After the addition was over, the reaction mixture was heated in an oil bath at 40 °C for 16 hours. The heating was discontinued and the reaction mixture was cooled in an ice bath and treated with ice-cold water. The reaction mixture was then extracted with methylene chloride and the organic layer dried over anhydrous sodium sulfate and concentrated to remove volatiles. The residue was treated with methanol affording a precipitate which was filtered, washed with methanol and dried to give 12.4 g of the product. The NMR and mass analysis of the product showed it to consist of a mixture of monotetralin-bischloro-triazine (Compound A), bistetralin-monochloro-triazine (Compound B) and tristetralin-triazine (Compound C).
Example 1 Alternate Procedure: Use of Monochlorobenzene as Solvent
A mixture of 47.7 g (0.256 mole) of cyanuric chloride and 67.6 g (0.507 mol) of aluminum chloride in 360 mL of chlorobenzene under nitrogen was heated to 40°C. Tetralin (68 mL, 0.500 mole) was added over the course of two hr. During this time the temperature increased to 50°C. The temperature was maintained at 50°C until an exotherm occurred.
After the exotherm had subsided, 200 mL of 10% aqueous HCl was added drop-wise such that the temperature was maintained below 50°C. The resulting mixture was filtered. The aqueous layer from the filtrate was extracted with methylene chloride. The combined organic layers were washed with water, dried over anhydrous magnesium sulfate, and treated with activated carbon. After filtration, the filtrate was concentrated in vacuo.
The residue was taken up in 300 mL of tetrahydrofuran, and cooled to 0°C. The precipitate was removed by filtration. The filtrate was concentrated in vacuo to give an oil which slowly crystallized to a dark yellow to brown solid, which contained P-4036 (50 - 70 area % by HPLC) plus tris-tetralin triazine and unreacted cyanuric chloride.
Example 2: Bistetralin-monoresorcinol-triazine (Compound D):
Example 1 product mixture
Figure imgf000071_0001
D
A mixture of 132.3 g of the product of Example 1 Alternate Procedure (Compound B) and 38.7 g of resorcinol in 300 mL of chlorobenzene was heated to 60°C. Aluminum chloride (61.0 g) was added over a 2 hr. during which time the temperature increased to 80°C. The mixture has held at 80°C for an additional 2 hr. After cooling to 60°C, the reaction mixture was poured into 400 mL of ice water. The mixture was concentrated in vacuo. The residue was triturated with 400 mL of water, and the resulting slurry was filtered. The solid was air-dried and then dried in vacuo. A Soxhlet extraction of the solid was done with refluxing chloroform. A solid precipitated from the chloroform extract. The solid was filtered, washed with cold chloroform, and dried to give Compound D as a light yellow powder in >92% purity by HPLC.
Example 3: Bistetralin-fmonoresorcinol-4-O-octyl)-triazine derivative (Compound E)
Figure imgf000071_0002
D
A mixture of 400 mg of the product of Example 2 (Compound D), 1.38 g of anhydrous potassium carbonate, 0.2 mL of 1 -iodooctane and 10 mL of acetone was heated to reflux for 24 hours. The reaction mixture was then cooled to room temperature and diluted with methylene chloride. The resulting mixture was filtered through Celite, and concentrated to dryness to give 422 mg of a crude product. The crude product was purified by column chromatography over silica gel to give a pure compound which was identified to be the bistetralin-(monoresorcinol-4-O-octyl)-triazine derivative (Compound E) by NMR and mass spectra.
Example 4: Monotetralin-bisresorcinol-triazine (Compound G .
Figure imgf000072_0001
To a 3-necked 250-mL round bottomed flask was charged with 14.0 g of monotetralin-bischloro-triazine (Compound F), 11.56 g of resorcinol, and 130 mL of chlorobenzene and then purged with nitrogen. Into the solids addition funnel was placed 18.76 g of anhydrous aluminum chloride. The solution was heated to 49°C and addition of aluminum chloride was begun in portions. The aluminum chloride was added over the course of two hours and the temperature allowed to slowly climb to 65 °C. The reaction mixture was then heated to 90-95 °C and held in that range for 3 hours. The mixture was a dark red slurry at this point.
At the end of the reaction period, the heat was removed and the temperature allowed to fall to about 60 °C. The attachments were then removed from the reaction flask and the mixture was poured into 200 mL of cold water. The mixture was shaken, discharging the red color and leaving a yellow emulsion. When this had cooled completely, it was transferred to a round bottomed task and the chlorobenzene-water azeotrope was removed on a rotary evaporator until no further chlorobenzene was observed in the condensate. The resultant light yellow slurry was filtered, washed with water and dried in vacuo to give the desired product (Compound G). Example 5: Preparation of Compounds H and I
Figure imgf000073_0001
C„HI7I; 2C03; Acetone; reflux
Figure imgf000073_0002
H I
A mixture of 4.27 g of Compound G, 5.28 g of 1 -iodooctane, 6.9 g of anhydrous potassium carbonate, 0.5 g of Aliquat 336 and 50 mL of acetone was heated to reflux for 20 hr. At this stage additional 1 L of 1 -iodooctane and 3.5 g of anhydrous potassium carbonate were added and the refluxing was continued for an additional 8 hr. A TLC analysis at this stage showed almost complete disappearance of Compound G and formation of two new products. The reaction mixture was allowed to cool to room temperature, diluted with methylene chloride and filtered through Celite. The filtrate was concentrated under reduced pressure to give a crude product which consisted of compounds H and I as analyzed by NMR and mass spectra. The mixture is separable by column chromatography over silica gel. Example 6: Preparation of 4-(2-hvdoxyethyl ether of Bis-Tetralin-mono-Resorcinol Triazine (Compound J)
Figure imgf000074_0001
A mixture of 10.0 g of bis-tetralin-mono-resorcinol triazine (Compound D), 130 mL of DMF, 2.6 g of anhydrous sodium carbonate, 0.25 g of potassium iodide, 0.88 g of PEG-400 (polyethylene glycol), and 7.5 g of 2-chloroethanol was heated to 120°C for 15 hr. After the first 9 hr, an additional 2.5 g of 2-chloroethanol was added and heating was continued. After completion of the reaction, the mixture was poured into 300 mL of ice water. The precipitated solids were filtered, washed with water, and dried. HPLC and NMR analyses indicated that Compound J was obtained in >90% purity.
Example 7: Preparation of 4-(6-hvdroxyhexyl)ether of Bis-Tetralin-mono-Resorcinol Triazine (Compound K
Figure imgf000074_0002
A mixture of 10 g of bis-tetralin-mono-resorcinol triazine (Compound D, 0.02 mole) and 80 mL of MIBK was heated to 90 °C. Sodium hydroxide 1.0 g (0.031 mole) was slowly added, resulting in a nearly clear solution. Then 0.25 g (0.0015 mole) of potassium iodide and 0.88 g of PEG-400 (polyethylene glycol, approx. 0.0022 mole) were added. After the solution again became clear, 5.7 g (0.031 mole) of 6-chlorohexanol were added. The mixture was heated at 107-111 °C for 18 hr. The mixture was then washed with 1 N HCl and with water. The resulting solution was dried over magnesium sulfate, filtered and cooled to O°C. The resulting pale yellow solid was filtered, dried. HPLC and NMR analyses indicated that the Compound K was obtained in >90% purity.
Example 8: Preparation of 4-Lauroyl Ester Derivative of Bis-Tetralin-mono-Rcsorcinol Triazine (Compound LI
Figure imgf000075_0001
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene were added 11.0 mL of lauroyl chloride (Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture was heated at 150°C for 9 hr . The mixture was then cooled to 100°C and 200 mL of ethanol were added. The resulting precipitate was filtered, washed with ethanol, and allowed to air affording 21.3 g of Compound L as a pale yellow solid.
The solid was dissolved in 50 mL of hot toluene. The slurry was warmed in a water bath until all of the solid dissolved. Methanol (300 mL) was added to the mixture maintained at reflux temperature. The solution was then cooled to room temperature. The resulting solid was filtered, washed with several portions of methanol, and dried in vacuo to give 20.25 g of the title compound as a pale yellow solid.
Example 9: Preparation of 4-Hexanoyl Ester Derivative of Bis-Tetralin-mono-Resorcinol Triazine (Compound M)
Figure imgf000075_0002
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene were added 8 mL of hexanoyl chloride (Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture was heated at 150 °C for 12.5 hr. The product was isolated by the procedure of Example 9 to give 14.1 g of the Compound M as a pale yellow solid.
Example 10: Preparation of 4-Octanoyl Ester Derivative of Bis-Tetralin-mono-Resorcinol Triazine (Compound N)
Figure imgf000076_0001
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene were added 8 mL of octanoyl chloride (Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture was heated at 150°C for 23.5 hr. The product was isolated by the procedure of Example 2 to give 17.8 g of the Compound N as a pale yellow solid.
Example 11 : 4-(2-EthylhexanoyO Ester Derivative of Bis-Tetralin-mono-Resorcinol Triazine (Compound O)
Figure imgf000076_0002
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene were added 8 mL of 2-ethylhexanoyl chloride (Aldrich) and 10 mL of ortho- dichlorobenzene. The stirred mixture was heated at 150°C for 20 hr. The mixture was then cooled to 100°C and 200 mL of ethanol was added. Upon cooling to 0°C overnight an oil precipitated. The supernatant was decanted off. The oil was dissolved in a refluxing hexanes-toluene mixture, and then cooled to 0°C. The resulting solid was filtered, washed with methanol, and air dried to give 21.4 g of a pale yellow solid. The solid was recrystallized from hexanes-toluene, filtered, washed with methanol, and dried in vacuo to give 15.8 g of Compound O as a pale yellow solid.
Example 12: 4-(3,5,5-trimethylhexanoyl) Ester Derivative of Bis-Tetralin-mono-Resorcinol Triazine (Compound P
Figure imgf000077_0001
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene were added 9 mL of 3,5,5-trimethylhexanoyl chloride (Aldrich) and 10 mL of ortho- dichlorobenzene. The stirred mixture was heated at 150°C for 7 hr. The mixture was then cooled to 100°C and 200 mL of ethanol was added. Upon cooling to 0°C overnight, an oil precipitated. The supernatant was decanted off. The oil was washed with five 150 mL portions of methanol and dried in vacuo. The resulting glass was recrystallized twice from hexanes to give 13.1 g of the Compound P as a pale yellow solid.
Example 13: Preparation of 2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6- bis(tretralin - 1,3, 5-triazine (Compound 0)
Figure imgf000077_0002
To a mixture of 9 g of Compound D, 6.9 g of anhydrous potassium carbonate, 0.3 g of potassium iodide and 50 mL of acetone was added 2.4 mL (2.7 g) of ethyl chloroacetate. The mixture was stirred at reflux for six hours. HPLC analysis indicated full conversion of Compound D. After cooling, the mixture was diluted with 100 mL of methylene chloride and filtered through a bed of diatomaceous earth, which was washed with an additional 50 mL of methylene chloride. The combined filtrates were concentrated in vacuo. The product was recrystallized from ethyl acetate and dried in vacuo to give 8.4 g of Compound Q as a near white solid in 94% purity (HPLC area % at 290 nm). The structure was verified by 13C and 'H-NMR spectroscopy.
Example 14: Preparation of 2-[2-hydroxy-4-(N-(n-butyl)-N-(2-hydroxyethyD- methanamidooxy)phenyl]-4,6-bis(tetralin)- 1,3, 5-triazine) (Compound R)
Figure imgf000078_0001
A mixture of 5 g of Compound Q, 1.66 g of butyl ethanolamine, 0.12 g of 4-dimethylaminopyridine, and 30 mL of xylenes was stirred at reflux. After 26 hr, 2 g of butyl ethanolamine was added. After 48 hr, HPLC analysis showed 99.5% conversion of Compound P (area % at 290 nm). The mixture was allowed to cool. The precipitated solids were diluted with 175 mL of hexanes and stirred for 3 hr. The mixture was filtered and the collected solid was air dried. The solid was stirred with 150 mL of methanol for several hours, filtered, washed with methanol, and dried in vacuo to give 5 g of Compound R as a white solid in 96% purity (HPLC area % at 290 nm). The structure was verified by 13C and 'H-NMR spectroscopy.
Example 15: Preparation of bis-tetralin-mono-resorcinol triazine 4-O-propanesulfonate ester (Compound S
Figure imgf000078_0002
To a stirred mixture of 11.6 g of Compound D, 9 g of anhydrous potassium carbonate, and 100 mL of tetrahydrofuran (THF), cooled to 4°C was added a solution of 3.15 mL of propanesulfonyl chloride in 30 mL of THF over 22 min. The resulting mixture was stirred for 40 hr at room temperature. An additional 1 mL of propanesulfonyl chloride was added, and the mixture was stirred for 24 hr. HPLC analysis showed complete conversion of starting material. The solids were removed by filtration and the product was crystallized from the filtrate. The filtered solids were extracted with chloroform, and the chloroform was removed in vacuo to afford additional product. The combined yield was 8.5 g. Recrystallization from ethyl acetate afforded Compound S in 99% purity as determined by HPLC (area % at 290 nm). The structure was verified by IR, 13C, and 'H-NMR spectroscopy.
Example 16: Preparation of bis-tetralin-mono-resorcinol triazine 4-O-phenylsulfonate ester (Compound T)
Figure imgf000079_0001
To a mixture of 15 g of Compound D, 13.8 g of anhydrous potassium carbonate and 100 mL of tetrahydrofuran, cooled to 4°C, was added a solution of 5.2 mL (7.1 g) of benzenesulfonyl chloride in 30 mL of THF over 37 minutes. The resulting mixture was allowed to warm to room temperature and stirred for 19 hr. An additional 1 mL of benzenesulfonyl chloride was added, and the mixture was stirred for 3 hr. Methanol (5 mL) was added. The mixture was filtered, and the solids washed with THF.
The product was crystallized from the combined filtrates, filtered, and dried. Compound T (1 1.3 g) was obtained as a white solid by recrystallization from chloroform/hexanes (1 :3 v/v). HPLC analysis showed 99% purity (area at 290 nm). The structure was verified by I3C and 'H-NMR spectroscopy. Example 17: Preparation of monotetralin-monoresorcinol-monochloro-1.3, 5-triazine (Compound U)
Figure imgf000080_0001
*■ U
To a stirring mixture of 2.8 g of monotetralin-bischloro- 1 ,3, 5-triazine (Compound F), 1 g of resorcinol, and 25 mL of chlorobenzene was added 1.34 g of aluminum chloride at ice-bath temperature. The reaction mixture was allowed to warm to 15 15 °C and stirred for 3 hr. The reaction mixture was then allowed to warm to room temperature and stirred for 20 hr. The reaction mixture was quenched with ice-cold 2% aqueous hydrochloric acid. A precipitate formed, whcih was collected by filtration, washed with water, and dried. The precipitate was analyzed by thin layer chromatography (TLC), HPLC, and mass spectroscopy, which identified Compound U as the major product.
20
Example 18: Preparation of a hindered phenol adduct of bistetralin-monoresorcinol- 1,3, 5-triazine (Compound V)
Figure imgf000080_0002
35 To a stirring mixture of 2.25 g of compound D, 2.76 g of anhydrous potassium carbonate, and 50 mL of acetone was added 1.24 g of 3-chloromethyl-2,4- dimethyl-6-tert-butylphenol, 150 mg of sodium iodide and 250 mg of Aliquat® 336 (triscaprylmethylammonium chloride). The reaction mixture was heated to reflux for 3 hr. No starting material and only one major product was detected using TLC and HPLC analysis. The reaction mixture was allowed to cool to room temperature, diluted with 50 mL of methylene chloride, and filtered through Celite® brand filter agent. The filtrate was concentrated under reduced pressure. The residue was dissolve in 100 mL of methylene chloride, washed with water, dried over anhydrous sodium sulfate, and concentrated to dryness to give Compound V, which was analyzed by mass spectroscopy.
Example 19: Preparation of hindered phenol adducts of monotetralin-bisresorcinol-1, 3, 5-triazine (Compounds W and X)
Figure imgf000081_0001
W and X
Figure imgf000081_0002
To a stirring mixture of 2.14 g of Compound G, 5.5 g of anhydrous potassium carbonate, and 40 mL of MIBK was added 2.49 g of 3-chloromethyl-2,4- dimethyl-6-tert-butylphenol, 150 mg of sodium iodide, and 250 mg of Aliquat® 336. The reaction mixture was heated to reflux for 8 hr. After 8 hr, TLC analysis showed almost no starting material. The reaction mixture was allowed to cool to room temperature, diluted with methylene chloride, and filtered through Celite® brand filter agent. The filtrate was concentrated under reduce pressure, to give a mixture of Compounds W and X as determined by TLC.
Example 20: Preparation of 2,4-bistetralin-6-(2,4-dihydroxy-3-diallylaminomethyl)-l, 3,5- triazine (Compound Y)
Figure imgf000082_0001
To a stirring suspension of 2.2.5 g of Compound D in 50 mL of toluene was added 3 mL of diallylamine and 5 mL of aqueous formaldehyde. The reaction mixture was heated to reflux for 4 hr. After 4 hr, TLC analysis detected almost no starting material and the formation of one major product. The reaction mixture was allowed to cool to room temperature and concentrated under reduced pressure. The residue was dissolved in 100 mL of methylene chloride, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduce pressure to give Compound X, which was analyzed by mass spectroscopy.
Example 21 : Preparation of bis-tetralin-mono-resorcinol- 1,3, 5-triazine dimer (Compound Z)
Figure imgf000082_0002
To a mixture of 10 g of Compound D, 12.2 g of anhydrous potassium carbonate, 3.9 g of 1,5-diiodopentane, a catalytic amount of Aliquat® 336, and 60 mL of dioxane was stirred at reflux for 24 hr. HPLC analysis indicated full conversion of compound D. After cooling, the mixture was diluted with 150 mL of methylene chloride and filtered through a bed of diatomaceous earth. The filtrate was concentrated under reduced pressure to give compound U.
PERFORMANCE TESTING EXAMPLES
Example 22:
3% Toluene solutions of the stabilizers were prepared. The colors of these solutions were measured in a 1-cm cell using a Byk-Gardner Liquid Color
Spectrophotometer. As can be seen from Table I, tetralin triazine UV absorbers Compound E and Compound J have lower color than Tinuvin 1577, a current art triazine UV absorber.
Table I. Color Values Of 3% Toluene Solutions Of Stabilizers
Stabilizer APHA Color Gardner Color CIE b value
Tinuvin 1577 485 3 17.1
Compound E 364 2 13.2
Compound O 218 1 7.9
Example 23:
Thermogravimetric analysis was carried out. Duplicate specimens were heated in a Perkin-Elmer 7 Series thermobalance from 30 - 500°C at 10°C/ min in both air. The purge gas flow rate was ~25 mL/min. Compound E was compared against the major current art stabilizers for polycarbonate. As can be seen from Table II, Compound E is significantly less volatile than Tinuvin 1577, a current art stabilizer. (T-10% and T-20% are the temperatures at which 10% and 20%, respectively, of weight loss occurs during the above heating protocol.)
Figure imgf000084_0001
10
Example 24:
Polycarbonate plaques were prepared as follows. GE Lexan 105 barefoot natural flake polycarbonate resin (melt temperature 310 - 333 °C) was dry blended with
0.35% stabilizer plus 0.10 wt% Mark® 2112 phosphite. The blended compositions were j melt-mixed and extruded in a Haake torque rheometer equipped with a a 0.75-inch 25 : 1 single mixing screw extruder. The zone temperatures were 246, 265, 295, and 304 °C. The extruded polycarbonate was pulled through a water bath, dried, pelletized, and redried at 120°C for 4 - 48 hr in a forced air oven. The pellets were injection molded at 340 °C with a 40 second dwell time using an Arburg "Allrounder" hydraulic injection molder to form 2 x
2ø 2.5 0.100-inch plaques. The mold temperature was 100 °C. The injection barrel temperature of 340 °C was selected to simulate extremely harsh conditions. Yellow indices and delta E data were obtained using a Macbeth Color Eye Colorimeter with illuminate C, 2 ° observer, specular component excluded, and UV component included. As can be seen from Table III, Compound E is more resistant to thermal yellowing than Tinuvin 1577, a
25 current art triazine UV absorber.
TABLE III: Color Of Stabilized Polycarbonate Plaques Injection Molded At 340 °C
30
Figure imgf000084_0002
Example 25:
Stabilized polycarbonate plaques were prepared as in Example 3 with the 35 exception that the injection molding temperatures were lower. The temperatures were: nozzle - 305 °C; nozzle side - 310°C; middle - 300°C; and feed - 290°C. The plaques were subjected to 18 days of oven aging at 100°C. As can be seen from Table IV, Compound E inhibits thermal yellowing of polycarbonate and has performance equal or better than current art triazine UV absorbers Tinuvin 1577 and UV-1164.
Table IV. Oven Aging of Stabilized Polycarbonate Compositions at 100°C
Figure imgf000085_0001
Example 26:
Stabilized polycarbonate plaques were prepared as in Example 4. They were exposed in a xenon-arc WeatherOmeter following ASTM G-26 using Test Method B (Miami, Fla. conditions). The conditions were an irradiance of 0.35 W/m2 at 340 nm, alternating cycles of light and darkness, intermittent water spray, and a black panel temperature of 63 ± 3 °C. Delta E (total color change) was measured after 400 hr. of exposure. The results, summarized in Table V show that Compound E is more effective in reducing total color change than current art stabilizers Tinuvin 1577 and Tinuvin 234.
Table V. Accelerated Weathering of Stabilized Polycarbonate Compositions
Figure imgf000085_0002
Example 27: Stabilized Coating Compositions
Stabilized clear acrylic melamine compositions were prepared and coated onto steel panels for accelerated weathering testing as follows. Compound E (2% based on total resin solids) was pre-dissolved in xylenes, alone and in combination with Sanduvor® 3058 HALS (0.67% or 1.0% based on total resin solids), and added to the clear acrylic melamine formulation given in Table VI. Steel panels pre-coated with ED5050A E-coat, 764204 primer, and 542DF716 white base-coat and measuring 4" x 12" were obtained from ACT Laboratories, Inc. (Hillsdale, Michigan). The panels were coated with the clear coat formulations using the draw-down technique (WC-52 Wire-Cators™ obtained from Leneta Co., Ho-Ho-Kus, N.J.). The clear coats were allowed to flash for 10 min. at ambient temperature and cured for 30 min. at 135°C.
Table VI. Acrylic Melamine Clear Coat Formulation
Material Amount
Doresco® TA 39-14 acrylic resin 81.25 g
Cymel® 303 cross-linker 35.0 g
Cycat® 4040 catalyst l .O g n-Butanol 20.0 g
Xylene 16.0 g
UV Absorber 0.364 ga
Sanduvor® 3058b 0.182 gb
a) Amount for 2% based on total resin solids b) Amount for 1% based on total resin solids
Accelerated weathering is carried out with a QUV following ASTM G53 (GM cycle), which is weathering under alternate cycles of (i) UV light at 70 C for 8 hours and (ii) condensation with no UV light at 50 C for 4 hr. Specular properties (gloss and distinctness of image, or DOI) are measured as a function of weathering time. Compositions containing either Compound E or Compound J both have improved gloss and DOI retention relative to the unstabilized control. Compositions containing HALS S-3058 in addition to Compound E or Compound J also exhibit improved gloss and DOI retention. Although the present invention is described with reference to certain preferred embodiments, it is apparent that modifications and variations thereof may be made by those skilled in the art without departing from the scope and spirit of this invention as defined by the appended claims.

Claims

THE CLAIMS What is claimed is:
1. A compound of formula (I)
Figure imgf000087_0001
wherein each A is independently nitrogen or methine optionally substituted with R2, and at least two A are nitrogen; each of T and T' is independently a direct bond, carbon, oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or functional groups containing these elements.
X is independently selected from hydrogen and a blocking group; each of R' and R2 is independently a hydrocarbyl group, a functional hydrocarbyl group, hydroxy, alkoxy, hydrogen, halogen, cyano, or isocyano; each of Y, R3 and R4 are independently a hydrogen, hydrocarbyl group, a functional hydrocarbyl group, halogen, hydroxyl, cyano, -O(hydrocarbyl), -O(functional hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl), -N(hydrocarbyl)(ftιnctional hydrocarbyl), -S(hydrocarbyl), -S(functional hydrocarbyl), -SO2(hydrocarbyl), -SO2(hydrocarbyl), -SO3 (hydrocarbyl), -SO3(functional hydrocarbyl), -COO(hydrocarbyl), -COO(functional hydrocarbyl), -CO(hydrocarbyl), -CO(functional hydrocarbyl, -OCO(hydrocarbyl), -OCO(functional hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -CONH2, -CONH(hyrdocarbyl), -CONH(functional hyrdocarbyl), -CON(hydrocarbyl)(hyrdocarbyl), -CON(hydrocarbyl)(functional hyrdocarbyl), -CON(functional hydrocarbyl)(functional hyrdocarbyl), 67225
-S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups;
Z is Y,
(
Figure imgf000088_0001
or
Figure imgf000088_0002
wherein
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms;
X is independently selected from hydrogen and a blocking group; and
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano; each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous, boron, silicon, selenium, tellurium, or functional groups containing these elements; each of m, n, and o is independently an integer between 0 and 4, provided that when both G are direct bonds, the sum of m, n and o is between 2 and 10, and that when one G is a direct bond, the sum of m, n and o is between 1 and 9, and when neither G is a direct bond, the sum of m, n and o is between 0 and 8; WO 99/67225
p is an integer between 0 and 3; and q is an integer between 0 and 20.
2. A compound according to claim 1 wherein each G is a direct bond; m is 4; n, o, p, and q are 0.
3. A compound according to claim 1 wherein T' is an oxygen atom and Y is a group L, said compound having formula (II):
Figure imgf000089_0001
wherein L is Y, Z, R or R as defined above.
4. A compound according to claim 3 wherein L is selected from the group consisting of hydrogen; an alkyl of 1 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; 67225
an aralkyl of 7 to 24 carbon atoms optionally substituted by one or more hydroxy, alkoxy, chloro, cyano, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; a polyoxyalkylene radical of the formula XII (XII)
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-D, wherein D, is hydrogen, -CH2-CH(OH)-CH2-OH,
-CH2-CH2 CH2
V or R25; a polyoxyalkylene radical of the formula XIII
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D2 (XIII) wherein D2 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula VIII
-YY-O-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D3 (XIV) wherein D3 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula XV
-(CH2)kk-CH(R2')-CO-B1-(CnnH2„n-0-)mm-CnnH2nn-B1-D4 (XV) wherein D4 is hydrogen of R25; a polyoxyalkylene radical of the formula XVI
-CO-CH2-CH2-NH-(CnnH2nn-O-)mm-CnnH2nn-D5 (XVI) wherein D5 is -NH2, -NH-(CH2)2-COO-R23 or -O-R25; a polyoxyalkylene radical of the formula XVII
-YY-O-CO-CH2-CH2-NH-(CnnH2nn-O-)mm-CnnH2nn-D5 (XVII) wherein D5 is as defined under formula (XVI); a polyoxyalkylene radical of the formula XVIII
-(CnnH2nn-O-)mm-CnnH2nn-D6 (XVIII) wherein D6 is -NH-CO-R24, -OR25, OH or H; a polyoxyalkylene radical of the formula XIX
-CH-CH2-(OCH-CH2)m-D7 (XIX) k17 R17
wherein D7 is -OR25, -NHCOR24 or -OCH2CH2OR25; /67225
R2' is hydrogen or C,-C,6 alkyl;
R22 is halogen or -O-R23;
R23 is hydrogen, C,-C6 alkyl, C3-C6 alkenyl, aryl, or aryl-C,-C4-alkyl; R24 is hydrogen, C,-C12 alkyl or aryl; R25 is C,-C,6 alkyl, C5-C12 cycloalkyl, C3-C6 alkenyl,
C,-C,2 alkylaryl or aryl-C,-C4 alkyl; R26 is hydrogen or C,-C4 alkyl; R27 is hydrogen, C,-C18 alkyl, C3-C6 alkenyl, C,-Clg alkoxy, halogen or aryl-C,-C4- alkyl; R28 and R29 independently of one another are hydrogen,
C,-C18 alkyl, C3-C6 alkenyl, C,-C18 alkoxy, or halogen; R30 is hydrogen, C,-C4 alkyl or CN; YY is unsubstituted or substituted C2-C20 alkyl; kk is zero or an integer from 1-16; B, is O or NH; mm is an integer from 2 to 60; nn is an integer from 2 to 6; u is an integer from 1 to 4.
5. A compound according to claim 3 wherein TZ is
Figure imgf000091_0001
wherein
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms;
X is independently selected from hydrogen and a blocking group; and
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), 67225
-CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano.
6. A compound according to claim 5 wherein all G are direct bonds, m are 0, and all A are nitrogen, so that said compound has formula:
Figure imgf000092_0001
wherein
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms;
X is independently selected from hydrogen and a blocking group; and
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S (functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano. 7225
A compound according to claim 1 wherein T is a direct bond and Z is:
Figure imgf000093_0001
so that said compound has formula:
Figure imgf000093_0002
wherein A, G, T', X, Y, R1 to R4, and subscripts m, n, o, p, and q, are defined as defined in claim 1.
8. A compound according to claim 7 wherein all G are direct bonds; m=4; n, o, p, and q are 0; and all A are nitrogen, said compound having formula:
Figure imgf000094_0001
wherein
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms;
X is independently selected from hydrogen and a blocking group; and R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl),
-S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano.
67225
A compound of formula (VII):
Figure imgf000095_0001
wherein
A, T, T', R', R2, Y, Z, R3, R4, G, m, n, o, p, q, are defined as in claim 1 ; r is 2 or 3;
X', when r is 2 is — CO— R16— CO— , — CO2— R'6— CO — , — SO2— R16— SO2— , — CO — NH — R'7 — NH — CO — , a polyoxyalkylene bridge member of formula -CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-CO-, or
-COCHCH2NH(CnnH2nnO)mCnnH2nn-NHCH2-CHCO- (XXIV)
R21 k>
when r = 3, X' is:
-(-CO2-R'6)R'9, -(-CONH-R16)R'9, -(-SO2-R16)R19;
R16 is C2-CI0 alkylene, C2-C10 oxaalkylene or C2-C10 dithiaalkylene, phenylene, naphthylene, diphenylene or C2-C6 alkenylene; R'7 is C2-C]0 alkylene, phenylene, naphthylene, methylenediphenylene or C7-C,5 alkylphenylene; and R'8 is C2-C10 alkylene or C4-C20 alkylene which is interrupted by one or more oxygen atoms; R19 is C3-C10alkanetriyl; and R20 is C4-C10alkanetetryl. 67225
10. A compound of formula (VI)
Figure imgf000096_0001
wherein
A, T, X, Z, R1, R2, R3, R4, G, m, n, o, p, q are defined as in claim 1 ; r is an integer between 2 and 4; D when r is 2, is selected from the group consisting of C2-C16 alkyl, C4-C,2 alkenyl, xylylene, C3-C20 alkyl which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20 alkyl which is interrupted by one or more oxygen atoms, — CH2CH(OH)CH2O— R15— OCH2CH(OH)CH2,
— CO— R16— CO— , — CO— NH— R'7— NH— CO— ,
— (CH2) — COO— R' 8— OCO— (CH2) — a polyoxyalkylene bridge member of the formula XX
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-CH2-CH(OH)-CH2- (XX), a polyoxyalkylene bridge member of the formula XXI
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-CO- (XXI), a polyoxyalkylene bridge member of the formula XXII
-YY-O-CO(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-COO-YY- (XXII), a polyoxyalkylene bridge member of the formula XXIII
-(CH2)kk-CH(R2')-CO-B -(CnnH2nn-O-)mmCnnH2nn-B,-CO-CH(R21)- (CH2)kk- (XXIII), a polyoxyalkylene bridge member of the formula XXIV 67225
-COCHCH2NH(CnnH2nnO)mCnnH2nn-NHCH2-CHCO- (XXIV) k» R221
a polyoxyalkylene bridge member of the formula XXV
-YY-O-CO-(CH2)2-NH-(CnnH2nn-O-)mm-CnnH2nn-NH-
(CH2)2COO-YY- (XXV), a polyoxyalkylene bridge member of the formula XXVI
-(CnnH2nn-O-)mm-CnnH2nn- (XXVI), and a polyoxyalkylene bridge member of the formula XXVII
-CH(CH3)-CH2-(O-CH(CH3)-CH2)a-(O-CH2-CH2)b-(O-CH2- CH(CH3)C- (XXVII), wherein a + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0, R2' is hydrogen or C,-C]6 alkyl, R22 is halogen or -O-R23,
R23 is hydrogen, C,-Cft alkyl, C3-Cή alkenyl, aryl, or aryl-C,-C4-alkyl, R24 is hydrogen, C,-C12 alkyl or aryl, R25 is C,-C16 alkyl, C5-C12 cycloalkyl, C3-C6 alkenyl,
C,-C|j alkylaryl or aryl-C,-C4 alkyl, R26 is hydrogen or C,-C4 alkyl, R27 is hydrogen, C,-C18 alkyl, C3-C6 alkenyl, C,-C,8 alkoxy, halogen or aryl-C,-C4 alkyl, R28 and R29 independently of one another are hydrogen, C C^ alkyl, C3-C6 alkenyl, or C,-Cι8 alkoxy, or halogen; R30 is hydrogen, C,-C4 alkyl or CN, YY is unsubstituted or substituted C2-C20 alkyl, kk is zero or an integer from 1-16, B, is O or NH, mm is an integer from 2 to 60, nn is an integer from 2 to 6, u is an integer from 1 to 4; when r is 3, D is
(CH2)s-COO- R 19 67225
and when r is 4, D is
(CH2)s-COO- R 20
wherein R19 is C3-C10 alkanetriyl and R20 is C4-C10 alkanetetryl; and s is 1-6;
R'5 is C2-C,0 alkyl, C2-C10 oxaalkyl or C2-C10 dithiaalkyl, phenyl, naphthyl, diphenyl, or C2-C6 alkenyl, or phenylene-XX-phenylene wherein XX is — O— , — S— , — SO2— , — CH2— , or — C(CH3)2— ; R16 is C2-C10 alkyl, C2-CI0 oxaalkyl or C2-C,0 dithiaalkyl, phenyl, naphthyl, diphenyl, or C2-C6 alkenyl provided that when r is 3 the alkenyl has at least 3 carbons; R'7 is C2-CI0 alkyl,phenyl, naphthyl, diphenyl, or C2-C6 alkenyl, methylenediphenylene, or C4-C]5 alky lphenyl; and R'8 is C2-C,0 alkyl, or C4-C20 alkyl interrupted by one or more oxygen atoms.
11. A compound of formula (IX):
Figure imgf000098_0001
wherein
A, T, T, X, Y, R1, R2, R3, R4, G, m, n, o, p, and q are defined as in claim 1 ; r is an integer between 2 and 4;
D, when r is 2, is selected from the group consisting of C2-C16 alkylene, C4-CI2 alkenylene, xylylene, C3-C20 alkylene which is interrupted by one or more oxygen 67225
atoms, hydroxy-substituted C3-C20 alkylene which is interrupted by one or more oxygen atoms, — OOCR'4COO— , — CH2CH(OH)CH2O— R'5— OCH2CH(OII)CH2, — CO— R16— CO— , — CO— NH— R17— NH— CO— , and — (CH2) — COO— R18— OCO— (CH2) — ; and when r is 3, D is
19
(CH2)s-COO- ■ R'
and when r is 4, D is
20
(CH2)s-COO- •R
wherein R'9 is C3-C10 alkanetriyl and R20 is C4-C,0 alkanetetryl; s is 1-6; r is an integer between 2 and 4;
D, when r is 2, is selected from the group consisting of C2-CI6 alkylene, C4-C12 alkenylene, xylylene, C3-C20 alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20 alkylene which is interrupted by one or more oxygen atoms, — CH2CH(OH)CH2O— R15— OCH2CH(OH)CH2, — CO— R16— CO— , — CO— NH— R'7— NH— CO— , and — (CH2) - COO— R18— OCO— (CH2) — ; and when r is 3, D is
(CH2)s-COO- •R 1'9
and when r is 4, D is
(CH2)s-COO- 20
■ R'
wherein R19 is C3-C10 alkanetriyl and R20 is C4-C10 alkanetetryl; s is 1-6;
R8 is C,-C18 alkyl, C3-C,8 alkenyl, C3-C20 alkyl, which is interrupted by O, N, or S, and/or substituted by OH, C,-C4 alkyl which is substituted by — P(O)(OR14)2, — N(R9) (R10), or — OCOR", and or OH, or is glycidyl, cyclohexyl or C7-C„ phenylalkyl; R9 and R'° are each independently of the other, C,-C12 alkyl, C3-C12 alkoxyalkyl,
C4-C,6 dialkylaminoalkyl or C5-CI2 cycloalkyl, or R9 and R'°, when taken together, are C3-C9 alkylene or C3-C9 oxaalkylene of C3-C9 azaalkylene; R" is C|-C18 alkyl, C2-C)g alkenyl or phenyl; R'2 is C|-C,g alkyl, C2-CI8 alkenyl, phenyl, C,-C12 alkoxy, phenoxy, C,-C12 alkylamino; phenylamino, tolylamino or naphthylamino; R13 is C,-C,2 alkyl, phenyl, naphthyl or C7-C,4 alkylphenyl; R'4 is C,-C12 alkyl or phenyl; R'5 is C2-C10 alkylene phenylene or a phenylene-x-phenylene- group, wherein X is
-O- -SO 2 > -CH — , or — C(CH3> 2 '
R16 is C2-C10 alkylene, C2-C!0 oxaalkylene or C2-C!0 dithiaalkylene, phenylene, naphthylene, diphenylene or C2-C6 alkenylene; R'7 is C2-C|0 alkylene, phenylene, naphthylene, methylenediphenylene or C7-C,5 alkylphenylene, and R'8 is C2-CI0 alkylene or C4-C20 alkylene which is interrupted by one or more oxygen atoms.
12. A compound according to claim 9 wherein T is a direct bond and Z is a substituent of general formula III:
Figure imgf000100_0001
( Ilia ) ( Illb)
wherein
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms;
X is independently selected from hydrogen and a blocking group; and
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), „„„„„„ PCT/US9
WO 99/67225
-CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano.
13. A compound according to claim 10 wherein T is a direct bond and Z is a substituent of general formula III:
Figure imgf000101_0001
15 wherein
R1, R2, G, m, n, o, p, and q are defined as in claim 10;
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms; 20 X is independently selected from hydrogen and a blocking group; and
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), 25 -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3 (functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano.
30 14. A compound according to claim 12 wherein L is selected from the group consisting of hydrogen; an alkyl of 1 to 24 carbon atoms optionally substituted by one or more hydroxyl, carboxyl, carboalkoxy, amide, epoxy or amino groups and optionally 35 67225
containing one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atoms optionally substituted by hydroxyl, carboxyl, epoxy or amino group(s) and optionally containing one or more carbonyl groups, oxygen or nitrogen atoms in the chain; a cycloalkyl of 5 to 24 carbon atoms optionally substituted by hydroxyl, carboxyl, or amino group(s), and optionally containing carbonyl, oxygen, or nitrogen in the ring; and an aralkyl of 7 to 24 carbon atoms optionally substituted by hydroxyl, carboxyl or amino group(s) and may contain carbonyl, oxygen and/or nitrogen in the ring; a polyoxyalkylene radical of the formula XII
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-D, wherein D, is hydrogen,
-CH2-CH(OH)-CH2-OH, -CH2-CH2— CH2 V or R25; a polyoxyalkylene radical of the formula XIII
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D2 wherein D2 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula VIII
-YY-O-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D3 wherein D3 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula XV
-(CH2)kk-CH(R2')-CO-B1-(CnnH2nπ-O-)mm-CnnH2nn-B1-D4 wherein D4 is hydrogen of R25; a polyoxyalkylene radical of the formula XVI
-CO-CH2-CH2-NH-(CnnH2nn-O-)mm-CnnH2nn-D5 wherein D5 is -NH2, -NH-(CH2)2-COO-R23 or -O-R25; a polyoxyalkylene radical of the formula XVII -YY-O-CO-CH2-CH2-NH-(CnnH2nn-O-)mm-CnnH2nn-D5 wherein D5 is as defined under formula XVI; a polyoxyalkylene radical of the formula XVIII
"(CnnH2nn-O-)mm-CnnH2nn-D6 wherein D6 is -NH-CO-R24, -OR25, OH or H; a polyoxyalkylene radical of the formula XIX 7225
Figure imgf000103_0001
wherein D7 is -OR25, -NHCOR24 or -OCH2CH2OR25; a polyoxyalkylene bridge member of the formula XX
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-CH2-CH(OH)-CH2-; a polyoxyalkylene bridge member of the formula XXI
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-CO- ; a polyoxyalkylene bridge member of the formula XXII - Y Y-O-CO(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-COO- Y Y- ; a polyoxyalkylene bridge member of the formula XXIII
-(CH2)kk-CH(R2')-CO-B1-(CnπH2nn-O-)mmCnnH2nn-B1-CO-CH(R2')- (CH2)kk-; a polyoxyalkylene bridge member of the formula XXIV ;
Figure imgf000103_0002
a polyoxyalkylene bridge member of the formula XXV
-YY-O-CO-(CH2)2-NH-(CnnH2nn-O-)mm-CnnH2nn-NH-(CH2)2COO-YY- ; a polyoxyalkylene bridge member of the formula XXVI
"(Cnnn2nn-U- mm-Cnnn2nn- ; a polyoxyalkylene bridge member of the formula XXVII
-CH(CH3)-CH2-(O-CH(CH3)-CH2)a-(O-CH2-CH2)b-(O-CH2- CH(CH3)C- wherein a + c = 2.5 and b = 8.5 to 40.5, or a + c = 2 to 33 and b = 0; R2' is hydrogen or C,-C,6 alkyl; R22 is halogen or -O-R23;
R23 is hydrogen, C,-C6alkyl, C3-C6 alkenyl, aryl, or aryl-C,-C4-alkyl;
R24 is hydrogen, C,-C12 alkyl or aryl;
R25 is C,-C16 alkyl, C5-C12 cycloalkyl, C3-C6 alkenyl,
CrC]2 alkylaryl or aryl-C,-C4 alkyl; R26 is hydrogen or C,-C4 alkyl; R27 is hydrogen, C,-C18 alkyl, C3-C6 alkenyl, C,-C18 alkoxy, halogen or aryl-C,-C4 alkyl; R28 and R29 independently of one another are hydrogen,
C,-C18 alkyl, C3-C6 alkenyl, C,-C18 alkoxy or halogen; R30 is hydrogen, C,-C4 alkyl -CH2-CH2— CH2 or CN; °
YY is unsubstituted or substituted C2-C20 alkylene; kk is zero or an integer from 1-16; mm is an integer from 2 to 60; nn is an integer from 2 to 6; u is an integer from 1 to 4.
15. A compound according to claim 13 wherein L is selected from the group consisting of hydrogen; an alkyl of 1 to 24 carbon atoms optionally substituted by one or more hydroxyl, carboxyl, carboalkoxy, amide, epoxy or amino groups and optionally containing one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atoms optionally substituted by hydroxyl, carboxyl, epoxy or amino group(s) and optionally containing one or more carbonyl groups, oxygen or nitrogen atoms in the chain; a cycloalkyl of 5 to 24 carbon atoms optionally substituted by hydroxyl, carboxyl, or amino group(s), and optionally containing carbonyl, oxygen, or nitrogen in the ring; and an aralkyl of 7 to 24 carbon atoms optionally substituted by hydroxyl, carboxyl or amino group(s) and may contain carbonyl, oxygen and/or nitrogen in the ring; a polyoxyalkylene radical of the formula XII
-CH.-CH^^-CH.-O-^H.-^H^-O-^^D, wherein D, is hydrogen,
-CH2-CH(OH)-CH2-OH, -CH2-CH2— CH2
V or R25; a polyoxyalkylene radical of the formula XIII -CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D2 wherein D2 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula VIII
-YY-O-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-D3 wherein D3 is -(CH2)u-CO-R22 or R25; a polyoxyalkylene radical of the formula XV
-(CH2)kk-CH(R2')-CO-Br(CnnH2nn-O-)mm-CnnH2nn-B,-D4 wherein D4 is hydrogen of R25; a polyoxyalkylene radical of the formula XVI
-CO-CH2-CH2-NH-(CnnH2n, O-)mm-CnnH2nn-D5 wherein D5 is -NH2, -NH-(CH2)2-COO-R23 or -O-R25; a polyoxyalkylene radical of the formula XVII
-YY-O-CO-CH2-CH2-NH-(CnnH2nn-O-)mm-CnnH2nn-D5 wherein D5 is as defined under formula XVI; a polyoxyalkylene radical of the formula XVIII -(CnnH2nn-0-)mm-CnnH2nn-D6 wherein D6 is -NH-CO-R24, -OR25, OH or H; a polyoxyalkylene radical of the formula XIX
Figure imgf000105_0001
wherein D7 is -OR25, -NHCOR24 or -OCH2CH2OR25; a polyoxyalkylene bridge member of the formula XX
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-CH2-CH(OH)-CH2-; a polyoxyalkylene bridge member of the formula XXI -CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-CO- ; a polyoxyalkylene bridge member of the formula XXII
-YY-O-CO(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-COO-YY- ; a polyoxyalkylene bridge member of the formula XXIII
-(CH2)kk-CH(R21)-CO-Br(CnnH2nn-O-)mmCnnH2nn-BrCO-CH(R21)- (CH2)kk a polyoxyalkylene bridge member of the formula XXIV
-COCHCH2NH(CnnH2nnO)πιCnnH2nn-NHCH2-CHCO- ;
R21 R21
a polyoxyalkylene bridge member of the formula XXV -YY-O-CO-(CH2)2-NH-(CnnH2nn-O-)mm-CnnH2nn-NH-(CH2)2COO-YY- ; a polyoxyalkylene bridge member of the formula XXVI
a polyoxyalkylene bridge member of the formula XXVII -CH(CH3)-CH2-(O-CH(CH3)-CH2)a-(O-CH2-CH2)b-(O-CH2-
CH(CH3)C- wherein a + c = 2.5 and b = 8.5 to 40.5, or a + c = 2 to 33 and b = 0; R2' is hydrogen or C,-C,6 alkyl; R22 is halogen or -O-R23;
R23 is hydrogen, C,-C6 alkyl, C3-C6 alkenyl, aryl, or aryl-C,-C4-alkyl; R24 is hydrogen, C,-C12 alkyl or aryl; R25 is C,-C16 alkyl, C5-C12 cycloalkyl, C3-C6 alkenyl, C|-C12 alkylaryl or aryl-C,-C4alkyl;
R26 is hydrogen or C,-C4 alkyl; R27 is hydrogen, C,-C18 alkyl, C3-C6 alkenyl, C,-CI8 alkoxy, halogen or aryl-C,-C4 alkyl; R28 and R29 independently of one another are hydrogen, C,-C18 alkyl, C3-C6 alkenyl, C,-C,8 alkoxy or halogen;
R30 is hydrogen, C,-C4 alkyl or CN; YY is unsubstituted or substituted C2-C20 alkylene; kk is zero or an integer from 1-16; mm is an integer from 2 to 60; nn is an integer from 2 to 6; u is an integer from 1 to 4.
67225
16. A compound of formula (VIII):
Figure imgf000107_0001
wherein
A, T, T, X, Y, Z, R', R2, R3, G, m, n, o, p, and q are as defined in claim 1 ;
R4 is selected from the group consisting of straight chain alkylene of 1 to 12 carbon atoms, branched chain alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkylene substituted by cyclohexyl, alkylene interrupted by cyclohexyl, alkylene substituted by phenylene, alkylene interrupted by phenylene, benzylidene, — S — , — S — S — , — S — E — S — , — SO — , — SO2— , — SO— E— SO— , — SO2— E— SO2— , — CH2— NH— E— NH— CH — , and
Figure imgf000107_0002
wherein
E is selected from the group consisting of alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkylene interrupted by cyclohexylene of 8 to 12 carbon atoms, alkylene terminated by cyclohexylene of 8 to 12 carbon atoms; and r is an integer between 2 and 4. „„_„„,. PCT/US99/13
WO 99/67225
17. A compound according to claim 1 wherein all G are direct bonds; - m=4; n, o, p, and q arc 0; and all A are nitrogen, said compound having formula:
Figure imgf000108_0001
wherein
X is independently selected from hydrogen and a blocking group; and L, R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl), -SO2(hydrocarbyl), -SO3(hydrocarbyl), -COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl),
-OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional hydrocarbyl) or cyano.
18. A compound of formula (XXXV)
Figure imgf000108_0002
wherein
A, R', R2, G, m, n, o, p, q are defined as in claim 1; and each Hal is bromine, chlorine, or iodine. A compound of formula (XXXVI)
(R 2)q
Figure imgf000109_0001
wherein
A, R1, R2, G, m, n, o, p, q are defined as in claim 1 ; and each Hal is bromine, chlorine, or iodine.
20. A method of stabilizing a material which is subject to degradation by 5 actinic radiation by incorporating into said material of an actinic radiation stabilizer composition in an amount effective to stabilize the material against the effects of actinic radiation.
0 D 0
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