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WO2018190381A1 - Matériau de revêtement absorbant les ultraviolets et film revêtu dudit matériau de revêtement - Google Patents

Matériau de revêtement absorbant les ultraviolets et film revêtu dudit matériau de revêtement Download PDF

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Publication number
WO2018190381A1
WO2018190381A1 PCT/JP2018/015272 JP2018015272W WO2018190381A1 WO 2018190381 A1 WO2018190381 A1 WO 2018190381A1 JP 2018015272 W JP2018015272 W JP 2018015272W WO 2018190381 A1 WO2018190381 A1 WO 2018190381A1
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Prior art keywords
benzotriazole
group
ultraviolet
carbon atoms
monomer
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English (en)
Japanese (ja)
Inventor
孝仁 〆野
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Shin Nakamura Chemical Co Ltd
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Shin Nakamura Chemical Co Ltd
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Priority to KR1020197033431A priority Critical patent/KR102345990B1/ko
Priority to CN201880024882.1A priority patent/CN110546172B/zh
Publication of WO2018190381A1 publication Critical patent/WO2018190381A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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 light in a wide wavelength range and visible light short wavelength range, a paint containing the same, and a film coated with the paint. It is.
  • 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 and 2).
  • Monomer containing one or more sesamol type benzotriazole-based UV-absorbing monomers as having an absorption in the vicinity of 400 nm in a relatively long wavelength range, which was insufficient with alkanolphenol-type benzotriazole-based copolymers A benzotriazole copolymer obtained by copolymerizing the composition is used (for example, Patent Document 3).
  • UV-absorbing monomers are generally used in, for example, display devices to add a UV absorber to an optical film such as a polarizing plate protective film to prevent discoloration of these optical films. It is used. Moreover, in order to prevent the near-infrared absorber contained in the antireflection film from being deteriorated by ultraviolet rays, an ultraviolet absorber is added to the antireflection film. In addition, 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. .
  • ultraviolet absorbers are applied to eyeglass lenses or contact lenses. It is common practice to add to prevent the ultraviolet rays from reaching the eyes.
  • Patent Documents 4 to 5 can be used as compounds having absorption in such a wavelength region.
  • Indole derivatives, pyrrolidine-amide derivatives, xanthone derivatives are mentioned.
  • these compounds generally have low light resistance, and are deteriorated by exposure to sunlight, resulting in a decrease in light absorption ability. Therefore, these compounds cannot be used for a long time.
  • Patent Documents 4 to 5 do not describe light resistance.
  • the sesamol type benzotriazole copolymer generally known as high light resistance of Patent Document 3 can absorb ultraviolet light and light in the short wavelength region of visible light, but has weak absorption of 420 nm or more, and 300 to There is a problem that the absorption in the ultraviolet region near 330 nm is slightly weak.
  • alkanolphenol type benzotriazole polymers and sesamol type benzotriazole polymers described in these publications do not have absorption performance in the visible light short wavelength region of 420 to 450 nm.
  • the visible light short wavelength region blocking performance of the obtained film was insufficient.
  • a problem in the present invention is that a benzotriazole-based (co) polymer having absorption performance in a wide ultraviolet wavelength region of 300 to 400 nm while absorbing light in the visible short wavelength region up to around 450 nm, and a paint containing the same, and The object is to provide 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 methoquinone-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 methoquinone-type benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 2 represents an alkyl group having 1 to 8 carbon atoms
  • R 3 represents an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms
  • it represents a methacryloyloxyalkyl group having 1 to 2 alkyl carbon atoms.
  • methoquinone type benzotriazole monomer refers to a phenol having an alkoxy at the meta position on the nitrogen atom at the 2-position of the benzotriazole ring, as represented by the general formula (1).
  • 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.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents a linear or branched alkylene group having 1 to 6 carbon atoms
  • R 6 represents a hydrogen atom or a carbon atom having 1 to 18 carbon atoms
  • R 7 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 methoquinone-type benzotriazole monomer represented by the general formula (1) has two maximum absorption wavelengths ⁇ max near 310 nm and 380 nm, and covers a wide range of ultraviolet wavelength region and visible region including 300 to 450 nm. It has an absorption spectrum in the light short wavelength region, and has a visible light short wavelength absorption ability up to around 450 nm.
  • the benzotriazole-based (co) polymer of the present invention the paint containing the benzotriazole-based (co) polymer, and the film on which the coating is coated have a wide wavelength range of 300 to 450 nm that can correspond to the spectral irradiance distribution of the ultraviolet part of sunlight on the ground.
  • the absorption performance in the short wavelength region of visible light is excellent, and the coating material including the coating material and the film coated with the coating material are excellent in the absorption performance and ultraviolet blocking performance of ultraviolet and visible light short wavelength.
  • the alkanolphenol-type benzotriazole monomer represented by the general formula (2) is an existing known benzotriazole monomer that is generally used in benzotriazole UV-absorbing polymers.
  • a representative 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 paint containing the same and the 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 a methoquinone type benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer. Further, it is obtained by copolymerizing a raw material containing an alkanolphenol type benzotriazole monomer represented by the general formula (2) as a polymerizable monomer. In addition, the said raw material may also contain other polymerizable monomers as needed.
  • the substituent represented by R 1 is composed of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • represented by R 2 consists of a substituent group is an alkyl group having 1 to 8 carbon atoms which is, acryloyloxy alkyl group substituents C 1 to alkyl carbon 2 represented by R 3 or alkyl having 1 or 2 carbon atoms, methacryloyloxy group
  • R 1 is composed of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 2 consists of a substituent group is an alkyl group having 1 to 8 carbon atoms which is, acryloyloxy alkyl group substituents C 1 to alkyl carbon 2 represented by R 3 or alkyl having 1 or 2 carbon atoms, methacryloyloxy group
  • R 3 alkyl having 1 or 2 carbon atoms
  • methoquinone type benzotriazole monomers include 2-methacryloyloxyethyl 2- (2-hydroxy-5-methoxyphenyl) -2H-benzotriazole-5-carboxylate, 2-acryloyloxy Ethyl 2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole-5-carboxylate, 2-methacryloyloxyethyl 2- (3-tert-butyl-2-hydroxy-5- Examples include methoxyphenyl) -2H-benzotriazole-5-carboxylate, but are not limited to the above specific examples. Moreover, these methoquinone type benzotriazole monomers can be used alone or in combination of two or more.
  • 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-5- Methacryloyloxybutyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxybuty
  • 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 ultraviolet absorbing polymer of the present invention is obtained by (co) polymerizing a raw material containing the methoquinone type benzotriazole monomer represented by the general formula (1) as a polymerizable monomer. It is the composition which consists of. 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.
  • 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 a methoquinone 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.
  • the film coated with the paint containing the benzotriazole-based (co) polymer of the present invention is formed by (co) polymerizing a raw material containing a methoquinone 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 200 ml four-necked flask was equipped with a condenser with a ball, a thermometer and a stirrer, 100 ml of water, 6.5 g (0.061 mol) of sodium carbonate, 20.0 g of 4-amino-3-nitrobenzoic acid (0.110) Mol) was added and dissolved, and 22.7 g (0.118 mol) of 36% aqueous sodium nitrite solution was added.
  • a 500 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirrer, and 100 ml of water and 43.0 g (0.274 mol) of 62.5% sulfuric acid were mixed and mixed to 3-7 ° C.
  • the solution was added dropwise to the cooled product and stirred at the same temperature for 2 hours to obtain a diazonium salt aqueous solution.
  • Attach a condenser with a ball, a thermometer, and a stirrer to a 1000 ml four-necked flask add 18.0 g (0.100 mol) of 2-tert-butyl-4-methoxyphenol, 10 ml of isopropyl alcohol, and 140 ml of water and mix.
  • a diazonium salt aqueous solution was added dropwise at 5 to 10 ° C., and the mixture was stirred at 5 to 10 ° C. for 2 hours, and then stirred at 10 to 15 ° C.
  • a 300 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, and 20.3 g of 5-carboxy-2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole (0.059 mol), toluene (100 ml), thionyl chloride (13.0 g, 0.109 mol) and N, N-dimethylformamide (2.0 ml) were added, and the mixture was stirred at 60 to 70 ° C. for 3 hours.
  • the solvent was recovered under reduced pressure, 100 ml of toluene, 14.0 g (0.108 mol) of 2-hydroxyethyl methacrylate and 8.3 g (0.105 mol) of pyridine were added, and the mixture was stirred at 60 to 70 ° C. for 1 hour. 20 ml of water and 9.0 g (0.057 mol) of 62.5% sulfuric acid were added, and the lower aqueous layer was separated and removed at 60 to 70 ° C. Further, 20 ml of water was added and the mixture was added at 60 to 70 ° C.
  • Compound (b) was obtained in a yield of 5% (from 4-methoxyphenol) in the same manner as in Synthesis Example 1 except that 2-tert-butyl-4-methoxyphenol was changed to 4-methoxyphenol.
  • the melting point was 94 ° C.
  • the maximum absorption wavelength ⁇ max was 309.8 nm and 373.2 nm
  • the molar extinction coefficients ⁇ at the wavelengths were 14700 and 13100, respectively.
  • 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 obtained.
  • MMA methyl methacrylate
  • 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 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 0.5 g of the UV-absorbing copolymer solution obtained in an aluminum dish, dried at 100 ° C. for 1 hour, and further dried 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 HLC-8320GPC EcoSEC (Tosoh Corporation), the eluent is tetrahydrofuran, the separation column is TSKgelGMHXL-L (Tosoh Corporation), the polystyrene-converted weight average molecular weight (Mw), Number average molecular weight (Mn) and polydispersity (Mw / Mn) were measured.
  • the maximum absorption wavelength ⁇ max and the UV absorption spectrum were obtained by removing the solvent from the obtained UV-absorbing copolymer solution by drying under reduced pressure, and then 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 dye of the transfer film due to ultraviolet irradiation was measured by using a xenon weather meter (Suga Test Instruments 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 defined as ink dissipation disappearance.
  • 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. In addition, it has absorption in the visible light short wavelength range of about 400 to 450 nm, which has been pointed out to damage organic substances and human bodies. Therefore, the coating material using the coating material and the film coated with the coating material also have an absorption wavelength region of a wide wavelength range of 300 nm to 450 nm and a short wavelength of visible light.
  • the object to be protected can be protected from ultraviolet rays at a very high level. It was also found that the elution and bleeding out of the ultraviolet absorbing component from the coating film, the crystallization of the ultraviolet absorbing component in the coating film, and the compatibility problem with other compounding materials did not occur.
  • 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 capable of absorbing in the short wavelength region of visible light of about 400 to 450 nm, which has been pointed out to damage organic substances and the human body.
  • 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 light in the ultraviolet and visible light short wavelength region, and in particular, it can be suitably used for optical films for display, eyeglass lenses and the like.

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

Abstract

La présente invention concerne un (co)polymère de benzotriazole qui est obtenu par polymérisation d'un matériau de départ qui contient un monomère de benzotriazole de type méthoquinone représenté par la formule générale, et qui a une absorption dans une large région de longueur d'onde ultraviolette de 300 à 400 nm, tout en absorbant la lumière dans une région de lumière visible à courte longueur d'onde jusqu'à environ 450 nm. (Dans la formule, R1 représente un atome d'hydrogène ou un groupe alkyle ; R2 représente un groupe alkyle ; et R3 représente un groupe acryloyloxyalkyle ou un groupe méthacryloyloxyalkyle.)
PCT/JP2018/015272 2017-04-13 2018-04-11 Matériau de revêtement absorbant les ultraviolets et film revêtu dudit matériau de revêtement Ceased WO2018190381A1 (fr)

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CN201880024882.1A CN110546172B (zh) 2017-04-13 2018-04-11 紫外线吸收性涂料以及涂布有该涂料的膜

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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
JP7362049B2 (ja) * 2019-11-14 2023-10-17 国立大学法人福井大学 ベンゾトリアゾール系共重合体およびこれを用いた紫外線吸収剤
JP7488863B2 (ja) * 2022-09-27 2024-05-22 日本製紙株式会社 ハードコートフィルム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63227575A (ja) * 1987-03-03 1988-09-21 アイオーラブ・コーポレーシヨン ベンゾトリアゾール化合物、その共重合体および紫外線吸収用組成物
WO2007108347A1 (fr) * 2006-03-20 2007-09-27 Konica Minolta Opto, Inc. Film optique d'acylate de cellulose, sa méthode de production, plaque polarisante utilisant ledit film et dispositif d'affichage à cristaux liquides
JP2009114430A (ja) * 2007-10-17 2009-05-28 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム、偏光板、及び表示装置
JP2012025811A (ja) * 2010-07-21 2012-02-09 Shinnakamura Kagaku Kogyo Kk 紫外線吸収性のベンゾトリアゾール系（共）重合体及びこれを含む塗料並びに該塗料がコーティングされたフィルム

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1965042A1 (de) * 1969-12-27 1971-07-15 Konishiroku Photo Ind Lichtempfindliches,farbfotographisches Aufzeichnungsmaterial
JP4118261B2 (ja) 2004-07-07 2008-07-16 大日本印刷株式会社 保護層熱転写フィルム
JP2006264312A (ja) 2005-02-28 2006-10-05 Nippon Shokubai Co Ltd 高耐光性記録材料用紫外線吸収性ポリマー
JP4997816B2 (ja) 2006-04-14 2012-08-08 東洋インキＳｃホールディングス株式会社 紫外線遮断性樹脂組成物及びその利用
WO2008126699A1 (fr) * 2007-04-10 2008-10-23 Konica Minolta Opto, Inc. Polymère absorbant des ultraviolets, film optique d'ester de cellulose, procédé pour produire un film optique d'ester de cellulose, plaque de polarisation et affichage à cristaux liquides
JPWO2008126700A1 (ja) * 2007-04-10 2010-07-22 コニカミノルタオプト株式会社 光学フィルム、偏光板、液晶表示装置、及び紫外線吸収性ポリマー
JP5650963B2 (ja) 2010-09-13 2015-01-07 タレックス光学工業株式会社 保護眼鏡用遮光レンズ
JP6093949B2 (ja) * 2013-01-29 2017-03-15 新中村化学工業株式会社 ベンゾトリアゾール誘導体化合物及びそれらの重合体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63227575A (ja) * 1987-03-03 1988-09-21 アイオーラブ・コーポレーシヨン ベンゾトリアゾール化合物、その共重合体および紫外線吸収用組成物
WO2007108347A1 (fr) * 2006-03-20 2007-09-27 Konica Minolta Opto, Inc. Film optique d'acylate de cellulose, sa méthode de production, plaque polarisante utilisant ledit film et dispositif d'affichage à cristaux liquides
JP2009114430A (ja) * 2007-10-17 2009-05-28 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム、偏光板、及び表示装置
JP2012025811A (ja) * 2010-07-21 2012-02-09 Shinnakamura Kagaku Kogyo Kk 紫外線吸収性のベンゾトリアゾール系（共）重合体及びこれを含む塗料並びに該塗料がコーティングされたフィルム

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JP2018177976A (ja) 2018-11-15

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