JP2018177976A - Benzotriazole (co)polymer, ultraviolet absorbing coating material containing the same, and film coated with the coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having absorption in a wide ultraviolet wavelength region of 300-400 nm, while absorbing light in a short-wavelength visible light region up to around 450 nm.SOLUTION: A benzotriazole (co)polymer is obtained by polymerizing a starting material that contains a methoquinone-type benzotriazole monomer of the general formula in the figure. (In the formula, Rrepresents a hydrogen atom or an alkyl group; Rrepresents an alkyl group; and Rrepresents an acryloyloxyalkyl group or a methacryloyloxyalkyl group.)SELECTED DRAWING: Figure 1

Description

  The present invention relates to a benzotriazole (co) polymer having ultraviolet absorbing ability and absorbing ultraviolet light in a wide wavelength range and light in a visible short wavelength range, a paint containing the same, and a film coated with the paint It is.

  Traditionally, absorption and blocking of ultraviolet light, prevention of elution and bleed out of ultraviolet light absorbing component from coating film, prevention of crystallization of ultraviolet light absorbing component in coating film, improvement of weather resistance of coating film, other resins and compounding materials Ultraviolet-absorbing (co) polymers are used for the purpose of improving the compatibility with these.

  Benzotriazole formed by copolymerizing a monomer composition containing one or more kinds of alkanolphenol-type benzotriazole-based ultraviolet absorbing monomer having ultraviolet absorptivity in a relatively short range centered on about 300 nm to 360 nm The copolymer is mainly used (for example, patent documents 1-2).

  A monomer containing one or more sesamol-type benzotriazole-based ultraviolet absorbing monomers as having absorption near 400 nm in a relatively long wavelength range, which was insufficient with alkanolphenol-type benzotriazole-based copolymers A benzotriazole copolymer obtained by copolymerizing a composition is used (for example, Patent Document 3).

  These benzotriazole-based ultraviolet absorbing monomers are generally used, for example, for preventing discoloration of optical films by adding an ultraviolet absorber to an optical film such as a polarizing plate protective film in a display device. It is used. Moreover, in order to prevent the deterioration by the ultraviolet ray of the near-infrared absorber contained in an antireflection film, the ultraviolet absorber is added to the antireflection film. In addition, various organic substances such as fluorescent materials and phosphorescent materials are used in the light emitting element of the organic EL display, and in order to prevent the deterioration of the organic substances by ultraviolet rays, an ultraviolet absorber is added to the surface film of the display. .

  In the human body, it is well known that ultraviolet rays cause sunburn of the skin and eyes and causes various diseases. In order to prevent various diseases of the eyes due to ultraviolet rays, an ultraviolet absorber is used as a spectacle lens or a contact lens It is common practice to add to prevent ultraviolet light from reaching the eye.

  In addition, in recent years, it has been pointed out that not only ultraviolet rays of 400 nm or less among sunlight but also light in the short wavelength region of visible light of about 400 to 450 nm will damage organic substances and the human body, including the above applications In the above applications, a light absorbing agent capable of absorbing light in the short wavelength range of visible light is required.

  In each of the above applications, a light absorbing agent for efficiently absorbing ultraviolet light and light in a short wavelength range of visible light is proposed, and as a compound having absorption in such a wavelength range, for example, Patent Documents 4 to 5 As described in indole derivatives, pyrrolidine-amide derivatives, xanthone derivatives are mentioned. However, since these compounds generally have low light resistance, they are deteriorated by exposure to sunlight and their light absorbing ability is reduced, and thus they can not be used for a long time. Moreover, there is no description of light resistance in patent documents 4-5.

  The sesamol-type benzotriazole-based copolymer generally known as high light resistance of Patent Document 3 can absorb ultraviolet light and light in the short wavelength range of visible light, but has a weak absorption at 420 nm or more, and 300 to 300 There is a problem that the absorption in the ultraviolet region around 330 nm is somewhat weak.

JP, 2006-021402, A

Unexamined-Japanese-Patent No. 2006-264312

JP, 2012-25811, A

JP 2012-58643 A

JP 2007-284516 A

  The alkanolphenol-type benzotriazole-based polymer and the sesamol-type benzotriazole-based polymer described in these publications do not have absorption capability in the visible short wavelength region of 420 to 450 nm, and a paint using these and a paint thereof are coated The visible light short wavelength region blocking performance of the film was insufficient.

  In addition, even if a paint and a film coated with the same are added in a visible light short wavelength range of 400 nm to 450 nm and added in a compounded state, elution or bleeding of the UV absorbing component from the coating film is caused. There is a problem of out, crystallization of the absorbing component in the coating film and compatibility with other compounding materials.

  Then, the subject in the present invention is a benzotriazole (co) polymer having absorption performance in a wide ultraviolet wavelength range of 300 to 400 nm while absorbing light in the visible short wavelength range up to around 450 nm, a paint containing the same, It is in providing the film which coated the paint.

  MEANS TO SOLVE THE PROBLEM In order to solve said subject, as a result of examining this invention about the coating film which coated the ultraviolet absorption benzotriazole type copolymer, it, and the coating material, the conventional benzotriazole type monomer is obtained. We have found a benzotriazole-based (co) polymer formed by polymerizing or copolymerizing a raw material monomer containing a benzotriazole-based monomer having a novel molecular structure different from the above.

  That is, according to the present invention, it is most preferable to use a benzotriazole-based ultraviolet-absorbing polymer formed by polymerizing a raw material containing a methoquinone-type benzotriazole-based monomer represented by the general formula (1) as a polymerizable monomer. It is the main feature.

・・・・・一般式（１）
（式中、Ｒ_１は水素原子または炭素数１〜８のアルキル基を表す。Ｒ_２は炭素数１〜８のアルキル基を表す。Ｒ_３はアルキル炭素数１〜２のアクリロイルオキシアルキル基、またはアルキル炭素数１〜２のメタクリロイルオキシアルキル基を表す。）

......... General formula (1)
(Wherein, 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, Or alkyl having 1 to 2 carbon atom methacryloyloxyalkyl groups).

  The term "methoquinone-type benzotriazole-based monomer" as used herein refers to a phenol having an alkoxy at the meta-position at the 2-position nitrogen atom of the benzotriazole ring as represented by the general formula (1). It is a derivative from the compound to which it couple | bonded, and the molecular structure which introduce | transduced the polymerizable double bond into the carboxyl group introduce | transduced into the benzene site of this benzotriazole ring is said.

  Furthermore, as the above-mentioned polymerizable monomer, an alkanolphenol-type benzotriazole-based monomer represented by the general formula (2) [Formula 2] is further contained as a raw material, and a benzo obtained by copolymerizing this It is preferable to set it as a triazole type ultraviolet-absorbing polymer.

・・・・・一般式（２）
（式中、Ｒ_４は水素原子またはメチル基を表し、Ｒ_５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_６は水素原子または炭素数１〜１８の炭化水素基を表し、Ｒ_７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）

......... General formula (2)
(Wherein, 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, and R ₆ represents a hydrogen atom or carbonized 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)

  The “alkanolphenol-type benzotriazole-based monomer” referred to in the present specification is a compound in which 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 which is a derivative and in which a polymerizable double bond is introduced to the alkanol phenol moiety.

  The methoquinone type benzotriazole monomer represented by the above general formula (1) has two maximum absorption wavelengths λmax in the vicinity of 310 nm and 380 nm, and a wide range of ultraviolet wavelength range and visible range covering 300 to 450 nm wavelength range It has an absorption spectrum in the light short wavelength region, and has the ability to absorb visible light short wavelengths up to around 450 nm.

  Therefore, the benzotriazole-based (co) polymer of the present invention, the paint containing the same, and the film coated with the same have a wide wavelength range of 300 to 450 nm that can correspond to the spectral irradiance distribution of the ultraviolet portion of sunlight on the ground. The coating composition of the present invention is excellent in the absorption performance in the visible light short wavelength region, and the paint containing the same and the film coated with the coating are excellent in the absorption performance and the ultraviolet blocking performance of the ultraviolet light and the visible light short wavelength.

  The alkanolphenol-type benzotriazole-based monomer represented by the general formula (2) is an existing known benzotriazole-based monomer generally used for benzotriazole-based ultraviolet absorbing polymers at present. A typical industrial product is 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole. The maximum absorption wavelength λmax has an ultraviolet absorption spectrum in the range covering 338 nm and 250 to 380 nm, but the ultraviolet absorption ability in the long wavelength region of 380 nm or more is extremely low.

  Therefore, in a preferred embodiment of the benzotriazole (co) polymer of the present invention, a methoquinone type benzotriazole monomer represented by the general formula (1) [Chemical formula 1] as a raw material monomer, and the above general formula (2) By the copolymerization with a raw material monomer containing an alkanolphenol type benzotriazole-based monomer represented by [Chemical formula 2], the absorption performance is excellent in a further broad ultraviolet region of 250 to 450 nm. The paint containing the same and the film coated with the paint are further excellent in the ultraviolet absorbing performance and the ultraviolet blocking performance.

  In addition, the benzotriazole (co) polymer of the present invention is a polymer and therefore can form a coating film by itself. Therefore, there is no problem of elution or bleeding out of the UV absorbing component from the coating film. Furthermore, it is possible to freely change the polarity of the polymer by appropriately selecting a monomer other than the ultraviolet ray absorbing monomer constituting the polymer to make a copolymer. Therefore, there is no problem of crystallization of the UV absorbing component in the coating film or compatibility with other resins or compounding materials.

1 is an ultraviolet absorption spectrum of a compound of Example 1 of the present invention. It is a ultraviolet-ray absorption spectrum of a compound of example 2 of the present invention. It is an ultraviolet absorption spectrum of the compound of this invention Example 3. It is an ultraviolet absorption spectrum of the compound of this invention Example 4. 5 is an ultraviolet absorption spectrum of a compound of Comparative Example 1; 7 is an ultraviolet absorption spectrum of a compound of Comparative Example 2.

  The details of the present invention will be described below. The benzotriazole type ultraviolet absorbing polymer of the present invention is formed by polymerizing or copolymerizing a raw material containing the methoquinone type benzotriazole type monomer represented by the general formula (1) as a polymerizable monomer. Further, it is obtained by copolymerizing a raw material further represented by the general formula (2) and containing an alkanolphenol type benzotriazole type monomer as a polymerizable monomer. In addition, the said raw material may also contain another polymerizable monomer as needed.

In the methoquinone type benzotriazole-based monomer represented by the above general formula (1), the substituent represented by R ₁ is composed of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and is represented by R ₂ The substituent to be substituted is composed of an alkyl group having 1 to 8 carbon atoms, and the substituent represented by R ₃ is an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms, or a methacryloyloxyalkyl group having 1 to 2 alkyl carbon atoms. And benzotriazoles.

  As a specific substance name of the methoquinone type benzotriazole monomer, 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-) Although methoxyphenyl) -2H-benzotriazole-5-carboxylate etc. can be mentioned, it is not limited to the above-mentioned specific example. Further, these methoquinone type benzotriazole monomers can be used alone or in combination of two or more.

In the alkanolphenol-type benzotriazole monomer represented by the general formula (2), in the formula, the substituent represented by R ₄ is a hydrogen atom or a methyl group, and the substituent represented by R ₅ is a carbon A linear or branched alkylene group of 1 to ₆ ; 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; They are benzotriazoles constituted by 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 a specific substance name of the alkanol phenol type benzotriazole monomer, 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- ( Tacryloyloxybutyl) 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-t-butyl-5- (methacryloyloxyethyl) phenyl] ] -2H-benzotriazole, 2- [2-hydroxy-3-t-butyl-5- (acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl ] -5-Chloro-2H-benzotriazo , 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 Examples include -hydroxy-5- (acryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole and the like, but are not limited to the above specific examples. Moreover, these alkanol phenol type benzotriazole type monomers can also be used by one type, and can also use two or more types.

  The benzotriazole copolymer of the present invention may be copolymerized with a polymerizable monomer other than the above benzotriazole monomer as a polymerizable monomer which is a raw material of the copolymer. The other polymerizable monomers that can be copolymerized with the benzotriazole-based monomer are 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 And (meth) acrylic acid alkyl esters such as nonyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate. Examples include hydroxyl group-containing unsaturated monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl ethyl (meth) acrylate, hydroxybutyl (meth) acrylate and caprolactone modified hydroxy (meth) acrylate. Further, oxide ring-containing unsaturated monomers such as glycidyl (meth) acrylate and oxetane (meth) acrylate can be mentioned. Furthermore, nitrogen-containing unsaturated compounds such as (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, (meth) acryloyl morpholine, vinylpyridine, vinylimidadol, N-vinylpyrrolidone and the like Monomers are mentioned. Furthermore, halogen-containing unsaturated monomers such as vinyl chloride and vinylidene chloride can be mentioned. Furthermore, aromatic unsaturated monomers such as styrene and α-methylstyrene can be mentioned. Further, carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and the like can be mentioned. Further, 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) acryloyloxyethyl phenyl phosphate And phosphoric acid group-containing unsaturated monomers.

  A known method can be used for the method of adjusting the raw material, such as the method of mixing the raw material containing the above-mentioned benzotriazole-based monomer, and the method is not particularly limited.

  As the polymerization method for copolymerizing the monomer composition containing the above benzotriazole-based monomer, it is possible to adopt conventionally known solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method, etc. There is no particular limitation.

  The radical polymerization initiator to be used in the polymerization reaction is not particularly limited, and, for example, 2,2'-azobis- (4-methoxy-2.4-dimethylvaleronitrile), 2,2'-azobis- (2,2, 4-Dimethylvaleronitrile), dimethyl 2,2′-azobis- (2-methyl propionate), 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. And hydrogen peroxide, dibenzoyl peroxide, dilauroyl peroxide, diisobutyryl peroxide, bis (3,5,5-) trimethylhexanoyl peroxide, methyl ethyl ketone peroxide, and the like. Methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone 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-cumylper Oxide, di-α-cumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxide Organic peroxide based radical polymerization initiators such as oxyacetate, t-butylperoxybenzoate, bis- (2-ethylhexyl) peroxydicarbonate and the like can be mentioned. Further, persulfate-based radical polymerization initiators such as potassium persulfate, ammonium persulfate, sodium persulfate and the like can be mentioned. The amount of polymerization initiator used is also not particularly limited.

  In the aqueous polymerization method such as the 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, if necessary. Chain transfer agents and polymerization regulators include n-dodecyl mercaptan, n-dodecyl mercaptan, methyl β-mercaptopropionate-3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl-3 -Mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, thioglycolic acid, ammonium thioglycollate, monoethanolamine thioglycollate, alpha methyl styrene dimer, etc. It is not particularly limited. Further, the amounts of chain transfer agent and polymerization regulator used are not particularly limited.

  Examples of the solvent that can be used in the solution polymerization method include toluene, xylene, ethyl acetate, butyl acetate, cellosolve acetate, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and the like, but are not particularly limited. Also, the amount of the solvent used is not particularly limited.

  As surfactants which can be used in the emulsion polymerization method, sodium lauryl sulfate, ammonium lauryl sulfate, polyoxyethylene lauryl ether sodium acetate, polyoxyethylene lauryl ether ammonium acetate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether Ammonium sulfate, sodium dodecyl benzene sulfonate, ammonium dodecyl benzene sulfonate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl dodecyl ether, lauryl trimethyl ammonium chloride, Stearyl trimethyl ammonium chloride, cetyl chloride Ammonium, octadecyloxypropyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, partially saponified polyvinyl alcohol, completely 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 And polyvinyl pyrrolidone and the like, but are not particularly limited. The amount of surfactant used is also not particularly limited.

  Examples of the dispersant that can be used in the suspension polymerization method include partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, sodium polyacrylate, methyl cellulose, carboxymethyl cellulose, polyethylene oxide and the like, 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., and 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 conditions may be appropriately set to complete the polymerization reaction according to the composition of the monomer composition to be used, the type of the polymerization initiator, and the like.

  As described above, 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. Configuration. More preferably, it is the structure formed by (co) polymerizing the raw material which further contains the alkanol phenol type benzotriazole type monomer represented by General formula (2) as a polymerizable monomer. That is, since it is (co) polymerized with a raw material containing an ultraviolet absorbing monomer having an ultraviolet absorbing ability in the entire wavelength region of 280 to 400 nm, a wide range of ultraviolet light covering the entire wavelength region of 280 to 450 nm It has absorption in the wavelength range and the visible short wavelength range, and has the ability to absorb visible short wavelengths up to around 450 nm.

  A paint containing a benzotriazole (co) polymer according to the present invention is a benzotriazole (co) obtained by (co) polymerizing a raw material containing a methoquinone type benzotriazole monomer represented by the general formula (1). A) containing a polymer. More preferably, the composition contains a benzotriazole-based copolymer obtained by copolymerizing the above-mentioned raw material which further contains an alkanolphenol-type benzotriazole-based monomer represented by the general formula (2). The form of the paint includes water-based paint, solvent-based paint, UV-curable paint, thermosetting paint, clear paint, pigment paint, dye paint and the like, but is not particularly limited. In addition, materials other than the benzotriazole (co) polymer constituting the paint, such as resins, solvents, crosslinking agents, curing agents, catalysts, fillers, leveling agents, plasticizers, stabilizers, dyes, pigments, etc., are particularly limited. It can be selected appropriately and used.

  A film coated with a paint containing the benzotriazole (co) 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). It is a film coated with a paint having a configuration containing a benzotriazole (co) polymer. More preferably, it is a film coated with a paint comprising a benzotriazole copolymer obtained by copolymerizing a raw material further containing an alkanolphenol type benzotriazole monomer represented by the general formula (2). . Types of films include polyester films, cellulose films, polyolefin films, polyamide films, polystyrene films, vinyl chloride films, vinylidene chloride films, polyvinyl alcohol films, polycarbonate films, polyimide films, etc. However, it is not particularly limited.

  As a method of coating a paint containing a benzotriazole (co) polymer on the above film, a paint containing the above benzotriazole (co) polymer may be 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 coating, electrodeposition coating extrusion coater, Langmuir-Blodgett (LB) method, etc. However, it is not particularly limited. Furthermore, as the existence site of the coating film containing the benzotriazole (co) polymer of the present invention, the front surface, back surface, both surfaces of the film, between layers, etc. may be mentioned, but it is not particularly limited.

  The present invention will be described in more detail by the following examples and comparative examples of benzotriazole-based (co) polymers, and paints containing the same and films coated with the paints, but the present invention is limited to these embodiments. It is not a thing. In addition, "%" as described in a synthesis example and an Example and a comparative example shows "weight%", and "part" shows a "weight part."

・・・化合物（ａ） [1. Synthesis of benzotriazole-based monomer]
Synthesis Example 1
[Compound (a): Synthesis of 2-methacryloyloxyethyl 2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole-5-carboxylate]

... Compound (a)

  A 200-ml four-necked flask is equipped with a condenser with ball, thermometer and stirrer, and 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 a 36% aqueous solution of sodium nitrite was added. Attach this solution to a 500 ml four-necked flask, attach a ball condenser, thermometer, and stirrer, add 100 ml of water, 43.0 g (0.274 mol) of 62.5% sulfuric acid, and mix to 3-7 ° C. It was added dropwise to the cooled one and stirred at the same temperature for 2 hours to obtain an aqueous diazonium salt solution. Attach a beaded condenser, 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. After adding an aqueous solution of diazonium salt dropwise at 5 to 10 ° C. and stirring at 5 to 10 ° C. for 2 hours, the solution is stirred at 10 to 15 ° C. for 12 hours, 2-tert-butyl-6- (4-carboxy-2-nitro) A slurry of phenylazo) -4-methoxyphenol was obtained. 27.8 g (0.222 mol) of a 32% aqueous sodium hydroxide solution and 200 ml of isopropyl alcohol were added, and the lower aqueous layer was separated and removed at 70 ° C. Add 30.0 g (0.222 mol) of a 32% aqueous solution of sodium hydroxide, 200 ml of water, and 0.4 g of hydroquinone, and add 6.0 g (0.072 mol) of 60% hydrazine monohydrate at 40 to 50 ° C. for 1 hour The mixture was added dropwise and allowed to stir at the same temperature for 2 hours. The pH is adjusted to 4 with 62.5% sulfuric acid, and the precipitate formed is filtered, washed with water, dried and 5-carboxy-2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole 23.6 g of N-oxide were obtained.

  Attach a beaded condenser, thermometer, and stirrer to a 500 ml four-necked flask, and attach 5-carboxy-2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole N-oxide Add 23.6 g (0.066 mol), 100 ml of isopropyl alcohol, 100 ml of water, 24.0 g (0.192 mol) of 32% aqueous sodium hydroxide solution, and add 12.0 g (0. 111 mol) were added over 3 hours. The mixture is stirred at the same temperature for 1 hour, the lower aqueous layer is separated and removed, adjusted to pH 4 with 62.5% sulfuric acid, and the formed precipitate is filtered, washed with water and dried to give 5-carboxy-2- 20.3 g of (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole was obtained.

  Attach a beaded condenser, thermometer, and stirrer to a 300 ml four-necked flask, and 20.3 g of 5-carboxy-2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole (0.059 mol), 100 ml of toluene, 13.0 g (0.109 mol) of thionyl chloride, and 2.0 ml of N, N-dimethylformamide were added and 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 are added, the lower aqueous layer is separated and removed at 60 to 70 ° C., and 20 ml of water is further added to obtain 60 ° to 70 ° C. The lower aqueous layer was separated and removed, toluene was recovered under reduced pressure, 90 ml of isopropyl alcohol was added, and the formed precipitate was filtered, washed and dried to obtain 23.1 g of crude crystals. The crude crystals were recrystallized with isopropyl alcohol to obtain 22.2 g of compound (a). The yield was 49% (from 2-tert-butyl-4-methoxyphenol).

In addition, the purity of the compound (a) was measured by HPLC analysis.
<Measurement conditions>
Device: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUMIPAX ODS A-212 6.0 × 150 mm 5 μm
Column temperature: 40 ° C
Mobile phase: Methanol / water = 95/5 (phosphoric acid 3 ml / L)
Flow rate: 1.0 ml / min
Detection: UV 250 nm
<Measurement result>
HPLC surface purity 98.5%

Further, as a result of conducting NMR measurement of the compound (a), the result of supporting the above-mentioned structure was obtained. The measurement conditions are as follows.
<Measurement conditions>
Device: JEOL JNM-AL300
Resonance frequency: 300 MHz (1H-NMR)
Solvent: chloroform-d
As an internal standard substance of 1 H-NMR, tetramethylsilane was used, a chemical shift value was indicated by δ value (ppm), and a coupling constant was indicated by Hertz. Also, s is a singlet, d is a doublet, and m is an abbreviation of multiplet. The same applies to the following embodiments. In the following Examples 2 to 6, NMR measurement was performed under the same measurement conditions as in this example. The contents of the obtained NMR spectrum are as follows.
δ = 11.44 (s, 1 H, phenol-OH), 8.73 (s, 1 H, benzotriazol-H), 8.13 (d, 1 H, J = 9.0 Hz, benzotriazol-H), 7.98 (D, 1 H, J = 11.1 Hz, benzotriazol-H), 7.82 (s, 1 H, phenol-H), 7.05 (s, 1 H, phenol-H), 6.18 (s, 1 H, _{C = CH 2 -H), 5.62} (s, 1H, C = CH 2 -H), 4.65 (m, 2H, methacryloyl-O-CH 2 -H), 4.56 (m, 2H, _{benzotriazol-CO-O-CH 2} -H), 3.93 (s, 3H, phenol-O-CH 3 -H), 1.98 (s, 3H, CH 2 = C-CH 3 -H), 1 .56 (s, 9H, tert-b utyl-H)

・・・化合物（ｂ） (Composition example 2)
[Compound (b): Synthesis of 2-methacryloyloxyethyl 2- (2-hydroxy-5-methoxyphenyl) -2H-benzotriazole-5-carboxylate]

... Compound (b)

  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 wavelengths λmax were 309.8 nm and 373.2 nm, and the molar absorption coefficients ε of the wavelengths were 14700 and 13100, respectively.

The purity of compound (b) was also measured by HPLC analysis.
<Measurement conditions>
Device: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: Inertsil ODS-3 4.6 × 150 mm 5 μm
Column temperature: 25 ° C
Mobile phase: acetonitrile / water = 9/1 (phosphoric acid 3 ml / L)
Flow rate: 1.0 ml / min
Detection: UV 250 nm
<Measurement result>
HPLC surface purity 93.4%

Further, as a result of NMR measurement of the compound (b), the result of supporting the above-mentioned structure was obtained. The contents of the obtained NMR spectrum are as follows.
δ = 10.71 (s, 1 H, phenol-OH), 8. 73 (s, 1 H, benzotriazole-H), 8.12 (d, 1 H, J = 9.6 Hz, benzotriazole-H), 7.98 (d, 1H, J = 9.6Hz , benzotriazole-H), 7.15 (m, 3H, phenol-H), 6.18 (s, 1H, C = CH 2 -H), 5.62 (s , 1H, C = CH ₂ -H), 4.65 (m, 2H, methacryloyl-O-CH ₂ -H), 4.57 (m, 2H, benzotriazole-CO-O-CH ₂ -H), 3 _{.89 (s, 3H, phenol-} O-CH 3 -H), 1.98 (s, 3H, CH 2 = C-CH 3 -H)

[2. Benzotriazole monomer commercial product]
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. Cesamol type benzotriazole monomer commercially available product]
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 (Sipro Chemical R26) was used. Hereinafter, 2- [2- (6-hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3 benzotriazol-5-yl] ethyl methacrylate is referred to as “compound (d)”. It is written.
[4. Synthesis of benzotriazole (co) polymer]

Example 1
A four-necked flask is equipped with a Dimroth condenser, a mercury thermometer, a nitrogen gas blowing tube, a stirrer, and 20 parts of a compound (a) as a monomer composition, methyl methacrylate (hereinafter referred to as "MMA") 20 Part, and 60 parts of methyl ethyl ketone (hereinafter referred to as "MEK") as a solvent, and 2,2'-azobis-methylbutyro nitrile (hereinafter referred to as "AMBN") 1 as a polymerization initiator After putting 5 parts into the flask and substituting nitrogen in the flask for 1 hour at a nitrogen gas flow rate of 10 ml / min while stirring, the polymerization reaction was carried out under reflux 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)
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") of the monomer composition in Example 1 The same polymerization reaction procedure as in Example 1 was carried out except using the above, to obtain a UV-absorbing copolymer solution.

(Example 3)
The monomer composition in Example 1 is 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- The same polymerization reaction procedure as in Example 1 was carried out except that 2 parts of pentamethyl piperidyl methacrylate (hereinafter referred to as "HALS") was used, to obtain a UV-absorbing copolymer solution.

(Example 4)
Example 1 is the same as Example 1 except that the monomer composition in Example 1 is 1 part of compound (b) and 19 parts of MMA, 80 parts of MEK as a solvent, and 0.8 parts of AMBN as a polymerization initiator. The following polymerization reaction procedure was carried out to obtain a UV-absorbing copolymer solution.

(Comparative example 1)
The same polymerization reaction procedure as in Example 1 was carried out except that the monomer composition in Example 1 was changed to 20 parts of compound (c) and 20 parts of MMA, to obtain a UV-absorbing copolymer solution.

(Comparative example 2)
The same polymerization reaction procedure as in Example 1 was carried out except that the monomer composition in Example 1 was changed to 20 parts of compound (d) and 20 parts of MMA, to obtain a UV-absorbing copolymer solution.

[4. Evaluation]
Nonvolatile content, solution viscosity, molecular weight, and maximum absorption wavelength λmax of ultraviolet absorbing copolymer, ultraviolet light absorption of the ultraviolet absorbing copolymer solution obtained by the above Examples 1 to 4 and Comparative Examples 1 and 2 The spectrum was measured. Furthermore, a coating film is prepared by coating a polyester film with a coating containing an ultraviolet absorbing copolymer, and a coating film is prepared, and an ultraviolet blocking function confirmation test for the purpose of confirming the protective performance of dyes used in sublimation transfer printing, Elution, bleeding out, crystallization of the UV absorbing component from the above, and a confirmation test of the compatibility of the blended materials were conducted.

  The nonvolatile content was calculated from the amount of residual resin after weighing 0.5 g of the obtained ultraviolet absorbing copolymer solution in an aluminum pan, drying at 100 ° C. for 1 hour, and further drying at 150 ° C. for 5 hours.

  The viscosity was measured for the solution viscosity at 25 ° C. using an EH viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.).

  The molecular weight is the weight average molecular weight (Mw) in terms of polystyrene using a polystyrene calibration curve, using a GPC system HLC-8320GPC EcoSEC (Tosoh Corp.), the eluent as tetrahydrofuran, and the separation column as TSKgel GMHXL-L (Tosoh Corp.) The number average molecular weight (Mn) and the polydispersity (Mw / Mn) were measured.

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

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

  5 parts of toluene and 5 parts of MEK were added to 10 parts of the ultraviolet absorbing copolymer solution obtained in Examples 1 to 3 and Comparative Examples 1 and 2 to prepare a paint containing the ultraviolet absorbing copolymer, The above paint is applied to a glass plate (TP Giken, thickness 2 mm) with a bar coater # 20, dried at 80 ° C. for 1 minute, and further dried at 100 ° C. for 30 seconds, and a coating containing an ultraviolet absorbing copolymer I got a film. The film thickness of the coating film containing the ultraviolet absorbing copolymer using a film thickness meter (FILMETRICS F20) was about 3 μ.

  Subsequently, a yellow dye, a cyan dye, a magenta dye, and a transfer film of three colors used in a commercially available sublimation transfer type compact photo printer (Canon SELPHY CP600) were obtained. The deterioration of the dye of the transfer film due to ultraviolet irradiation according to JIS K 5701-1: 2000, irradiance 180 W, black panel temperature 63 ± 3 ° C, ultraviolet light 100 hours using a xenon weather meter (Suga Test Instruments SX-75) Continuous irradiation. From this result, the color degradation of the dye was used as the evaluation standard for the resistance to ultraviolet rays.

  Similarly, using a dye transfer film, the transfer film is protected with a glass plate coated with the coating material containing each of the ultraviolet absorbing copolymers prepared above, and in the same manner as described in JIS K5701-1: 2000. The ultraviolet color fading was confirmed. The evaluation was made in 5 steps in consideration of the degree of visual observation of fading. Level 5: no change, level 4: slight ink fading can be confirmed, level 3: ink fading can be confirmed, level 4: almost ink fading, Level 1 was ink decomposition loss.

  Elution of the UV absorbing component from the coating film, bleeding out, crystallization, change in the coating material compatibility of the mixed material confirmatory tests were made of the film coated with the coating containing the respective UV absorbing copolymer prepared above The change over time was observed using an optical microscope. The evaluation was a visual sensitivity evaluation of the coating state for one month after film preparation.

  Nonvolatile content, molecular weight, maximum absorption wavelength λmax, absorbance at wavelength regions 300 nm, 360 nm, 400 nm, 420 nm, and 450 nm of the ultraviolet absorbing copolymer solution obtained from the above Examples 1 to 4 and Comparative Examples 1 and 2 Evaluation results of UV blocking function test, elution of UV absorbing component from coating film, bleeding out, crystallization, change of coating film status of mixed material compatibility test results Table 1 shows UV absorption spectrum Figure 1-Figure 6 It was shown to.

The meanings of the symbols in Table 1 are as follows.
"Compound (a)": 2-methacryloyloxyethyl 2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole-5-carboxylate "Compound (b)": 2-methacryloyl Oxyethyl 2- (2-hydroxy-5-methoxyphenyl) -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-1,2,3 benzotriazol-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 to the ultraviolet wavelength range of 300 nm to 400 nm of the sunlight irradiance distribution reached from the sun on the ground. It has an area. Moreover, it has absorption of the visible light short wavelength area | region of about 400-450 nm which is pointed out that it gives damage to organic substance and a human body. Accordingly, the paint using the same and the film coated with the paint also have a broad ultraviolet and visible short wavelength absorption wavelength range of 300 nm to 450 nm. Therefore, it has been found that when used as a UV absorbing and shielding protective material, it is possible to protect an object to be protected from UV light at a very high level. It was also found that there were no problems of elution or bleeding out of the UV absorbing component from the coating, crystallization of the UV absorbing component in the coating or compatibility with other compounding materials.

  The benzotriazole-based (co) polymer of the present invention absorbs a wide wavelength range of 300 to 400 nm, which can correspond to the spectral irradiance distribution of the ultraviolet portion of sunlight, out of the ultraviolet range of sunlight which has been difficult to absorb conventionally It is a material that can be absorbed in the visible light short wavelength range of about 400 to 450 nm, which is pointed out to cause damage to organic substances and the human body. Further, in the benzotriazole (co) polymer of the present invention obtained by further copolymerizing a conventionally known benzotriazole monomer absorbing a UV region of 250 nm to 380 nm as a raw material monomer, Excellent absorption performance in a wide range of ultraviolet light. It can also be coated as a paint. Therefore, it can be suitably used for protection of materials that deteriorate with ultraviolet light and light in the short wavelength range of visible light and the human body, and in particular, it can be suitably used for optical films for displays, spectacle lenses and the like.

Claims (4)

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

......... General formula (1)
(Wherein, 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, Or alkyl having 1 to 2 carbon atom methacryloyloxyalkyl groups). The benzotriazole-based copolymer according to claim 1, further comprising an alkanolphenol-type benzotriazole-based monomer represented by the general formula (2) as the polymerizable monomer.

......... General formula (2)
(Wherein, 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 carbonization 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)   An ultraviolet absorbing paint comprising the benzotriazole (co) polymer according to claim 1 or 2.   A film coated with the ultraviolet absorbing paint according to claim 3.

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