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WO2003035703A1 - Systemes de fixation par collage ininflammables et incombustibles adherant a des surfaces a faible energie - Google Patents

Systemes de fixation par collage ininflammables et incombustibles adherant a des surfaces a faible energie Download PDF

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Publication number
WO2003035703A1
WO2003035703A1 PCT/US2002/033839 US0233839W WO03035703A1 WO 2003035703 A1 WO2003035703 A1 WO 2003035703A1 US 0233839 W US0233839 W US 0233839W WO 03035703 A1 WO03035703 A1 WO 03035703A1
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WIPO (PCT)
Prior art keywords
composition according
composition
meth
initiator system
phenyl
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PCT/US2002/033839
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English (en)
Inventor
Eerik Maandi
Brendan Kneafsey
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Henkel Corporation
Loctite (R & D) Ltd.
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Publication date
Priority claimed from IE2001/0937A external-priority patent/IE83382B1/en
Priority claimed from IE20020286A external-priority patent/IE20020286A1/en
Priority claimed from IE20020293A external-priority patent/IE20020293A1/en
Application filed by Henkel Corporation, Loctite (R & D) Ltd. filed Critical Henkel Corporation
Priority to US10/419,250 priority Critical patent/US7098279B2/en
Publication of WO2003035703A1 publication Critical patent/WO2003035703A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • This invention relates to (meth) acrylate based polymerizable compositions and adhesive systems prepared therefrom, which include an aziridine-containing compound in a carrier material with which the aziridine-containing compound is unreactive.
  • the inventive compositions demonstrate a flash point above 140°F, desirably above 200°F, for each of the parts of the adhesive system.
  • the inventive compositions and adhesive systems also include a package for controlling the rate of cure and indicating the extent of cure.
  • the inventive compositions and adhesive systems are particularly well suited to bonding applications which involve at least one low energy bonding surface, for example, polyolefin, polyethylene, and polypropylene surf ces .
  • Low energy surfaces such as polyolefins, i.e, polyethylene, polypropylene, polybutene, polyisoprene, and copolymers thereof, are well known to be difficult to bond to each other and to other surfaces using adhesive bonding technology since they have few active bonding sites available at the free surfaces.
  • Low energy surfaces are defined as those having surface energies less than 45 mJ/m 2 , more typically less than 40 mJ/m 2 , or less than 35 mj/m 2 .
  • organoboranes such as the trialkylboranes including triethylborane and tributylborane for initiating and catalyzing the polymerization of vinyl monomers is well known.
  • organoborane compounds are known to be flammable in air so that the compounds and compositions containing them require special handling and the compositions have poor shelf stability [see e.g. U.S.
  • Patent No. 3,236,823 Jennes
  • U.S. Patent No. 5,935,711 Patent No. 5,935,711
  • Patent No. 2 Certain boron alkyl compounds and their use as initiators of polymerization are described in U.S. Patent Nos. 4,515,724, 4,638,092, 4,638,498, 4,676,858 and 4,921,921 (the "Ritter patents") .
  • U.S. Patent Nos. 5,106,928, 5,143,884, 5,286,821, 5,310,835 and 5,376,746 disclose a two-part initiator system for acrylic adhesive compositions, in which the first part includes a reportedly stable organoborane amine complex and the second part includes a destabilizer or activator such as an organic acid or an aldehyde .
  • Japanese Patent Publication No. S48-18928 describes a method for adhering polyolefin or vinyl polymers using an adhesive obtained by adding trialkylboron to a vinyl monomer, with or without vinyl polymer.
  • trialkylboron include triisopropylboron, tri-n-butylboron, tripropylboron and tri-tert- butylboron.
  • U.S. Patent No. 3,275,611 (Mottus) describes a process for polymerizing unsaturated monomers with a catalyst comprising an organoboron compound, a peroxygen compound and an amine complexing agent for the boron compound.
  • U.S. Patent No. 5,539,070 (Zharov) and U.S. Patent Nos. 5,616,796, 5,621,143, 5,681,910, 5,684,102, 5,686,544, 5,718,977, 5,795,657 and the ⁇ 711 patent describe organoborane amine complexes which can be used in systems that initiate the polymerization of acrylic monomers in compositions useful for bonding low surface energy plastics substrates such as polyethylene, polypropylene and polytetrafluoroethylene .
  • International Patent Publication No. WO 99/64528 describes low odor polymerizable compositions comprising monomer blends and organoborane amine complex initiators .
  • International Patent Publication No. WO 01/44311 also describes amine organoborane complex polymerization initiators in bonding compositions for low surface energy substrates.
  • International Patent Publication No. WO 01/32716 (“PCT 716") acknowledges that while complexes of an organoborane and an amine may be useful in many applications, certain problems may arise due to the use of amine complexing agents in such conventional complexes. For example, when the complexes contain a primary amine, adhesives prepared therefrom may be prone to discoloration, such as yellowing; further, when including reactive diluents, such as aziridines described in International Patent Publication No.
  • PCT 716 therefore proposes a complex of an organoborane and a complexing agent of at least one hydroxide or alkoxide, particularly a complex represented by the formula
  • R 1 is an alkyl group having 1 to about 10 carbon atoms
  • R 2 and R 3 may be the same or different and are selected from alkyl groups having 1 to about 10 carbon atoms and phenyl- containing groups
  • the value of w v" is selected so as to provide an effective ratio of oxygen atoms of the alkoxides and/or hydroxides to boron atoms in the complex
  • each R 4 is independently selected from hydrogen or an organic group (e.g. , an alkyl or alkylene group)
  • M ( +) represents a countercation [comprising a monovalent cation, such as a Group IA metal (e.g.
  • the complexing agent i.e. , the hydroxide or alkoxide
  • the complexing agent is used in the form of a salt.
  • the complexing agent is stabilized by a suitable countercation such that the complexing agent is capable of complexing the initiator.
  • M (In+) represents a countercation that stabilizes the complexing agent, not a cation that forms an ionic compound with the organoborane initiator.
  • PCT 716 states that hydroxides and alkoxides provide strong coupling to organometallic initiators, such as organoboranes, with the resulting complexes having excellent oxidative stability.
  • complexing agents of at least one hydroxide, alkoxide, or mixtures thereof are said to be particularly beneficial .
  • Such a complex is stated to be a tightly co-ordinated salt formed by association of a Lewis acid (the initiator) and a Lewis base (the hydroxide or alkoxide) .
  • a Lewis acid the initiator
  • a Lewis base the hydroxide or alkoxide
  • Tetraorganylborate salts of tetraalkyla monium, sodium or lithium are known as photoinitiators in photocurable compositions for imaging materials (see e.g. U.S. Patent Nos. 4,950,581, 6,110,987 and 6,171,700).
  • Tetraorganylborate salts do not however have a boron-hydrogen bond.
  • the present invention which is directed to a polymerizable composition, which includes a free radical polymerizable component, such as one based on (meth)acrylates, an alkylated borohydride or tetraalkyl borane as defined below, an aziridine-containing compound, and a carrier therefor which is unreactive toward the alkylated borohydride or tetraalkyl borane.
  • a free radical polymerizable component such as one based on (meth)acrylates, an alkylated borohydride or tetraalkyl borane as defined below, an aziridine-containing compound, and a carrier therefor which is unreactive toward the alkylated borohydride or tetraalkyl borane.
  • the inventive compositions demonstrate a flash point greater than 140°F (60°C) and desirably greater than 200°F (93.3°C).
  • another aspect of the invention provides an indicator system which controls the rate of cure by the addition of a
  • the terms (meth) acrylate and (meth) acrylic are used synonymously with regard to the monomer and monomer-containing component.
  • the terms (meth) acrylate and (meth) acrylic include acrylate, methacrylate, acrylic, and methacrylic.
  • non-flammable will mean a flash point of greater than about 200°F (94°C) , whereby heating is required for the material to catch fire; and the term “flammable” will mean the material is ignitable with a spark rather than by heating, and having a flash point of about less than 100°F (38°C) .
  • flammable will mean the material is ignitable with a spark rather than by heating, and having a flash point of about less than 100°F (38°C) .
  • compounds which have a flash point between 140°F-200°F (60°C-93°C) are classified as "combustible".
  • the present invention relates to polymerizable (meth) acrylate compositions and adhesive systems based on such (meth) acrylate compositions, which when applied onto a substrate results in the formation of a polymeric adhesive material which strongly adheres to surfaces, particularly low energy surfaces such as polyolefins.
  • the polymerization reaction promoted by the initiator systems also causes bonding of the adhesive to the surfaces being bonded.
  • the speed and extent of the polymerization can be controlled by varying the ratio of the various constituents.
  • the adhesive system of the present invention has shown average bond strengths to low energy surface materials such as polyethylene and polypropylene in excess of about 1,000 psi.
  • the rate of cure may be controlled by the addition of a halogen solution, such as an iodine solution, which also serves as an indicator for when cure begins .
  • the adhesive compositions disclosed herein are useful for bonding a large range of substrates including metals, plastics and glass to similar or different substrates and perform better than most previously available two-part (meth) acrylate based adhesives on many of these substrates, especially low energy surfaces having a surface energy of less than 45 mJ/m 2 .
  • these low energy surfaces include polyolefins, for example, acrylonitrile-butadiene-styrene and polytetrafluoroethylene, or relatively low surface energy substrates such as polycarbonate, ' to similar substrates, to each other, or to different substrates including metals, other plastics and glass.
  • kits comprising the (meth) acrylate compositions for use as adhesive systems, the resultant bonded assembly using the (meth) acrylate based adhesive system of the present invention, and a method of bonding low energy substrates with the (meth) acrylate based adhesive system of the present invention.
  • the ethylenically unsaturated, free radical polymerizable monomers useful in the present invention preferably comprise addition polymerizable, non-gaseous (boiling point above 100°C at normal atmospheric pressure) , ethylenically-unsaturated organic compounds containing at least one, and preferably at least two, terminal ethylenically unsaturated groups, and being capable of forming a high weight average molecular weight polymer by free radical initiated, chain propagating addition polymerization.
  • the (meth) acrylate component may be selected from mono (meth) acrylate monomers comprising formula I:
  • G is hydrogen, halogen, or an alkyl having from 1 to 4 carbon atoms
  • R 1 has from 1 to 16 carbon atoms and is an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, or aryl group, optionally substituted or interrupted with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, amine, amide, sulfur, sulfonate, sulfone or tetrahydrafurfuryl, such as citronellyl
  • (meth)acrylates tetrahydrodicyclopentadienyl (meth) acrylate, triethylene glycol (meth) acrylates, and tetrahydrafurfuryl
  • (meth) acrylates a di- or tri- (meth) acrylate monomers, such as those selected from polyethylene glycol di (meth) acrylates, bisphenol-A di (meth) acrylates, tetrahydrofurane di (meth) acrylates, hexanediol di (meth) acrylates, polythylene glycol di (meth) acrylates, such as triethylene glycol di (meth)acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, di- pent
  • R 2 is hydrogen, halogen, or an alkyl having about 1 to about 4 carbon atoms
  • R 3 is hydrogen, an alkyl having about 1 to about 4 carbon atoms, hydroxyalkyl having about 1 to about 4 carbon atoms or
  • R is hydrogen, hydroxy or
  • r is zero or a positive integer, s is zero or 1, t is an integer from 1 to 20, and p is 2, 3 or 4; G and R 4 are as defined above; and R 5 denotes an organic radical of valency s linked through a carbon atoms or carbon atoms thereof to the indicated t number of oxygen atoms.
  • r, s, and t are each 1
  • G is hydrogen or methyl
  • R 5 is a hydrocarbon residue of an aliphatic polyhydric alcohol having from 2 to 6 carbon atoms, such as a pentaerythrityl group.
  • a specific example of such compounds is pentaerythritoyl tetrakis (dimethylene glycol acrylate) ;
  • R 6 is hydrogen or methyl
  • R 7 is an organic radical of valency p, linked through a carbon atom thereof other than the carbon atom of a carbonyl group. More particularly, when s is zero, R 7 may denote the residue, containing from 1 to 60 carbon atoms, of an alcohol or phenol having p hydroxyl groups.
  • R 7 may thus represent an aromatic, araliphatic, alkaromatic, cycloaliphatic, heterocyclic, or heterocycloaliphatic group, such as an aromatic group containing only one benzene ring, optionally substituted by chlorine, bromine or an alkyl group of from 1 to 9 carbon atoms, or an aromatic group comprising a chain of two to four benzene rings, optionally interrupted by ether oxygen atoms, aliphatic hydrocarbon groups of 1 to 4 carbon atoms, or sulphone groups, each benzene ring being optionally substituted by chloride, bromine or an alkyl group of from 1 to 9 carbon atoms , or a saturated or unsaturated, straight or branched-chain aliphatic group, which may contain ether oxygen linkages and which may be substituted by hydroxyl groups, especially a saturated or monoethylenically unsaturated straight chain aliphatic hydrocarbon group of from 1 to 8 carbon atoms .
  • R 7 may represent the residue, containing from 1 to 60 carbon atoms, of an acid having p carboxyl groups, preferably a saturated or ethylenically unsaturated, straight chain or branched aliphatic hydrocarbon group of from 1 to 20 carbon atoms, which may be substituted by chlorine atoms and which may be interrupted by ether oxygen atoms and/or by carbonyloxy (-COO-) groups, or a saturated or ethylenically unsaturated cycloaliphatic or aliphatic-cycloaliphatic hydrocarbon group of at least 4 carbon atoms, which may be substituted by chlorine atoms, or an aromatic hydrocarbon group of from 6 to 12 carbon atoms which may be substituted by chlorine or bromine atoms .
  • an acid having p carboxyl groups preferably a saturated or ethylenically unsaturated, straight chain or branched aliphatic hydrocarbon group of from 1 to 20 carbon atoms, which may be substituted by chlorine atoms and
  • R 7 represents a saturated or ethylenically unsaturated straight chain or branched aliphatic hydrocarbon group of from 1 to 8 carbon atoms, optionally substituted by a hydroxyl group, or a saturated or ethylenically unsaturated straight chain or branched aliphatic hydrocarbon group of from 4 to 50 carbon atoms and interrupted in the chain by carbonyloxy groups, or a saturated or ethylenically unsaturated monocyclic or bicyclic cycloaliphatic hydrocarbon group of 6 to 8 carbon atoms, or an ethylenically unsaturated cycloaliphatic-aliphatic hydrocarbon group of from 10 to 51 carbon atoms, or a ononuclear aromatic hydrocarbon group of from 6 to 8 carbon atoms.
  • suitable compounds of the preceding formula are epoxy acrylates such as 1, 4-bis (2-hydroxy-3 (acryloyloxy)propoxy) butane, poly(2-hydroxy-3- (acryloyloxy)propyl) ethers of bis (4-hydroxyphenyl)methane (bisphenol F) , 2, 2-bis (4-hydroxyphenyl) ropane (bisphenol A) and phenol-formaldehyde novolaks, bis (2-hydroxy-3-acryloyloxypropyl) adipate and the methacryloyloxy analogues of these compounds; urethane acrylates and ureido acrylates comprising formula V: o o
  • R 8 denotes a divalent aliphatic, cycloaliphatic, aromatic, or araliphatic group, bound through a carbon atom or carbon atoms thereof indicated at the -0- atom and -X- atom or group
  • X denotes -0-, -NH-, or -N(alkyl)-, in which the alkyl radical has from 1 to 8 carbon atoms
  • z is an integer of at least 2 and at most 6
  • R 9 denotes a z-valent cycloaliphatic, aromatic, or araliphatic group bound through a carbon atom or carbon atoms thereof to the indicate NH groups .
  • R 8 denotes a divalent aliphatic group of 2 to 6 carbon atoms and R 9 denotes one of the following: a divalent aliphatic group of 2 to 10 carbon atoms, such as a group of formula: -(CH 2 ) 6 -, CH 2 C(CH 3 ) 2 CH 2 CH(CH 3 ) (CH 2 )-, or -CH 2 CH (CH 3 ) CH 2 C (CH 3 ) 2 CH 2 ) 2 - ; or a phenylene group, optionally substituted by a methyl group or a chlorine atom; a naphthylene group; a group of formula: -C6H4C6H 4 -, -C6H4CH2C 6 H 4 -, or -C 6 H 4 C(CH 3 )2C6H4-; or a mononuclear alkylcycloalkylene or alkyleyeloalkylalkylene group, such as a methylcyclohe
  • alkylated borohydrides and tetraalkyl boranes used as initiators of polymerization comprise formula VI:
  • R 1 is Ci-Cio alkyl, straight chain or branched
  • R 2 and R 3 which may be the same or different, are H, D, Ci- Cio alkyl or C 3 -C ⁇ o cycloalkyl, phenyl, or phenyl-substituted Ci- Cio alkyl or C 3 -C ⁇ o cycloalkyl, provided that any two of R 1 -R 3 may optionally be part of a carbocyclic ring, R 4 is H, D or Ci-Cio alkyl, and
  • M + is a metal ion or a quaternary ammonium ion comprising formula VII.
  • the metal ion may be an alkali metal ion such as lithium, sodium, potassium, or cesium, particularly lithium, sodium or potassium, although metallic elements in the second row of the Periodic Table such as barium, magnesium or calcium may be useable, as may transition metals such as copper, iron or cobalt.
  • the quaternary ammonium ion comprise formula VII below:
  • R 5 -R 8 which may be the same or different, are Ci-Cio alkyl, C 2 -C ⁇ o alkenyl, C 3 -C ⁇ o cycloalkyl, aryl, Ci-Cio alkylaryl, aryl Ci-Cio alkyl or aryl Ci-Cio cycloalkyl, provided that any two of R 5 -R 8 may be part of an optionally unsaturated carbocyclic ring.
  • Aryl is suitably optionally substituted phenyl, wherein the phenyl ring may be substituted, for example with Ci-Cio alkyl, particularly Ci-C ⁇ alkyl, or halo, particularly Cl, Br or F.
  • Examples of a quaternary ammonium cation include a tetra Ci-Cio alkylammonium cation, particularly a tetra C 1 -C 5 alkylammonium cation, for example tetramethylammonium, tetraethylammonium or tetra-n-butylammonium, or a tri C 1 -C1 0 alkylarylammonium cation wherein aryl is phenyl, substituted phenyl (with phenyl being substituted as above) , or phenyl-substituted C1-C 10 alkyl or C 3 -C ⁇ o cycloalkyl .
  • Tetramethylammonium cation i.e. where R 5 - R 8 in formula VII are each Ci alkyl
  • the invention relates to the use of initiators comprising formula VIII below:
  • R 1 -R 8 are as defined above.
  • An alkyl group may suitably have 1-6 carbon atoms, for instance 2-4 carbon atoms, and may be straight chain or branched, provided a suitable number of carbon atoms are available for branching.
  • a carbocyclic ring may be bridged by the boron atom.
  • at least two, and desirably three, and in some instances four, of R 1 -R 4 are C 1 -C 10 alkyl.
  • the alkylated borohydride is of formula VI;
  • M is an alkali metal ion such as lithium, sodium, potassium, or cesium, particularly lithium, sodium or potassium, although metallic elements in the second row of the Periodic Table such as barium, magnesium or calcium may be useable, as may transition metals such as copper, iron or cobalt;
  • R 1 -R 3 may suitably be the same or different alkyl group and each may suitably be a C ⁇ -C 6 alkyl group, particularly a C 2 -C 4 alkyl group. Desirably the three alkyl groups R x -R 3 are the same group.
  • a cycloalkyl group may suitably be C5-C6 group.
  • Examples of suitable metal salts in which R 1 -R 3 are the same alkyl group include lithium triethylborohydride, sodium triethylborohydride, potassium triethylborohydride, lithium tri- sec-butylborohydride, sodium tri-sec-butylborohydride, potassium tri-sec-butylborohydride, lithium trisiamylborohydride, potassium trisiamylborohydride and lithium triethylborodeuteride.
  • a particularly suitable example is lithium tri-sec- butylborohydride.
  • R 2 is an alkyl group and R 1 and R 3 are H is lithium thexylborohydride .
  • An example of a compound in which R 1 and R 3 form part of a cyclic ring is lithium 9-borabicyclo [3.3.1] -nonane ("9BBN") hydride.
  • 9BBN 9-borabicyclo [3.3.1] -nonane
  • Desirably at least one of R 2 and R 3 is a C 1 -C10 alkyl group or phenyl, provided that not more than one of R 2 and R 3 is phenyl.
  • a phenyl group may be substituted in the ring by one or more substituents, which do not affect the activity of the compound of formulae VI or VII as a polymerization initiator.
  • substituents include C 1 -C10 alkyl, for example C ⁇ -C 6 alkyl, particularly methyl .
  • the above-identified compounds are commercially available from various suppliers such as Aldrich Chemical Co., e.g. , under tradenames such as Super-hydride, Selectride, and Super-deuteride, or Callery Chemicals of Evans City, PA, under trade names such as CalSelect.
  • the commercially available compounds are in flammable solvents, which however are not reactive toward the alkylated borohydrides and tetraalkyl boranes .
  • THF and diethyl ether - both combustible and flammable solvents are the ones chosen.
  • Suitable compounds include the metal borohydrides analogous to the boron compounds as described in the Ritter patents such as diisopinocamphenylborane, dicyclohexylborane, and diisoamylborane .
  • the quantity of alkylated borohydride or tetraalkyl borane may suitably be such as to provide 0.01% to 5% by weight, particularly 0.01% to 2% by weight, such as 0.1 to 1% by weight, of boron in the total composition.
  • the alkylated borohydride or tetraalkyl borane is suitably used in a solution of a carrier whose flash point is above 140°F, desirably above 200°F, in a concentration up to about 1.5M, such as about IM, although the person skilled in the art will select a suitable concentration depending upon the carrier used.
  • the alkylated borohydrides or tetraalkyl boranes are placed in a carrier, which may be in the liquid or solid state, provided that when in the solid state, the carrier is capable of being solubilized by some or all of the remaining components in the inventive composition and provided that the flash point of the carrier is above 140 2 F, desirably above 200 2 F.
  • Waxes useful as some or all of the carrier in the present invention include petroleum waxes, vegetable waxes, insect waxes, animal waxes and synthetic waxes. While waxes are generally solid at ambient temperature conditions, they find utility as some or all of the carrier, to the extent they are soluble in or more of the constituents used to make the compositions, or in the compositions themselves.
  • Petroleum wax includes a range of relatively high- molecular-weight hydrocarbons (approximately C ⁇ 6 to C 50 ) , is solid at room temperature, and is derived from higher boiling petroleum fractions.
  • Three basic categories of petroleum-derived or shale- oil-derived waxes include paraffin (crystalline) wax, microcrystalline wax and petrolatum wax.
  • Paraffin waxes are produced from the lighter lube oil distillates, generally by chilling the oil and filtering the crystallized wax. Paraffin waxes have a distinctive crystalline structure and a melting point range generally between 48°C (118°F) and 71°C (160°F) . Paraffin wax is macrocrystalline and is composed of about 40-90% normal alkanes with a remainder of Ci8-C 35 isoalkanes and cycloalkanes .
  • Paraffin wax is a petroleum- derived wax usually consisting of high-molecular-weight normal paraffins; distinct from other natural waxes, such as beeswax and carnauba wax (palm tree) , which are composed of high-molecular- weight esters, in combination with high-molecular-weight acids, alcohols, and hydrocarbons.
  • Refined paraffin waxes are low oil, or low liquid paraffin, content waxes, generally with an oil content of 1.0 weight percent or less, under conditions prescribed by test method ASTM D 721. Fully refined paraffin waxes generally have even lower oil content of about 0.5 weight percent or less under the same conditions.
  • Microcrystalline waxes are produced from heavier lube distillates and residua usually by a combination of solvent dilution and chilling. They differ from paraffin waxes in having poorly defined crystalline structure, darker color, higher viscosity, and higher melting points which typically range from 63°C (145°F) to 93°C (200°F) . Microcrystalline waxes contain more branched and cyclic compounds than paraffin waxes and also vary more widely than paraffin waxes in their physical characteristics. Microcrystalline waxes can be somewhat ductile, but are also often brittle and crumble easily. [0052] Petrolatum waxes (CAS Registry No. 8009-0-8) are derived from heavy residual lube stock by propane dilution and filtering or centrifuging. They are microcrystalline in character, semisolid at room temperature and consist predominantly of saturated crystalline and liquid hydrocarbons having carbon numbers greater than C25.
  • Useful insect and animal waxes include, but are not limited to, beeswax, spermaceti wax, Chinese wax, wool wax, and shellac wax.
  • the major components of beeswax (CAS Registry No. 8012-89-3) are esters of C 30 and C 32 alcohols with Ci6 acids, free C 2 5 to C 3 ⁇ carboxylic acids, and C25 to C 3 ⁇ hydrocarbons.
  • Beeswax typically has a melting point of about 60 to 70°C.
  • Spermaceti wax (CAS Registry Nos. 8002-23-1 and 68910-54-3) is derived from the sperm whale and has a melting point of about 42 to 50°C.
  • Chinese wax (CAS Registry No.
  • Useful vegetable waxes include, but are not limited to, carnauba wax, candelilla wax, Japan wax, ouricury wax, rice-bran wax, jojoba wax, castor wax, bayberry wax, and soy bean wax.
  • Carnauba wax (CAS Registry No. 8015-86-9) is produced from fronds of a palm tree. The major components of carnauba wax are aliphatic and aromatic esters of long-chain alcohols and acids, with smaller amounts of free fatty acids and alcohols, and resins. Carnauba wax is very hard with a melting point of about 83 to 86°C.
  • Candelilla wax (CAS Registry No.
  • candelilla wax is produced from shrubby spurges (Euphorbia, antisyphilitica) native to southwest Texas and Mexico.
  • the major components of candelilla wax are hydrocarbons, esters of long-chain alcohols and acids, long-chain alcohols, sterols, and neutral resins, and long-chain acids.
  • candelilla wax has a melting point of about 67 to 70°C.
  • Japan wax (CAS Registry No. 8001-39-6) is derived from the berries of a small tree native to Japan and China cultivated for its wax. Japan wax is composed of triglycerides, primarily tripalmitin. Japan wax typically has a melting point of about 48 to 53°C.
  • Ouricury wax (CAS Registry No.
  • 68917-70-4) is a brown wax obtained from the fronds of a palm tree which grows in Brazil and has a melting point of about 79 to 84°C.
  • Rice-bran wax (CAS Registry No. 8016-60-2) is extracted from crude rice-bran oil and has a melting point of about 75 to 80°C. The wax is primarily composed of e ⁇ acid, behenic acid, and C 2 -C 3 6 alcohols.
  • Jojoba wax (CAS Registry No. 61789-91-1) is obtained from the seeds of the jojoba plant.
  • Castor wax (CAS Registry No. 8001-78-3) is catalytically hydrogenated castor bean oil.
  • Bayberry wax (CAS Registry No.
  • the wax is made up primarily of lauric, myristic, and palmitic acid esters.
  • the wax has a melting point of about 45 to 49°C.
  • Useful mineral waxes include, but are not limited to, montan wax, peat wax, ozokerite wax and ceresin wax.
  • Montan wax (CAS Registry Nos. 8002-53-7) is derived by solvent extraction of lignite.
  • the wax components of montan is a mixture of long chain (C 24 -C 3 o) esters, long-chain acids, and long chain alcohols, ketones, and hydrocarbons .
  • Crude montan wax from Germany typically has a melting point of about 76 to 86°C.
  • Peat waxes are much like montan waxes and are obtained from peat and has a melting point of about 73 to 76°C.
  • Ozokerite wax (CAS Registry No.
  • Ceresin wax (CAS Registry No. 8001-75-0) originally was a refined and bleached ozokerite wax.
  • Synthetic waxes include, but are not limited to, polyethylene waxes a-olefin waxes, carbowaxes and halowaxes .
  • Polyethylene waxes (CAS Registry No. 8002-72-4) are obtained polymerization of polyethylenes or by Fischer-Tropsch synthesis. The waxes have melting points ranging from about 45-106°C. These waxes may also be chemically modified to vary properties, such as acid number.
  • Polymerized a-olefins can be produced to have waxlike properties and are sold as synthetic waxes. The polymerization process yields highly branched materials, with broad molecular weight distributions.
  • Carbowaxes (CAS Registry Nos.
  • Halowaxes (CAS Registry Nos. 1321-65-9, 1335-87-1, 1335-88-2, 12616-35-2, 12616-36-3, 25586-43-0, 57817- 66-7 and 58718-67-5) are chlorinated naphthalenes.
  • particularly desirable carriers include generally those selected from certain ethers, epoxies, and hydrocarbons, and more specifically poly(tetrahydofurane) , 2- haloalkyl phenyl ethers, such as 2-bromoethyl phenyl ether [flash point, 150°F (65.3°C)], 2-chloro ethyl phenyl ethyl, glycidoxy alkyltrialkoxyl silanes, such as 3- glycidoxypropyltrimethoxysilane, certain glycidyl ethers, such as glycidyl heptyl ether, glycidyl undecyl ether, glycidyl ether, glycidyl heptyl ether, propanediol diglycidyl ether, butene diol glycidyl ether, cyclohexane dimethanol diglycidyl
  • triglyme flash point, 175°F
  • tetraglyme flash point, 230°F
  • the use of tetraglyme as a carrier for the alkylated borohydrides or tetraaklyl boranes has proven particularly desirably from the standpoint of processing ease and flammability/combustibility reduction.
  • Carriers useful in the present invention solubilize the alkylated borohydride or tetraaklyl borane at the amount intended to be used, is unreactive toward the alkylated borohydrides or tetraaklyl boranes and has a flash point greater than 140°F, desirably greater than 200°F.
  • the quantity of carrier may suitably be in the range from about 2% to about 50% by weight, for example 2% to 40% by weight, particularly 2% to 30% by weight, of the total composition.
  • the alkylated borohydrides or tetraaklyl boranes used in the present invention are not contacted with amines, which have been used in the past to form covalent complexes with organoboranes .
  • the amine can cause yellowing of a cured composition after aging.
  • a reduction or elimination of yellowing is a particular advantage for adhesives that are to be used in locations where appearance is important, e.g. , in automobile manufacture.
  • Primary and/or secondary amines may also give rise to odor problems.
  • Compositions containing the metal alkyl borohydrides have good shelf stability.
  • alkylated borohydrides or tetraaklyl boranes and the carrier do not react together or start to cross-link, causing a change in viscosity, before polymerization of the total polymerizable composition is initiated.
  • the alkylated borohydrides or tetraaklyl boranes and carrier are suitable for packaging together in Part B -- the initiator component — of a two-part composition.
  • an indication system for use in moderating the cure speed of the adhesive system as well as determining when the cure is complete.
  • the present invention provides a free radical polymerizable composition, such as one having a (meth) acrylate component, and adhesives based on such free radical polymerizable compositions.
  • the compositions include a (meth) acrylate component, an alkylated borohydride or tetraaklyl borane, a carrier for the alkylated borohydride or tetraaklyl borane, respectively, in which the alkylated borohydride or tetraaklyl borane, respectively, is soluble, which is unreactive toward the alkylated borohydride or tetraaklyl borane, respectively, and which has a flash point above 140°F, desirably above 200°F, and an indicator system that may control the rate, and indicate the beginning, of cure.
  • the indicator system is substantially dissolved in the composition, particularly the (meth) acrylate part thereof (Part A), to provide a first color to the (meth) acrylate component, where after mixing with the initiator part (Part B) for a predetermined amount of time, the composition undergoes a color change as an indication that cure is beginning to occur.
  • Part A the composition, particularly the (meth) acrylate part thereof (Part A), to provide a first color to the (meth) acrylate component, where after mixing with the initiator part (Part B) for a predetermined amount of time, the composition undergoes a color change as an indication that cure is beginning to occur.
  • the inclusion in the inventive polymerizable composition of the indicator system provides the ability to control the rate of oxygen absorption which translates into rate of polymerization, as well as the ability to monitor when polymerization is complete, as the indictor system assumes one color initially in the uncured composition and a second color once polymerization is complete.
  • the polymerizable composition may suitably be a two- part composition in which the free-radically polymerizable monomer component is provided in one part and an alkylated borohydride or tetraaklyl borane is provided in the other part .
  • the alkylated borohydride or tetraaklyl borane may be provided as a primer, where the alkylated borohydride or tetraaklyl borane is applied to a substrate separately from the adhesive composition.
  • the invention provides a two- part polymerizable adhesive composition, which includes: part A -- (meth) acrylate component, optionally with an acid; and part B -- an effective amount of a polymerization initiator comprising an alkylated borohydride or tetraaklyl borane as defined herein, and a carrier for which inert to the alkylated borohydride or tetraaklyl borane as defined herein, where each part has a flash point greater than 140°F, preferably greater than 200°F.
  • Either part A, part B, or both may further include a toughener, filler and/or thickener.
  • the compound that is reactive with the alkylated borohydride or tetraaklyl borane as defined herein is present in part A of a two-part polymerizable acrylic adhesive composition as described above.
  • part B of the two-part adhesive composition is packaged in a moisture-free and moisture-impermeable applicator or other container.
  • compositions disclosed herein are useful for bonding a large range of substrates including metals, plastics and glass to similar or different substrates and indeed they give better performance than the previously discussed adhesives on many of these substrates, especially plastic of the invention are particularly useful for bonding low surface energy substrates, such as those having a surface energy of less than 45 mJ/m 2 , more particularly polyolefins including polyethylene and polypropylene, acrylonitrile-butadiene-styrene and polytetrafluoroethylene, or relatively low surface energy substrates such as polycarbonate, to similar substrates, to each other, or to different substrates including metals, other plastics and glass .
  • low surface energy substrates such as those having a surface energy of less than 45 mJ/m 2
  • polyolefins including polyethylene and polypropylene, acrylonitrile-butadiene-styrene and polytetrafluoroethylene
  • relatively low surface energy substrates such as polycarbonate
  • the invention relates to an adhesive composition as defined above for bonding a low surface energy substrate to a similar or different substrate.
  • an adhesive composition as defined above for bonding a low surface energy substrate to a similar or different substrate.
  • Ri and R 2 are straight chain C1-C4 alkyl.
  • the invention provides a method for bonding a substrate to a similar or different substrate, where the method comprises applying an adhesive composition as defined above to at least one of the substrates, bringing the substrates together and allowing the composition to cure.
  • the invention provides a method as defined above for bonding a low surface energy substrate such as a polyolefin substrate to a similar or different substrate.
  • the invention provides a method for bonding a substrate, particularly a low surface energy substrate, to a similar or different substrate, where the method includes mixing parts A and B of a two part adhesive composition prior to use in order to initiate polymerization, applying the mixed composition to at least one of the substrates, bringing the substrates together and allowing the composition to cure by completion of the polymerization initiated on mixing of the parts A and B.
  • the acid when added may be a weak acid, such as having a pKa no lower than about 0.5 with the desirable limit being about 0.9.
  • the upper limit normally is about 13, or less, such as about 11.5.
  • Carboxylic acids, which have a pKa of up to about 8, such as about 6 or about 7, are particularly useful.
  • An effective amount of the acid is about 0.1 to about 25%, preferably from about 0.1 to about 20%, and more preferably from about 0.5 to about 10% based on a total weight of the (meth) acrylate composition.
  • Suitable acids may be monobasic or polybasic. Examples of suitable acids are formic acid, acetic acid, propionic acid, maleic acid, malic acid, fumaric acid, acrylic acid and copolymers thereof, methacrylic acid and copolymers thereof, pyruvic acid, itaconic acid, nadic acid, benzoic acid, phthalic acids, cinnamic acid, trichloroacetic acid, and saccharin. [0078] Lewis acids may also be used. The acid may also be present as a latent acid, particularly a masked carboxylic acid compound hydrolyzable on contact with moisture, such as an acid anhydride, such as described in European Patent No. EP 356 875 and U.S. Patent No. 5,268,436, the contents of which are incorporated herein by reference .
  • alkylated borohydrides or tetraaklyl boranes are effective initiators without an acid
  • an acid which term includes a latent acid
  • the presence of an acid may be required.
  • the reaction takes place after mixing of the two parts, one containing the alkylated borohydride or tetraaklyl borane and the other containing the acid or other compound reactive therewith.
  • the aziridine-containing compound has at least one aziridine ring or group:
  • the carbon atom(s) may be optionally substituted with short chain alkyl groups having from one to ten carbon atoms, preferably methyl, ethyl or propyl such that methyl, ethyl or propyl aziridine moieties are formed.
  • Polyfunctional aziridines such as trimethylolpropane tris(3-(2- methylaziridino) propionate, are particularly useful.
  • the aziridine-containing compound is preferably soluble in the (meth) acrylate, such that the parts of a multi-part adhesive system can be readily mixed.
  • the aziridine-containing compound is a liquid at or near room temperature, i.e., within about 10°C of room temperature.
  • tougheners may be added. Suitable tougheners include elastomeric materials such as polybutadiene rubbers, polyisoprene, available under the trade name KRATON® from Shell Chemical Corp., Houston, Texas, acrylonitrile-butadiene-styrene ("AB ' S"), available under the trade name HYCAR®, or as core-shell polymers under the trade name BLENDEX®, or polystyrenes. [0071] For bonding polyolefins, it is desirable to use a core-shell polymer. The use of core-shell polymers in (meth) acrylate compositions is described, for example, in U.S. Patent Nos.
  • Core shell polymers are suitably graft copolymer resins, e.g., ABS graft copolymers, or others described in the ⁇ 546 and ⁇ 201 patents, in the form of particles that comprise rubber or rubberlike cores or networks that are surrounded by relatively hard shells.
  • core-shell polymers can also impart enhanced spreading and flow properties to the composition. These enhanced properties include a reduced tendency for the composition to leave an undesirable "string" upon dispensing from a syringe-type applicator, or sap or slump after having been applied to a vertical surface.
  • the quantity of toughener when used, may suitably be in the range from about 1% to about 40%, preferably about 5% to about 25%, based on a total weight of the composition.
  • Polymeric thickeners' may be present in the compositions in an amount up to about 50%, and may be polymers or prepolymers of low or high molecular weight.
  • Suitable polymeric thickeners are a commercially available methacrylate polymer sold under the trademark ELVACITE®, available from E.I. DuPont de Nemours, Wilmington, Delaware, as well as styrene-methyl methacrylate copolymers, polybisphenol A maleate, or propoxylated bisphenol-A- fumarate polyester sold under the trademark ATLAC®.
  • Inert fillers such as finely divided silica, fumed silica (treated or untreated), mont orillonite, clay, bentonite and the like, may also be added.
  • micronized silica can result in a paste-like thixotropic composition.
  • Polymeric thickeners or other thickeners such as silica may suitably be present as a thickener in both Parts A and B of a two-part composition.
  • Inert fillers such as wood flour, cornstarch, glass fibers, cotton lintners, mica, alumina, si like may be used to alter physical properties, such as modifying viscosity, improving impact resistance, and the like.
  • Such fillers may be incorporated in the inventive compositions in an amount within the range of from about 0.5% to about 20%, for example about 1% to about 10%, by weight of the composition.
  • polyolefin and other low surface energy materials can be used as fillers in the composition.
  • Polyolefin powders such as polyethylene powder are relatively inexpensive. In a composition which readily bonds to a polyolefin, the filler becomes securely adhered into the cured composition.
  • Polyethylene or polypropylene powders can be used with particle sizes in the range from about 0.01 microns to about 1 micron, particularly about 0.02 microns to about 0.3 microns, allowing for a good control of the gap between substrates, i.e., the depth of adhesive.
  • Particularly suitable polyethylene powders are commercially available under the trade name MICROTHENE® available from Equistar Chemicals LP, Houston, Texas.
  • Polyethylene flock and polyolefin chopped fibers can also be used as fillers.
  • the amount of polyolefin filler that may be used in the present invention is about 0.5% to about 20%, preferably about 1% to about 10% based on a total weight of the composition.
  • Parts A and B may be provided in a weight ratio in the range from about 1:10 to 10:1, preferably, about 1:5 to 1:1, more preferably from about 1:2 to 1:1, and even more preferably, from about 8:10 to about 10:8.
  • the two part adhesive system is provided in about a 1 : 1 ratio of Parts A and B for simple consumer use.
  • the composition may optionally include oxidizing agents, reducing agents, thickeners, non-reactive dyes and pigments, reaction indicators (as noted), fire retarders, stabilizers, such as quinones and hydroquinones , thixotropes, plasticizers and antioxidants.
  • oxidizing agents such as oxidizing agents, reducing agents, thickeners, non-reactive dyes and pigments, reaction indicators (as noted), fire retarders, stabilizers, such as quinones and hydroquinones , thixotropes, plasticizers and antioxidants.
  • a two part composition in accordance with the invention was prepared as follows:
  • Part A was prepared using the following components in the noted weight percentages: tetrahydrofurfuryl (meth) crylate. 45%, 2-ethyl hexyl (meth) acrylate, 15%, ATLAC® 22%, (meth) acryloyoxyethyl maleate, 12.5%, fumed silica (AEROSIL 200), 3.5%, and glass beads (125-150 urn), 2%.
  • Part B was prepared by lithium tri-sec-butyl borohydride (IM in THF) in an amount of 40 parts by weight adding at room temperature to trimethylol propane tri-3,2- methylaziridine propionate in an amount of 60 parts by weight.
  • IM in THF lithium tri-sec-butyl borohydride
  • Part A was mixed into Part B in a 10:1 ratio and dispensed into aluminum dishes. Polymerization was observed to occur immediately, with full cure confirmed after 3 days.
  • Part B were manually transferred from their mixing vessel, to a
  • the shear strength of the bonded assemblies was determined on an Instron, with the peak strength (in psi) and failure modes observed and recorded.
  • the bonded assemblies made from plastic substrates were tested at a shear rate of 0.5"/minute and those made from metals at a shear rate of 0.05"/minute.
  • PP polypropylene
  • LDPE low density polypropylene
  • HDPE high density polypropylene
  • PVC polyvinyl chloride
  • ABS acrylo-butadiene-styrene
  • PC polycarbonate
  • Part A from above was used, except the following weight percentages of each component were: THF (meth) acrylate, 48%, 2-ethylhexyl (meth) acrylate, 16.5%, ATLAC®, 22%, (meth)acryloyloxyethyl maleate, 8%, silica, 3.5% and glass beads (125-150 urn), 2%.
  • the individual components of Part B each have flash points greater than 140°F, and all but tetrahydrafurfuryl (meth) acrylate (195°F) and 2-ethyl hexyl (meth) acrylate (198°F) have a flash point greater than 200°F.

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  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des compositions polymérisables à base de (méth)acrylate et des systèmes adhésifs préparés à base de ces compositions, qui comportent un composé contenant aziridine dans un matériau support avec lequel ledit composé ne réagit pas. La composition selon l'invention présente un point d'éclair supérieur à 140 °F, de préférence supérieur à 200 °F, pour chacune des parties du système adhésif. Pour obtenir les propriétés physiques des compositions et des systèmes adhésifs selon l'invention, il est souhaitable que le matériau support ait de tels points d'éclair; toutefois, pour autant que, dans leur ensemble, ces compositions et systèmes adhésifs aient lesdits points d'éclair, il n'est pas nécessaire que le matériau support les ait également. Les compositions et les systèmes adhésifs selon l'invention comportent également un ensemble conçu pour réguler la vitesse de durcissement et indiquer l'étendue du durcissement. Ces compositions et systèmes adhésifs conviennent particulièrement pour des applications de collage impliquant au moins une surface de collage à faible énergie, par exemple des surfaces polyoléfiniques, en polyéthylène et en polypropylène.
PCT/US2002/033839 2001-10-23 2002-10-23 Systemes de fixation par collage ininflammables et incombustibles adherant a des surfaces a faible energie WO2003035703A1 (fr)

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IE2001/0980 2001-10-23
IE2001/0937A IE83382B1 (en) 2001-10-23 Polymerisation initiators, polymerisable compositions, and uses thereof
IE20010980A IE83859B1 (en) 2001-10-23 Polymerisation initiators, polymerisable compositions, and uses thereof for bonding low surface energy substrates
IE2001/0937 2001-10-23
IE20020286A IE20020286A1 (en) 2001-10-23 2002-04-19 Developments in polymerisation initiators, polymerisable compositions, and uses thereof for bonding low surface energy substrates
IE2002/0286 2002-04-19
IE2002/0293 2002-04-23
IE20020293A IE20020293A1 (en) 2002-04-23 2002-04-23 Initiator systems, polymerisable compositions, and uses thereof for bonding low surface energy substrates
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WO2005044867A1 (fr) 2003-11-11 2005-05-19 Huntsman Advanced Materials (Switzerland) Gmbh Systemes amorceurs pour compositions polymerisables
US20060122319A1 (en) * 2004-12-03 2006-06-08 Loctite (R&D) Limited Adhesive bonding systems having adherence to low energy surfaces
US7408012B1 (en) 2005-04-18 2008-08-05 Loctite (R&D) Limited Adhesive bonding systems having adherence to low energy surfaces
US7534843B2 (en) 2003-12-22 2009-05-19 Dow Global Technoloigies, Inc. Accelerated organoborane amine complex initiated polymerizable compositions
WO2012160452A1 (fr) 2011-05-26 2012-11-29 Henkel Ireland Limited Compositions polymérisables à deux parties
WO2020126442A1 (fr) 2018-12-21 2020-06-25 Henkel IP & Holding GmbH Compositions de (méth)acrylate photodurcissable en une partie

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US6210863B1 (en) * 1995-11-24 2001-04-03 Ciba Specialty Chemicals Corporation Borate coinitiators for photopolymerization
WO2001032716A1 (fr) * 1999-11-04 2001-05-10 3M Innovative Properties Company Complexes d'amorceur/hydroxyde et d'amorceur/alkoxyde, systemes comprenant ces complexes et compositions polymerisees les contenant
US6248815B1 (en) * 1998-06-04 2001-06-19 H. B. Fuller Licensing & Financing, Inc. Dry bond film laminate employing acrylic emulsion adhesives with improved crosslinker

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US5055372A (en) * 1990-04-23 1991-10-08 The Mead Corporation Photohardenable composition containing borate salts and ketone initiators
US6210863B1 (en) * 1995-11-24 2001-04-03 Ciba Specialty Chemicals Corporation Borate coinitiators for photopolymerization
US5935711A (en) * 1996-10-23 1999-08-10 3M Innovative Properties Company Organoborane amine complex initiator systems and polymerizable compositions made therewith
US6248815B1 (en) * 1998-06-04 2001-06-19 H. B. Fuller Licensing & Financing, Inc. Dry bond film laminate employing acrylic emulsion adhesives with improved crosslinker
WO2001032716A1 (fr) * 1999-11-04 2001-05-10 3M Innovative Properties Company Complexes d'amorceur/hydroxyde et d'amorceur/alkoxyde, systemes comprenant ces complexes et compositions polymerisees les contenant

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005044867A1 (fr) 2003-11-11 2005-05-19 Huntsman Advanced Materials (Switzerland) Gmbh Systemes amorceurs pour compositions polymerisables
US7534843B2 (en) 2003-12-22 2009-05-19 Dow Global Technoloigies, Inc. Accelerated organoborane amine complex initiated polymerizable compositions
US20060122319A1 (en) * 2004-12-03 2006-06-08 Loctite (R&D) Limited Adhesive bonding systems having adherence to low energy surfaces
US8202932B2 (en) 2004-12-03 2012-06-19 Loctite (R&D) Limited Adhesive bonding systems having adherence to low energy surfaces
US7408012B1 (en) 2005-04-18 2008-08-05 Loctite (R&D) Limited Adhesive bonding systems having adherence to low energy surfaces
WO2012160452A1 (fr) 2011-05-26 2012-11-29 Henkel Ireland Limited Compositions polymérisables à deux parties
WO2020126442A1 (fr) 2018-12-21 2020-06-25 Henkel IP & Holding GmbH Compositions de (méth)acrylate photodurcissable en une partie

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