JP2018168278A - Benzotriazole-based (co)polymer, ultraviolet-absorbing coating material containing the same, and film coated with coating material - Google Patents

Abstract

To provide a polymer having little coloration and excellent ultraviolet absorbing performance in the ultraviolet wavelength range of 300-400 nm, which may correspond to the spectral irradiance distribution of the ultraviolet components of sunlight arriving on the ground from the sun, in particular in the wavelength range of 330-400 nm, where the integrated energy is high.SOLUTION: Provided is a benzotriazole-based (co)polymer obtained by polymerizing a starting material comprising a resorcinol type benzotriazole monomer of the general formula in the figure. [Preferably, Rand Rare each H; Ris an alkyl group; and Ris H, an alkyl group, an alkyacryloyloxyalkyl group, or a methacryloyloxyalkyl group.]SELECTED DRAWING: Figure 1

Description

  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.

  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 properties in a relatively short region centered around 300 nm to 360 nm System copolymers are mainly used (for example, Patent Documents 1 to 3).

  In addition, 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).

  In a display device, 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. 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. .

  In addition, 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. In terms of protecting human eyes, it is a common practice to add ultraviolet absorbers to eyeglass lenses or contact lenses to prevent ultraviolet rays from reaching the eyes.

  In each of the above applications, it is required to sufficiently block ultraviolet rays, that is, it is required to sufficiently block light of 400 nm or less in sunlight. The 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 visible light short wavelength region 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.

JP 2006-021402 A

JP 2006-264212 A

JP 2000-034464 A

JP 2012-25811 A

  The alkanolphenol type benzotriazole-based polymers described in these publications have a weak wavelength absorption of 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 region of 400 to 420 nm and is colored yellow. Therefore, a paint using these and a paint thereof are coated. It has been difficult to use the film for optical film and spectacle lens applications.

  Moreover, even if a monomer that absorbs the ultraviolet wavelength region of 380 nm to 400 nm is added to the paint and a film coated with the paint and used in a blended state, elution and bleeding out of the ultraviolet absorbing component from the coating film, There were problems of crystallization of the absorbing component in the coating film and compatibility with other compounding materials.

  Therefore, the problem in the present invention is that the ultraviolet wavelength region of 300 to 400 nm that can correspond to the spectral irradiance distribution of the ultraviolet part of sunlight that reaches from the sun on the ground, particularly the ultraviolet absorption performance in the wavelength region of 330 to 400 nm with high accumulated energy. 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.

  In order to solve the above problems, 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.

  That is, 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.

一般式（１）
（式中、Ｒ_１およびＲ_２は、それぞれ独立して、水素原子、または炭素数１〜８のアルキル基を表し、Ｒ_３は水素原子、炭素数１〜１８のアルキル基、アルキル炭素数１〜７のカルボキシアルキル基、各アルキル炭素数の合計が２〜１５のアルキルオキシカルボニルアルキル基、炭素数１〜８のヒドロキシアルキル基、各アルキル炭素数の合計が２〜１５のアルキルカルボニルオキシアルキル基、ホルミル基、アルキル炭素数１〜７のアルキルカルボニル基、ベンゾイル基、またはトルオイル基を表し、Ｒ_４は、アルキル炭素数１〜４のアクリロイルオキシアルキル基、アルキル炭素数１〜４のアクリロイルオキシヒドロキシアルキル基、アルキル炭素数１〜４のメタクリロイルオキシアルキル基、またはアルキル炭素数１〜４のメタクリロイルオキシヒドロキシアルキル基である）

General formula (1)
(In the formula, R ₁ and R ₂ each independently represent 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; -7 carboxyalkyl group, alkyloxycarbonylalkyl group having 2 to 15 total alkyl carbon atoms, hydroxyalkyl group having 1 to 8 carbon atoms, alkylcarbonyloxyalkyl group having 2 to 15 total alkyl carbon atoms , A formyl group, an alkylcarbonyl group having 1 to 7 alkyl carbon atoms, a benzoyl group, or a toluoyl group, and R ₄ is an acryloyloxyalkyl group having 1 to 4 alkyl carbon atoms and an acryloyloxyhydroxy group having 1 to 4 alkyl carbon atoms. An alkyl group, an alkyl group having 1 to 4 carbon atoms, a methacryloyloxyalkyl group, or an alkyl group having 1 to 4 carbon atoms. Royloxyhydroxyalkyl group)

  As used herein, “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.

一般式（２）
（式中、Ｒ_５は水素原子またはメチル基を表し、Ｒ_６は炭素数１〜６の直鎖状または枝分かれ鎖状のアルキレン基を表し、Ｒ_７は水素原子または炭素数１〜１８の炭化水素基を表し、Ｒ_８は水素原子、ハロゲン基、炭素数１〜８の炭化水素基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表す） Further, 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)
(In the formula, 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)

  As used herein, “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). A molecular structure that is a derivative and has a polymerizable double bond introduced into the alkanolphenol moiety.

  The resorcinol-type benzotriazole monomer represented by the general formula (1) has a maximum absorption wavelength λmax of around 360 nm, a wide range of ultraviolet absorption spectrum covering 300 to 400 nm, and a length of around 400 nm. It has ultraviolet absorption ability up to the wavelength region.

  Therefore, 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 that can correspond 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 λmax 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.

  Therefore, in a preferred embodiment of the benzotriazole-based (co) polymer of the present invention, the resorcinol-type benzotriazole-based monomer represented by the general formula (1) [Chemical Formula 1] as the polymerizable monomer, By being copolymerized 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.

  Further, since the benzotriazole-based (co) polymer of the present invention is a polymer, it can form a coating film 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.

  Details of the present invention will be described below. 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.

In the resorcinol-type benzotriazole-based monomer represented by the general formula (1), 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 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 atoms and an acryloyloxyhydroxy group having 1 to 4 alkyl carbon atoms. It is a benzotriazole composed of an alkyl group, an alkyl group having 1 to 4 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-octyloxyphe) Nyl) -2H-benzotriazole-5-carboxylate and the like, but are not limited to the above specific examples. These benzotriazole monomers can be used alone or in combination of two or more.

Alkanol phenolic benzotriazole monomer of formula represented by the general formula (2), 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.

  Specific substance names of the alkanolphenol type benzotriazole monomer 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- (acryloyloxybutyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyhexyl) phenyl ] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (methacryloyloxyethyl) phenyl ] -2H-benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl ] -5-Chloro-2H-benzotri Sol, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -5-methoxy-2H -Benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -5-cyano -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -5 -T-butyl-2H-benzotriazole, 2- [2-hydroxy -5- (acryloyloxyethyl) phenyl] -5-t-butyl-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, 2- [2-Hydroxy-5- (acryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole and the like can be mentioned, but are not limited to the above specific examples. Moreover, these alkanol phenol type benzotriazole monomers can be used alone or in combination of two or more.

  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. For example, methyl (meth) acrylate, ethyl (Meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate (Meth) acrylic acid alkyl esters such as nonyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. 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. Furthermore, 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 α-methylstyrene are exemplified. Furthermore, carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and the like can be mentioned. Furthermore, sulfonic acid group-containing unsaturated monomers such as vinyl sulfonic acid and styrene sulfonic acid can be mentioned. Furthermore, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2- (meth) acryloyloxyethylphenyl phosphate And phosphoric acid group-containing unsaturated monomers.

  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-based monomer, and the method is not particularly limited.

  As a polymerization method when the monomer composition containing the benzotriazole monomer is copolymerized, 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.

  Although it does not restrict | limit especially as a radical polymerization initiator used when making it superpose | polymerize, For example, 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. Radical peroxide 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-tetramethyl Butyl hydroperoxide, di-t-butyl hydroperoxide, t-butyl-α-cumyl peroxide, di-t-butyl-α-cumylpa Oxide, di-α-cumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylper Examples thereof include organic peroxide radical polymerization initiators such as oxyacetate, t-butyl peroxybenzoate, and bis- (2-ethylhexyl) peroxydicarbonate. Furthermore, persulfate radical polymerization initiators such as potassium persulfate, ammonium persulfate, and sodium persulfate are listed. Further, the amount of the polymerization initiator used is not particularly limited.

  In an aqueous polymerization method such as an emulsion polymerization method, a redox initiator may be used by using sodium sulfite, L-ascorbic acid, Rongalite or the like as a reducing agent.

  When carrying out the copolymerization reaction, a chain transfer agent and a polymerization regulator may be used as necessary. Examples of chain transfer agents and polymerization regulators include n-dodecyl mercaptan, n-dodecyl mercaptan, β-mercaptopropionate 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. Moreover, 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, cetyltrimethyl chloride Ammonium chloride, octadecyloxypropyltrimethylammonium chloride, distearyldimethylammonium chloride, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, sodium polyacrylate, ammonium polyacrylate, styrene-sodium acrylate copolymer, styrene- Ammonium acrylate copolymer, styrene-alphamethylstyrene-sodium acrylate copolymer, styrene-alphamethylstyrene-ammonium acrylate copolymer, styrene-sodium maleate copolymer, styrene-ammonium maleate copolymer , Polyvinylpyrrolidone and the like are mentioned, but not particularly limited. Further, the amount of the surfactant used is not particularly limited.

  Examples of the dispersant that can be used in the suspension polymerization method 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.

  As described above, 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. That is, 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). ) A structure containing a polymer. More preferably, 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. In addition, 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.

  As a method for coating the film containing a benzotriazole-based (co) polymer with a paint, 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. However, it is not particularly limited. Furthermore, examples of the site where the coating film containing the benzotriazole-based (co) polymer of the present invention is present include, but are not particularly limited to, the front surface, back surface, both surfaces, and between layers.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples of benzotriazole-based (co) polymers, and paints including the same and films coated with the paints, but the present invention is limited to these aspects. It is not a thing. In the synthesis examples, examples and comparative examples, “%” indicates “% by weight” and “parts” indicates “parts by weight”.

[1. Synthesis of benzotriazole monomer)
(Synthesis Example 1)
[Intermediate (a); Synthesis of 5-carboxy-2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole]

  A 2000-ml four-necked flask was equipped with a condenser with a ball, a thermometer and a stirrer, and 875 ml of water, 56.5 g (0.533 mol) of sodium carbonate, 178.8 g of 4-amino-3-nitrobenzoic acid (0.982) Mol) was added and dissolved, and 197.1 g (1.028 mol) of 36% aqueous sodium nitrite solution was added. A 3000 ml four-necked flask was equipped with a condenser with a ball, a thermometer and a stirrer, and 875 ml of water and 372.0 g (2.370 mol) of 62.5% sulfuric acid were added and mixed. 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. Attach a condenser with a ball, a thermometer, and a stirrer to a 5000 ml four-necked flask, mix 139.4 g (1.009 mol) of 1,3-dimethoxybenzene, 900 ml of isopropyl alcohol, and 390 ml of water, and mix with a diazonium salt aqueous solution. Was added dropwise at 5 to 10 ° C., stirred at 5 to 10 ° C. for 2 hours, and then stirred at 10 to 15 ° C. for 15 hours. 280 ml of 32% aqueous sodium hydroxide solution was added, the lower aqueous layer was separated and removed at 70 ° C., and 75 ml of isopropyl alcohol and 875 ml of water were added, and the resulting precipitate was filtered, washed with water and dried. 218.3 g of carboxy-2-nitrophenylazo) -1,3-dimethoxybenzene was obtained.

  A condenser with a ball, a thermometer, and a stirrer were attached to a 3000 ml four-necked flask, 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. The pH was adjusted to 3 with 62.5% sulfuric acid, the lower aqueous layer was separated and removed at 70 ° C., the obtained organic layer was cooled to 25 ° C., 820 ml of water was added, and the mixture was stirred for 1 hour. The precipitate was filtered, washed with water and dried to obtain 158.9 g of 5-carboxy-2- (2,4-dimethoxyphenyl) -2H-benzotriazole N-oxide.

  A 3000 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirrer, and 156.8 g (0.497 mol) of 5-carboxy-2- (2,4-dimethoxyphenyl) -2H-benzotriazole N-oxide. ), 780 ml of isopropyl alcohol, 780 ml of water, 295.8 g (2.366 mol) of a 32% aqueous sodium hydroxide solution, and 255.9 g (2.367 mol) of thiourea dioxide at 70 to 80 ° C. over 30 minutes. added. Stir at the same temperature for 2 hours, adjust to pH 4 with 62.5% sulfuric acid, separate and remove the lower aqueous layer, add 480 ml of isopropyl alcohol and 480 ml of water, and cool the resulting organic layer to 25 ° C. Then, the produced precipitate was filtered, washed with water, and dried to obtain 107.4 g of 5-carboxy-2- (2,4-dimethoxyphenyl) -2H-benzotriazole. The yield was 37% (from 4-amino-3-nitrobenzoic acid).

(Synthesis Example 2)
[Intermediate (b); Synthesis of 5-carboxy-2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole]

  A condenser with a ball, a thermometer, and a stirrer were attached to a 2000 ml four-necked flask, 107.1 g (0.358 mol) of 5-carboxy-2- (2,4-dimethoxyphenyl) -2H-benzotriazole, acetic acid 540 ml, 62.5% sulfuric acid 365.2 g (2.327 mol) and 95% sulfuric acid 221.8 g (2.148 mol) were added and stirred at 130-140 ° C. for 20 hours. Was filtered and washed with water to obtain crude crystals. The obtained crude crystals were repulp washed with 130 ml of isopropyl alcohol and 300 ml of 4-methyl-2-pentanone to obtain 59.5 g of 5-carboxy-2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole. It was. The yield was 58% (from 5-carboxy-2- (2,4-dimethoxyphenyl) -2H-benzotriazole).

・・・化合物（ａ） (Synthesis Example 3)
[Compound (a); Synthesis of 2-methacryloyloxyethyl 2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole-5-carboxylate]

... Compound (a)

  A condenser with a ball, a thermometer, and a stirrer were attached to a 2000 ml four-necked flask, and 59.5 g (0.209 mol) of 5-carboxy-2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole. , 900 ml of toluene, 3.6 ml of N, N-dimethylformamide, 93.1 g (0.783 mol) of thionyl chloride were added, and the mixture was stirred at 60 to 65 ° C. for 20 hours. Subsequently, the solvent was recovered under reduced pressure, 415 ml of toluene and 271.9 g (2.089 mol) of 2-hydroxyethyl methacrylate were added, and the mixture was stirred at 80 ° C. for 15 hours. After adding 400 ml of water and separating and removing the lower aqueous layer at 70 ° C., and repeating the operation of adding 300 ml of water and separating the lower aqueous layer at 70 ° C. three times, the solvent was recovered under reduced pressure. Then, 190 ml of isopropyl alcohol and 40 ml of water were added and cooled to 5 ° C., and the resulting precipitate was filtered, washed and dried to obtain crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 19.2 g of compound (a). The yield was 23% (from 5-carboxy-2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole).

The purity of the compound (a) was measured by HPLC analysis.
<Measurement conditions>
Apparatus: LC-20AT (manufactured by Shimadzu Corporation)
Column used: SUMPAX ODS A-212 6.0 × 150 mm 5 μm
Column temperature: 25 ° C
Mobile phase: Methanol / water = 95/5 (phosphoric acid 3 ml / L)
Flow rate: 1.0 ml / min
Detection: UV250nm
<Measurement results>
HPLC area percentage purity 97.2%

Moreover, as a result of conducting NMR measurement of the compound (a), a result supporting the above structure was obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: JEOL JNM-AL300
Resonant frequency: 300 MHz (1H-NMR)
Solvent: chloroform-d
Tetramethylsilane was used as an internal standard of 1H-NMR, the chemical shift value was represented by δ value (ppm), and the coupling constant was represented by Hertz. S is a singlet, d is a doublet, t is a triplet, and m is a multiplet. The same applies to Examples 4 to 8 below. In addition, the following Examples 4-8 also performed NMR measurement on the measurement conditions similar to a present Example. The contents of the obtained NMR spectrum are as follows.
δ = 11.27 (s, 1H, phenol-OH), 8.71 (m, 1H, benzotriazole-H), 8.32 (d, 1H, J = 9.0 Hz, benzotriazole-H), 8.04 (M, 2H, benzotriazole-H, phenol-H), 6.71 (d, 1H, J = 3.0 Hz, phenol-H), 6.64 (m, 1H, phenol-H), 6.18 ( _{m, 1H, C = CH 2} -H), 5.62 (m, 1H, C = CH 2 -H), 4.60 (m, 4H, methacryloyl-O-CH 2 -CH 2 -H), 3 .94 (s, 3H, phenol-O—CH ₃ —H), 1.97 (m, 3H, CH ₂ ═C—CH ₃ —H)

(Synthesis Example 4)
[Compound (b); Synthesis of 2-methacryloyloxyethyl 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate]

  Attach a condenser with a ball, a thermometer, and a stirrer to a 1000 ml four-necked flask, add 106.0 g (1.340 mol) of pyridine, and then add 197.0 g (1.945 mol) of 36% hydrochloric acid over 15 minutes. The mixture was stirred for 1.5 hours, and 100 g of the solvent was recovered to obtain a slurry of pyridine hydrochloride. Subsequently, 20.0 g (0.067 mol) of 5-carboxy-2- (2,4-dimethoxyphenyl) -2H-benzotriazole was added, stirred at 160 ° C. for 21 hours, cooled to 70 ° C., and 250 ml of water was added. In addition, the pH was adjusted to 3 with a 32% aqueous sodium hydroxide solution. The precipitate formed upon cooling to 30 ° C. was filtered, washed with water, and dried to obtain 18.1 g of 5-carboxy-2- (2,4-dihydroxyphenyl) -2H-benzotriazole. The yield was 100% (from 5-carboxy-2- (2,4-dimethoxyphenyl) -2H-benzotriazole).

  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, 1.3 g of polyethylene glycol 400 were added, and 130- Stir at 140 ° C. for 3 hours. Add 100 ml of toluene and 100 ml of water, separate and remove the lower aqueous layer at 70 to 75 ° C., add 100 ml of water and 2 ml of acetic acid, and separate the lower aqueous layer at 70 to 75 ° C. Removed. Toluene was recovered under reduced pressure, 40 ml of isopropyl alcohol was added, and the resulting precipitate was filtered, washed and dried to obtain 5.6 g of crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 4.7 g of octyl 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate. The yield was 29% (from 5-carboxy-2- (2,4-dihydroxyphenyl) -2H-benzotriazole).

  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. 12.5 ml of 62.5% sulfuric acid was added to adjust the pH to 5, and the resulting precipitate was filtered, washed and dried to give 5-carboxy-2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole. 2.5 g was obtained.

  A 200 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, and 2.5 g (0.0065 mol) of 5-carboxy-2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole. ), 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. . 30 ml of water and 0.5 ml of 62.5% sulfuric acid were added, the lower aqueous layer was separated and removed at 70 to 75 ° C., toluene was recovered under reduced pressure, and 30 ml of isopropyl alcohol was added to form a precipitate. Was filtered, washed and dried to obtain 2.2 g of crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 1.4 g of compound (f). The yield was 42% (from octyl 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate).

Moreover, the purity of the compound (b) was measured by HPLC analysis.
<Measurement conditions>
Device: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUMPAX ODS A-212 6.0 × 150 mm 5 μm
Column temperature: 40 ° C
Mobile phase: Methanol / water = 99/1
Flow rate: 1.0 ml / min
Detection: UV250nm
<Measurement results>
HPLC area percentage purity 94.8%

Further, as a result of NMR measurement of the compound (b), a result supporting the above structure was obtained. The contents of the obtained NMR spectrum are as follows.
δ = 12.44 (s, 1H, phenol-OH), 8.70 (s, 1H, benzotriazole-H), 8.31 (d, 1H, J = 12.9 Hz, benzotriazole-H), 8.11 (D, 1H, J = 10.5 Hz, benzotriazole-H), 7.95 (d, 1H, J = 9.0 Hz, phenol-H), 6.69 (m, 2H, phenol-H), 6. _{18 (s, 1H, C =} CH 2 -H), 5.62 (s, 1H, C = CH 2 -H), 4.64 (m, 2H, methacryloyl-O-CH 2 -H), 4. _{56 (m, 2H, benzotriazole-} CO-O-CH 2 -H), 4.01 (t, 2H, phenol-O-CH 2 -H), 1.97 (s, 3H, CH 2 = C-CH ₃ -H), 1.4 5 (m, 12H, octyl-CH ₂ ), 0.90 (s, 3H, octyl-CH ₃ )

[2. Commercially available benzotriazole monomer)
As the alkanolphenol type benzotriazole-based monomer, commercially available 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole (Otsuka Chemical RUVA-93) was used. Hereinafter, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole is referred to as “compound (c)”.

[3. (Sesamol type benzotriazole-based monomer commercial product)
The sesamol type benzotriazole monomer is a commercially available 2- [2- (6-hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3benzotriazol-5-yl]. Ethyl methacrylate (Cypro Kasei R26) was used. Hereinafter, 2- [2- (6-hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3benzotriazol-5-yl] ethyl methacrylate is referred to as “compound (d)”. .

[4. Synthesis of benzotriazole (co) polymer]
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 .5 parts was added, 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 in a reflux state at a reaction solution 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.

(Example 2)
The monomer composition in Example 1 is 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)
In Example 1, 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.

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.

(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.

(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.

[4. Evaluation)
Nonvolatile content, solution viscosity, molecular weight, and maximum absorption wavelength λmax of the UV-absorbing copolymer, UV absorption of the UV-absorbing copolymer solutions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 above. The spectrum was measured. In addition, 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.

  The 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 polystyrene-converted weight average molecular weight (Mw) using a polystyrene calibration curve, Number average molecular weight (Mn) and polydispersity (Mw / Mn) were measured.

  The maximum absorption wavelength λmax and the ultraviolet absorption spectrum are obtained by removing the solvent from the obtained UV-absorbing copolymer solution by drying under reduced pressure to obtain a 40 ppm chloroform solution, and using a spectrophotometer (Hitachi High-Technologies Corporation U-3900H) It measured using.

  The ultraviolet ray blocking function test was performed using the ultraviolet absorbing copolymer solution obtained in Examples 1 to 3 and Comparative Examples 1 and 2 to prepare an ultraviolet absorbing copolymer-containing coating material, and coating the coating material. The ultraviolet absorption blocking performance of the dye used for sublimation transfer printing with a film was confirmed. The procedure is described below.

  To 5 parts of toluene and 5 parts of MEK were added to 10 parts of the UV-absorbing copolymer solution obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and a paint containing the UV-absorbing copolymer was prepared. A polyester film (Toyobo Co., Ltd., Cosmo Shine A-4300, 100 micron, double-sided easy adhesion treatment) was coated with the above-mentioned paint with a bar coater # 20, dried at 80 ° C. for 1 minute, and further at 100 ° C. for 30 The coating film containing the UV-absorbing copolymer was obtained by drying for 2 seconds. The film thickness of the coating film containing the ultraviolet absorbing copolymer using a film thickness meter (FILMETRICS F20) was about 3 μm.

  Subsequently, 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 (Canon SELPHY CP600) were obtained. In accordance with JISK5701-1: 2000, 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.

  Similarly, using the transfer film of the dye, the transfer film is protected with a glass plate coated with the paint containing the respective UV-absorbing copolymers prepared as described above. Similarly, 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

  For Examples 1 to 3 and Comparative Examples 1 and 2, coloring was measured. For the measurement of coloring, b * and YI values were measured using a color difference meter (Nippon Denshoku Industries Co., Ltd. SE6000). For the measurement, 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.

  Non-volatile content, molecular weight, maximum absorption wavelength λmax of the UV-absorbing copolymer solutions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 and absorbance at wavelength regions of 300 nm, 360 nm, 400 nm, 420 nm, and 450 nm. , UV blocking function test evaluation results, elution of ultraviolet absorbing component from coating film, bleed out, crystallization, blending material compatibility confirmation test results of coating state change are shown in Table 1, and UV absorption spectrum is shown in FIGS. It was shown to.

The meanings of the symbols in Table 1 are as follows.
“Compound (a)”: 2-methacryloyloxyethyl 2- (2-hydroxy-4-methoxyphenyl) -2H-benzotriazole-5-carboxylate “Compound (b)”: 2-methacryloyloxyethyl 2- (2 -Hydroxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate "Compound (c)": 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole "Compound ( d) ": 2- [2- (6-Hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3benzotriazol-5-yl] ethyl methacrylate" MMA ": methyl Methacrylate “St”: Styrene “HEMA”: 2-hydroxyethyl methacrylate “CHMA” Cyclohexyl methacrylate "HALS": 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine "AMBN": 2,2'-azobis - methylbutyronitrile "MEK": Methyl ethyl ketone

  As is clear from the results of Examples 1 to 4, 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. Further, it was found from the b * and YI values of the color difference measurement that there was less coloring compared with the conventional material having absorption in the vicinity of 400 nm. In addition, it was also found that there is no problem of elution or bleeding out of the ultraviolet absorbing component from the coating film, crystallization of the ultraviolet absorbing component in the coating film, or compatibility with other compounding materials.

  The benzotriazole-based (co) polymer of the present invention absorbs a wide wavelength region 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. Further, in 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.

Claims (5)

A benzotriazole-based (co) polymer obtained by polymerizing a raw material containing a resorcinol-type benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer.

General formula (1)
(In the formula, R ₁ and R ₂ each independently represent 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; -7 carboxyalkyl group, alkyloxycarbonylalkyl group having 2 to 15 total alkyl carbon atoms, hydroxyalkyl group having 1 to 8 carbon atoms, alkylcarbonyloxyalkyl group having 2 to 15 total alkyl carbon atoms , A formyl group, an alkylcarbonyl group having 1 to 7 alkyl carbon atoms, a benzoyl group, or a toluoyl group, and R ₄ is an acryloyloxyalkyl group having 1 to 4 alkyl carbon atoms and an acryloyloxyhydroxy group having 1 to 4 alkyl carbon atoms. An alkyl group, an alkyl group having 1 to 4 carbon atoms, a methacryloyloxyalkyl group, or an alkyl group having 1 to 4 carbon atoms. Royloxyhydroxyalkyl group) In the general formula (1), R ₁ and R ₂ are hydrogen atoms, R ₃ is an alkyl group having 1 to 8 carbon atoms, and R ₄ is an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms, or an alkyl carbon. The benzotriazole-based (co) polymer according to claim 1, which is a methacryloyloxyalkyl group having a number of 1 to 2. The benzotriazole copolymer according to claim 1 or 2, further comprising an alkanolphenol type benzotriazole monomer represented by the general formula (2) as the polymerizable monomer.

General formula (2)
(In the formula, 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)   The ultraviolet absorptive coating material containing the benzotriazole type | system | group (co) polymer in any one of Claims 1-3.   A film coated with the ultraviolet absorbing paint according to claim 4.

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