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WO2018181256A1 - (co)polymère à base de benzotriazole, matériau de revêtement absorbant les ultraviolets en contenant, et film revêtu dudit matériau de revêtement - Google Patents

(co)polymère à base de benzotriazole, matériau de revêtement absorbant les ultraviolets en contenant, et film revêtu dudit matériau de revêtement Download PDF

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Publication number
WO2018181256A1
WO2018181256A1 PCT/JP2018/012309 JP2018012309W WO2018181256A1 WO 2018181256 A1 WO2018181256 A1 WO 2018181256A1 JP 2018012309 W JP2018012309 W JP 2018012309W WO 2018181256 A1 WO2018181256 A1 WO 2018181256A1
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group
benzotriazole
carbon atoms
alkyl
ultraviolet
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PCT/JP2018/012309
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English (en)
Japanese (ja)
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孝仁 〆野
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新中村化学工業株式会社
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Priority to KR1020197032009A priority Critical patent/KR102320539B1/ko
Priority to CN201880022908.9A priority patent/CN110475792B/zh
Publication of WO2018181256A1 publication Critical patent/WO2018181256A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints

Definitions

  • the present invention relates to a benzotriazole-based (co) polymer having ultraviolet absorption performance and absorbing ultraviolet rays in a wide wavelength range, a paint containing the same, and a film coated with the paint.
  • UV-absorbing (co) polymers Conventionally, absorption and blocking of ultraviolet rays, prevention of elution and bleeding out of ultraviolet absorbing components from coating films, prevention of crystallization of ultraviolet absorbing components in coating films, improvement of weather resistance of coating films, other resins and compounding materials For the purpose of improving compatibility with UV, UV-absorbing (co) polymers are used.
  • Benzotriazole obtained by copolymerizing a monomer composition containing one or more alkanolphenol type benzotriazole-based UV-absorbing monomers having UV-absorbing property in a relatively short region centered around 300 nm to 360 nm Copolymers are mainly used (for example, Patent Documents 1 to 3).
  • a single- or multiple-type sesamol-type benzotriazole-based UV-absorbing monomer is considered to have absorption in the vicinity of 400 nm in a relatively long wavelength region, which was insufficient with an alkanolphenol-type benzotriazole-based copolymer.
  • a benzotriazole copolymer obtained by copolymerizing a monomer composition is used (for example, Patent Document 4).
  • an optical film such as a polarizing plate protective film is required to have high transparency, and an ultraviolet absorber is generally added to prevent deterioration due to ultraviolet rays.
  • an ultraviolet absorber is added to the antireflection film.
  • various organic materials such as fluorescent materials and phosphorescent materials are used for light emitting elements of organic EL displays. In order to prevent deterioration of these organic materials due to ultraviolet rays, an ultraviolet absorber is added to the surface film of the display. .
  • UV rays are also known to adversely affect the cornea and lens of the human eye, and exposure to sunlight in places with a large amount of UV rays outdoors can easily cause keratitis.
  • Cataracts may be caused by the accumulation of ultraviolet rays.
  • ultraviolet absorbers that have been used so far often have a low absorption in the long wavelength region of 350 to 400 nm, particularly 380 to 400 nm, and an insufficient ultraviolet blocking function.
  • Patent Document 4 shows that by modifying sesamol to a benzotriazole derivative, it is possible to efficiently absorb light in the long wavelength region, but the absorption in the short wavelength region of visible light of 400 to 420 nm is strong, and this compound is When added to an optical film or a spectacle lens, it is colored yellow, so that it is difficult to use it for each of the above applications.
  • the alkanolphenol type benzotriazole polymers described in these publications have a weak wavelength absorption at 380 nm to 400 nm and an insufficient ultraviolet blocking function.
  • the sesamol type benzotriazole-based polymer has a wavelength absorption of 380 to 420 nm, but has a strong absorption in the visible light range of 400 to 420 nm and is colored yellow. It has been difficult to use the film for optical film and spectacle lens applications.
  • an object of the present invention is to absorb ultraviolet light in the wavelength region of 300 to 400 nm, particularly in the wavelength region of 330 to 400 nm having a high accumulated energy, which can correspond to the spectral irradiance distribution of the ultraviolet portion of sunlight reaching from the sun on the ground.
  • An object of the present invention is to provide a benzotriazole-based (co) polymer that is excellent and less colored, a paint containing the same, and a film coated with the paint.
  • the present inventors have studied a UV-absorbing benzotriazole copolymer, a paint containing the same, and a film coated with the paint.
  • the present inventors have found a benzotriazole-based (co) polymer obtained by polymerizing or copolymerizing a raw material monomer containing a benzotriazole-based monomer having a novel molecular structure different from that of the present invention.
  • the present invention is most preferably a benzotriazole-based UV-absorbing polymer obtained by polymerizing a raw material containing a resorcinol-type benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer.
  • Main features a benzotriazole-based UV-absorbing polymer obtained by polymerizing a raw material containing a resorcinol-type benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer.
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl carbon number of 1
  • R 4 is an acryloyloxyalkyl group having 1 to 4 alkyl carbon atoms and an acryloyloxyhydroxy group having 1 to 4 alkyl carbon atoms.
  • resorcinol-type benzotriazole-based monomer refers to a derivative of a compound in which resorcinol is bonded to the nitrogen atom at the 2-position of the benzotriazole ring as represented by the general formula (1). And a molecular structure in which a polymerizable double bond is introduced into a carboxyl group introduced into the benzene moiety of the benzotriazole ring.
  • the polymerizable monomer further contains an alkanolphenol-type benzotriazole monomer represented by the general formula (2) [Chemical Formula 2] as a raw material, and a benzoate formed by copolymerizing the alkanolphenol type benzotriazole monomer. It is preferable to use a triazole-based ultraviolet absorbing polymer.
  • General formula (2) (Wherein R 5 represents a hydrogen atom or a methyl group, R 6 represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R 7 represents a hydrogen atom or a carbon atom having 1 to 18 carbon atoms.
  • R 8 represents a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group)
  • alkanolphenol-type benzotriazole monomer refers to a compound in which an alkanolphenol is bonded to the nitrogen atom at the 2-position of the benzotriazole ring, as represented by the general formula (2).
  • the resorcinol-type benzotriazole-based monomer represented by the general formula (1) has a maximum absorption wavelength ⁇ max of around 360 nm, a wide range of ultraviolet absorption spectrum covering 300 to 400 nm, and a long wavelength around 400 nm. It has ultraviolet absorption ability up to the wavelength region.
  • the resorcinol-type benzotriazole-based (co) polymer of the present invention, the paint containing the same, and the film coated with the polymer have a wide range of 300 to 400 nm capable of corresponding to the spectral irradiance distribution of the ultraviolet part of sunlight on the ground.
  • the absorption performance in the wavelength region is excellent, and the coating material containing the coating material and the film coated with the coating material have excellent ultraviolet absorption performance and ultraviolet blocking performance, and are less colored.
  • the alkanolphenol-type benzotriazole monomer represented by the general formula (2) is a known benzotriazole monomer that is currently generally used in benzotriazole-based UV-absorbing polymers, A typical industrial product is 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole.
  • the maximum absorption wavelength ⁇ max has an ultraviolet absorption spectrum in a range including 338 nm and 250 to 380 nm, but the ultraviolet absorption ability in a long wavelength region of 380 nm or more is extremely low.
  • the resorcinol-type benzotriazole-based monomer represented by the general formula (1) [Chemical Formula 1] as the polymerizable monomer By copolymerizing with a raw material containing an alkanolphenol type benzotriazole monomer represented by the formula (2) [Chemical Formula 2], it has excellent absorption performance in a wider ultraviolet region of 250 to 400 nm. And a film coated with the paint are more excellent in ultraviolet absorption performance and ultraviolet shielding performance.
  • the benzotriazole-based (co) polymer of the present invention is a polymer, a coating film can be formed by itself. Therefore, the problem of elution of ultraviolet absorbing components from the coating film and bleeding out does not occur. Furthermore, the polymer polarity can be freely changed by selecting a monomer other than the ultraviolet-absorbing monomer constituting the polymer in a timely manner to obtain a copolymer. Therefore, there is no problem of crystallization of the ultraviolet absorbing component in the coating film or compatibility with other resins or compounding materials.
  • 2 is an ultraviolet absorption spectrum of the compound of Example 1 of the present invention.
  • 2 is an ultraviolet absorption spectrum of the compound of Example 2 of the present invention.
  • 4 is an ultraviolet absorption spectrum of the compound of Example 3 of the present invention.
  • 4 is an ultraviolet absorption spectrum of the compound of Example 4 of the present invention.
  • 2 is an ultraviolet absorption spectrum of the compound of Comparative Example 1.
  • 3 is an ultraviolet absorption spectrum of the compound of Comparative Example 2.
  • the benzotriazole-based UV-absorbing polymer of the present invention is obtained by polymerizing or copolymerizing a raw material containing the resorcinol-type benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer. Further, it is obtained by copolymerizing a raw material further containing an alkanolphenol type benzotriazole monomer represented by the general formula (2) as the polymerizable monomer.
  • the raw material may contain other polymerizable monomers as necessary.
  • the substituent represented by R 1 and R 2 is composed of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • the substituent represented by R 3 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a carboxyalkyl group having 1 to 7 alkyl carbon atoms, an alkyloxycarbonylalkyl group having a total of 2 to 15 alkyl carbon atoms, carbon A hydroxyalkyl group having 1 to 8 carbon atoms, an alkylcarbonyloxyalkyl group having a total of 2 to 15 alkyl carbon atoms, a formyl group, an alkylcarbonyl group having 1 to 7 alkyl carbon atoms, a benzoyl group, or a toluoyl group
  • the substituent represented by R 4 is an acryloyloxyalkyl group having 1 to 4 alkyl carbon atom
  • Benzotriazoles composed of an alkyl group, a methacryloyloxyalkyl group having 1 to 4 alkyl carbon atoms, or a methacryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms.
  • Specific substance names of the resorcinol-type benzotriazole monomer include 2-acryloyloxyethyl 2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole-5-carboxylate, 2-methacryloyloxy Ethyl 2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole-5-carboxylate, 2-methacryloyloxyethyl 2- (4-benzoyloxy-2-hydroxyphenyl) -2H-benzotriazole-5 Carboxylate, 2-methacryloyloxyethyl 2- (2-hydroxy-4-methacryloyloxyphenyl) -2H-benzotriazole-5-carboxylate, 2-methacryloyloxyethyl 2- (2-hydroxy-4-octyloxy) Can be exemplified phenyl) -2H- benzotriazole-5-carboxylate, is not limited to the specific examples. These benzotriazo
  • substituents R 4 is a hydrogen atom or a methyl group represented by R4, the substituent represented by R 5 is a carbon A linear or branched alkylene group having 1 to 6 carbon atoms, a substituent represented by R 6 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, a substituent represented by R 7 is a hydrogen atom, Benzotriazoles composed of a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group.
  • alkanolphenol type benzotriazole monomer examples include 2- [2-hydroxy-5- (methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (Acryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl ] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxypropyl) phenyl] -2H-benzotriazole 2- [2-hydroxy- -(Methacryloyloxybutyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxymethyl
  • the benzotriazole copolymer of the present invention may be copolymerized with a polymerizable monomer other than the benzotriazole monomer as a raw material polymerizable monomer.
  • the other polymerizable monomer that can be copolymerized with the benzotriazole-based monomer is not particularly limited and can be appropriately selected and used.
  • Examples thereof include hydroxyl group-containing unsaturated monomers such as hydroxyethyl (meth) acrylate, hydroxypropylethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate. Furthermore, oxide ring containing unsaturated monomers, such as glycidyl (meth) acrylate and oxetane (meth) acrylate, are mentioned.
  • nitrogen-containing unsaturation such as (meth) acrylamide, N, N′-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, (meth) acryloylmorpholine, vinylpyridine, vinylimidazole, N-vinylpyrrolidone, etc.
  • Monomer Furthermore, halogen-containing unsaturated monomers such as vinyl chloride and vinylidene chloride are exemplified. Furthermore, aromatic unsaturated monomers such as styrene and ⁇ -methylstyrene are exemplified.
  • carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and the like can be mentioned.
  • sulfonic acid group-containing unsaturated monomers such as vinyl sulfonic acid and styrene sulfonic acid can be mentioned.
  • phosphoric acid group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and the like can be mentioned.
  • sulfonic acid group-containing unsaturated monomers such as vinyl sulfonic acid and s
  • a known method can be used for a method of adjusting the raw material such as a mixing method of the raw material containing the benzotriazole monomer, and the method is not particularly limited.
  • a conventionally known solution polymerization method emulsion polymerization method, suspension polymerization method, bulk polymerization method, or the like may be employed. There is no particular limitation.
  • the radical polymerization initiator used in the polymerization reaction is not particularly limited, and examples thereof include 2,2′-azobis- (4-methoxy-2.4-dimethylvaleronitrile), 2,2′-azobis- (2, 4-dimethylvaleronitrile), dimethyl 2,2′-azobis- (2-methylpropionate), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2-methylbutyronitrile) ), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 1-[(1-cyano-1-methyl) Ethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), etc.
  • Zeo radical polymerization initiators hydrogen peroxide, dibenzoyl peroxide, dilauroyl peroxide, diisobutyryl peroxide, bis (3,5,5-) trimethylhexanoyl) peroxide, methyl ethyl ketone peroxide , Methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetra Methyl butyl hydroperoxide, di-t-butyl hydroperoxide, t-butyl- ⁇ -cumyl peroxide, di-t-butyl- ⁇ -cumyl -Oxide, di- ⁇ -cumyl peroxide, 1,1-bis (t-butylperoxy) -3,
  • a redox initiator may be used by using sodium sulfite, L-ascorbic acid, Rongalite or the like as a reducing agent.
  • a chain transfer agent or a polymerization regulator may be used as necessary.
  • chain transfer agents and polymerization modifiers include n-dodecyl mercaptan, n-dodecyl mercaptan, ⁇ -mercaptopropionic acid methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3 -Mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, thioglycolic acid, ammonium thioglycolate, monoethanolamine thioglycolate, alphamethylstyrene dimer, etc. Not particularly limited.
  • the usage-amount of a chain transfer agent and a polymerization regulator is not specifically limited.
  • Solvents that can be used in the solution polymerization method include toluene, xylene, ethyl acetate, butyl acetate, cellosolve acetate, dimethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone, but are not particularly limited. Further, the amount of solvent used is not particularly limited.
  • Surfactants that can be used in the emulsion polymerization method include sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether acetate, ammonium polyoxyethylene lauryl ether acetate, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether Ammonium sulfate, sodium dodecylbenzenesulfonate, ammonium dodecylbenzenesulfonate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether, lauryltrimethylammonium chloride, Stearyltrimethylammonium chloride, cetyltrichloride Tillammonium chloride, octadecyloxypropyltrimethylammonium chloride, distearyldimethylammoni
  • dispersant examples include partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, sodium polyacrylate, methyl cellulose, carboxymethyl cellulose, and polyethylene oxide, but are not particularly limited. . Further, the amount of the dispersant used is not particularly limited.
  • the polymerization reaction temperature is preferably in the range of room temperature to 200 ° C., more preferably in the range of 40 ° C. to 140 ° C., but is not particularly limited to these ranges.
  • the reaction time is not particularly limited, and may be set appropriately according to the composition of the monomer composition to be used, the type of polymerization initiator, and the like so that the polymerization reaction is completed.
  • the benzotriazole-based UV-absorbing polymer of the present invention is obtained by (co) polymerizing a raw material containing the benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer. It is the composition which becomes. More preferably, it is a structure obtained by (co) polymerizing a raw material further containing an alkanolphenol type benzotriazole monomer represented by the general formula (2) as a polymerizable monomer.
  • it is formed by (co) polymerizing a monomer composition containing an ultraviolet absorbing monomer having an ultraviolet absorbing ability in the entire wavelength region of 300 to 400 nm, so that the entire wavelength region of 300 to 400 nm, particularly 330 nm to 400 nm. Excellent UV absorption performance near wavelength range.
  • the coating material containing the benzotriazole-based (co) polymer of the present invention has a benzotriazole-based (co-polymerized) obtained by (co) polymerizing a raw material containing the resorcinol-type benzotriazole-based monomer represented by the general formula (1).
  • the composition includes a benzotriazole copolymer formed by copolymerizing the above raw material further containing an alkanolphenol type benzotriazole monomer represented by the general formula (2).
  • Examples of the form of paint include water-based paint, solvent-based paint, ultraviolet curable paint, thermosetting paint, clear paint, pigment paint, and dye paint, but are not particularly limited.
  • materials such as resins other than benzotriazole-based (co) polymers constituting the paint, solvents, crosslinking agents, curing agents, catalysts, fillers, leveling agents, plasticizers, stabilizers, dyes, pigments, etc. are particularly limited. It is not a thing, but it can select suitably and can use it.
  • a film coated with a paint containing a benzotriazole-based (co) polymer of the present invention is formed by (co) polymerizing a raw material containing a resorcinol-type benzotriazole-based monomer represented by the general formula (1).
  • a film coated with a paint having a structure containing a benzotriazole-based (co) polymer More preferably, it is a film coated with a coating composition containing a benzotriazole copolymer obtained by copolymerizing a raw material further containing an alkanol phenol type benzotriazole monomer represented by the general formula (2). .
  • Types of film include polyester film, cellulose film, polyolefin film, polyamide film, polystyrene film, vinyl chloride film, vinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polyimide film, etc. However, it is not particularly limited.
  • the paint containing the benzotriazole-based (co) polymer is a roll coater, a reverse roll coater, a gravure coater, a knife coater, a blade coater, Rod-coater, air doctor coater, curtain coater, fountain coater, kiss coater, screen coater, spin coater, cast coating, spray coater, electrodeposition coating extrusion coater, Langmuir-Blodget (LB) method, etc.
  • LB Langmuir-Blodget
  • a 2000 ml four-necked flask was equipped with a ball condenser, a thermometer, and a stirrer, 875 ml of water, 56.5 g (0.533 mol) of sodium carbonate, 178.8 g (0.982) of 4-amino-3-nitrobenzoic acid. Mol) was added and dissolved, and 197.1 g (1.028 mol) of 36% aqueous sodium nitrite solution was added. Attach this solution to a 3000 ml four-necked flask with a ball condenser, thermometer, and stirrer, add 875 ml of water and 372.0 g (2.370 mol) of 62.5% sulfuric acid, and mix to 3-7 ° C.
  • the solution was added dropwise to the cooled product and stirred at the same temperature for 1 hour to obtain a diazonium salt aqueous solution.
  • a 3000 ml four-necked flask was equipped with a condenser with a ball, a thermometer and a stirrer, and 217.8 g (0.657 mol) of 6- (4-carboxy-2-nitrophenylazo) -1,3-dimethoxybenzene, 32 147.6 g (1.181 mol) of aqueous sodium hydroxide solution, 370 ml of water, 1100 ml of isopropyl alcohol, and 1.1 g of hydroquinone were added, and 52.6 g (0.630 mol) of 60% hydrazine monohydrate was added at 70 ° C. The solution was added dropwise over 1 hour and stirred at the same temperature for 3 hours.
  • a 300 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirring device, and 9.0 g (0.033 mol) of 5-carboxy-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, carbonic acid 4.4 g (0.042 mol) of sodium, 11.8 g (0.079 mol) of octyl chloride, 20 ml of N, N-dimethylformamide, 0.5 g of potassium iodide and 1.3 g of polyethylene glycol 400 were added, and Stir at 140 ° C. for 3 hours.
  • a 200 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirrer, and 3.3 g of octyl 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate (0. 0067 mol), 0.8 g (0.0200 mol) of sodium hydroxide, 25 ml of isopropyl alcohol and 25 ml of water were added and stirred at 70 to 75 ° C. for 2 hours.
  • a 200 ml four-necked flask was equipped with a ball condenser, thermometer, and stirring device, and 2.5 g (0.0065 mol) of 5-carboxy-2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole was attached. ), 2.0 g (0.0168 mol) of thionyl chloride, 50 ml of toluene, and 0.2 ml of N, N-dimethylformamide were added, and the mixture was stirred at 62 to 68 ° C. for 1 hour.
  • Toluene was recovered under reduced pressure, 50 ml of toluene, 1.8 g (0.0138 mol) of 2-hydroxyethyl methacrylate and 1.3 g (0.0164 mol) of pyridine were added, and the mixture was stirred at 72 to 78 ° C. for 1 hour. .
  • Add 30 ml of water and 0.5 ml of 62.5% sulfuric acid separate and remove the lower aqueous layer at 70 to 75 ° C., collect toluene under reduced pressure, add 30 ml of isopropyl alcohol, and form precipitate Was filtered, washed and dried to obtain 2.2 g of crude crystals.
  • the sesamol type benzotriazole monomer is a commercially available 2- [2- (6-hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3 benzotriazol-5-yl].
  • Ethyl methacrylate (Cypro Kasei R26) was used.
  • 2- [2- (6-hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3benzotriazol-5-yl] ethyl methacrylate is referred to as “compound (d)”. .
  • Example 1 A Dimroth condenser, a mercury warm clock, a nitrogen gas blowing tube, and a stirring device are attached to the four-necked flask, and 20 parts of the compound (a) as a monomer composition, methyl methacrylate (hereinafter referred to as “MMA”) 20 And 60 parts of methyl ethyl ketone (hereinafter referred to as “MEK”) as a solvent, and 2,2′-azobis-methylbutyronitrile (hereinafter referred to as “AMBN”) 1 as a polymerization initiator 0.5 part was added, and the inside of the flask was purged with nitrogen for 1 hour at a nitrogen gas flow rate of 10 ml / min while stirring, and then the polymerization reaction was carried out under reflux conditions at a reaction liquid temperature of 80 to 86 ° C. for 10 hours. After completion of the polymerization reaction, 101.5 parts of an ultraviolet absorbing copolymer solution was
  • Example 2 The monomer composition in Example 1 was 20 parts of compound (a), 8 parts of MMA, styrene (hereinafter referred to as “St”), and 8 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as “HEMA”). Except for the above, the same polymerization reaction operation as in Example 1 was performed to obtain a UV-absorbing copolymer solution.
  • Example 3 the monomer composition was 10 parts of compound (a), 10 parts of compound (c), 18 parts of cyclohexyl methacrylate (hereinafter referred to as “CHMA”), and 1,2,2,6,6- Except for using 2 parts of pentamethylpiperidyl methacrylate (hereinafter referred to as “HALS”), the same polymerization reaction operation as in Example 1 was performed to obtain a UV-absorbing copolymer solution.
  • CHMA cyclohexyl methacrylate
  • HALS pentamethylpiperidyl methacrylate
  • Example 4 Same as Example 1 except that the monomer composition in Example 1 was 2 parts of Compound (b) and 18 parts of MMA, 80 parts of MEK as a solvent and 0.8 parts of AMBN as a polymerization initiator. The polymerization reaction operation was performed to obtain a UV-absorbing copolymer solution.
  • Example 1 Comparative Example 1 Except that the monomer composition in Example 1 was 20 parts of compound (c) and 20 parts of MMA, the same polymerization reaction operation as in Example 1 was performed to obtain an ultraviolet-absorbing copolymer solution.
  • Example 2 (Comparative Example 2) Except that the monomer composition in Example 1 was 20 parts of compound (d) and 20 parts of MMA, the same polymerization reaction operation as in Example 1 was performed to obtain an ultraviolet-absorbing copolymer solution.
  • a coating film containing a UV-absorbing copolymer was prepared, and a coating film was prepared by coating this onto a polyester film. UV-blocking function confirmation test and coating film were used to confirm the protection performance of dyes used in sublimation transfer printing. The elution, bleeding out, crystallization, and compatibility of compounding materials were confirmed.
  • the nonvolatile content was calculated from the amount of residual resin after weighing 1 g of the UV-absorbing copolymer solution obtained in an aluminum dish, drying at 100 ° C. for 1 hour, and further drying at 150 ° C. for 5 hours.
  • Viscosity was determined by measuring the solution viscosity at 25 ° C. using an EH viscometer (Toki Sangyo Co., Ltd., TV-22).
  • the molecular weight is GPC system (Tosoh Corporation HLC-8320GPC EcoSEC), the eluent is tetrahydrofuran, the separation column is TSKgelGMHXL-L (Tosoh Corporation), the weight average molecular weight (Mw) in terms of polystyrene using a polystyrene calibration curve, Number average molecular weight (Mn) and polydispersity (Mw / Mn) were measured.
  • GPC system Tosoh Corporation HLC-8320GPC EcoSEC
  • the eluent is tetrahydrofuran
  • the separation column is TSKgelGMHXL-L (Tosoh Corporation)
  • Mw weight average molecular weight
  • Mn Number average molecular weight
  • Mn polydispersity
  • the maximum absorption wavelength ⁇ max and ultraviolet absorption spectrum are obtained by removing the solvent from the obtained UV-absorbing copolymer solution by drying under reduced pressure, and using a 40 ppm concentration chloroform solution as a spectrophotometer (Hitachi High-Technologies Corporation U-3900H) It measured using.
  • the ultraviolet ray blocking function test was carried out by preparing a UV-absorbing copolymer-containing paint using the UV-absorbing copolymer solutions obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and coating the paint The ultraviolet absorption blocking performance of the dye used for sublimation transfer printing with film was confirmed. The procedure is described below.
  • a yellow dye, a cyan dye, a magenta dye, and a three-color transfer film used in a commercially available sublimation transfer type compact photo printer were obtained.
  • the deterioration of the transfer film dye due to ultraviolet irradiation was measured using a xenon weather meter (Suga Tester SX-75) with an irradiance of 180 W, a black panel temperature of 63 ⁇ 3 ° C., and an ultraviolet ray of 100 hours Continuous irradiation. From this result, the fading deterioration of the dye was used as an evaluation standard for UV resistance.
  • the transfer film of the dye is protected with a glass plate coated with the paint containing the respective UV-absorbing copolymers prepared as described above.
  • the transfer of the dye is performed according to JISK5701-1: 2000. UV degradation was confirmed. The evaluation is made in 5 stages in consideration of the degree of visual confirmation of fading, level 5 has no change, level 4 can confirm slight ink fading, level 3 can confirm ink fading, level 4 has almost ink fading, Level 1 was the ink dissociation disappearance
  • coloring was measured.
  • a b * and YI value were measured using a color difference meter (Nippon Denshoku Industries Co., Ltd. SE6000).
  • a solution obtained by diluting 10 parts of the obtained UV-absorbing copolymer solution with 30 parts of toluene and a cell having an optical path length of 1 cm were used.
  • the elution, bleeding out, crystallization, and blending material compatibility change confirmation test of the coating material state of the UV-absorbing component from the coating film was performed on the film coated with the paint containing each UV-absorbing copolymer prepared above. The change with time was observed using an optical microscope. The evaluation was a visual sensitivity evaluation of the state of the coating film for one month from the film production.
  • Table 1 shows the results of the UV blocking function test evaluation, elution of ultraviolet absorbing components from the coating, bleed-out, crystallization, and changes in coating material compatibility, and UV absorption spectra are shown in Figs. It was shown to.
  • the benzotriazole-based (co) polymer of the present invention has a wide range of ultraviolet absorption wavelengths with respect to the ultraviolet wavelength region 300 nm to 400 nm of the solar irradiance distribution that reaches from the sun on the ground. Has a region. Therefore, the paint using this and the film coated with the paint also have a wide ultraviolet absorption wavelength region of 300 nm to 400 nm. Therefore, it was found that when used as an ultraviolet absorption blocking protective material, the object to be protected can be protected from ultraviolet rays at a very high level.
  • the benzotriazole-based (co) polymer of the present invention absorbs a wide wavelength range of 300 to 400 nm that can correspond to the spectral irradiance distribution of the ultraviolet portion of sunlight, which has been difficult to absorb conventionally. It is a material that can be used and is less colored.
  • the benzotriazole-based (co) polymer of the present invention obtained by copolymerization using a conventionally known benzotriazole-based monomer that absorbs an ultraviolet region of 250 nm to 380 nm as a raw material monomer, Excellent absorption performance over a wide ultraviolet range. It can also be used as a paint for coating. Therefore, it can be suitably used for protection of materials and human bodies that are deteriorated by ultraviolet rays, and among them, it can be suitably used for optical films for displays, eyeglass lenses and the like.

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention concerne un (co)polymère à base de benzotriazole obtenu par polymérisation d'un matériau de départ comprenant un monomère de benzotriazole de type résorcinol de formule générale suivante. Le (co)polymère à base de benzotriazole est un polymère présentant une faible coloration et d'excellentes performances en matière d'absorption de la lumière ultraviolette d'une longueur d'onde se situant dans la plage de 300 à 400 nm, ce qui correspond à la distribution d'irradiance spectrale des composantes ultraviolettes de la lumière du soleil arrivant au sol, en particulier d'excellentes performances en matière d'absorption de la lumière ultraviolette d'une longueur d'onde se situant dans la plage de 330 à 400 nm, plage dans laquelle l'énergie intégrée est élevée. [De préférence, R11 et R2 représentent chacun H, R33 représente un alkyle et R4 représente H, un alkyle, un alkylacryloyloxyalkyle ou un méthacryloyloxyalkyle.]
PCT/JP2018/012309 2017-03-29 2018-03-27 (co)polymère à base de benzotriazole, matériau de revêtement absorbant les ultraviolets en contenant, et film revêtu dudit matériau de revêtement WO2018181256A1 (fr)

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CN201880022908.9A CN110475792B (zh) 2017-03-29 2018-03-27 苯并三唑系(共)聚合物和含有其的紫外线吸收性涂料以及涂布有该涂料的膜

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JP7476520B2 (ja) * 2018-12-26 2024-05-01 ａｒｔｉｅｎｃｅ株式会社 紫外線吸収性単量体、アクリル重合体、樹脂組成物および成形体
JP7293753B2 (ja) * 2019-03-15 2023-06-20 東洋インキＳｃホールディングス株式会社 成型用樹脂組成物および成形体
WO2022039120A1 (fr) 2020-08-21 2022-02-24 富士フイルム株式会社 Composition polymérisable, polymère, matériau de protection contre les ultraviolets, stratifié, composé, agent absorbant les ultraviolets et procédé de production d'un composé

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CN110475792A (zh) 2019-11-19

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