JP2023149430A - Ultraviolet absorber and applications thereof - Google Patents

Abstract

To provide an ultraviolet absorber that absorbs ultraviolet rays of less than 400 nm and light in the short wavelength region of visible light with a wavelength of 400 to 420 nm, and has excellent heat resistance, bleeding resistance, and low colorability.SOLUTION: There is provided an ultraviolet absorber with a triazine ring directly bonded to a hydroxynaphthyl group, wherein the hydroxynaphthyl group is a group having a structure represented by the following general formula (1): *-X-Y-Z, wherein X represents -COO- or -CONH-, Y represents a divalent connecting group, Z represents a polymerizable unsaturated group, and * represents bonds with a hydroxynaphthyl group.SELECTED DRAWING: None

Description

The present invention relates to ultraviolet absorbers.

Various polymer materials are widely used for various purposes as molded objects, films, and coating materials. However, it is known that these materials are subject to quality deterioration such as discoloration and mechanical strength due to the action of ultraviolet rays contained in sunlight and the like. Therefore, UV absorbers are added to various polymer materials to prevent quality deterioration.

For example, UV absorbers are added to packaging materials for pharmaceuticals, cosmetics, and the like to protect the packaging materials themselves and the organic substances contained within them from deterioration and decomposition. Furthermore, in display devices, it is common practice to add ultraviolet absorbers to optical films such as polarizing plate protective films to prevent discoloration of these optical films. Conventionally, coating compositions such as paints and adhesives often contain ultraviolet absorbers to prevent deterioration caused by ultraviolet rays.

However, if UV absorbers are simply blended into polymer materials, the UV absorbers may bleed over time, and such UV absorbers should not be used in packaging materials for pharmaceuticals or cosmetics because of the human body. is nonconforming in terms of its impact on

In addition, polymer materials containing UV absorbers are often thermally decomposed during molding or coating by heat treatment, and the original UV absorber effect cannot be exerted. There is a need for ultraviolet absorbers with outstanding properties.

On the other hand, it has been pointed out that not only ultraviolet rays with a wavelength of less than 400 nm in sunlight, but also light in the visible short wavelength region of about 400 to 420 nm can damage organic matter and the human body, and certain applications including the above-mentioned applications There is a need for ultraviolet absorbers that can absorb even light in the short wavelength range of visible light.

As a method for suppressing bleeding of an ultraviolet absorber, a method is known in which the ultraviolet absorber is made into an ultraviolet absorbing unsaturated monomer and then polymerized. Moreover, as ultraviolet absorbers, there are benzophenone-based, benzotriazole-based, triazine-based, and other ultraviolet absorbers, and among these, triazine-based ultraviolet absorbers are known to have high heat resistance.

For example, Patent Document 1 discloses a triazine-based ultraviolet absorber having a (meth)acryloyl group capable of radical polymerization. In the synthesis method of Patent Document 1, when converting a triazine-based ultraviolet absorber into an unsaturated monomer, the monofunctionality of the polymerizable group tends to decrease due to the large number of hydroxy groups that are reaction sites, making it difficult to control the reaction. is often difficult. It is difficult to control the polymerization of ultraviolet absorbers with low monofunctionality, making it impossible to appropriately design ultraviolet absorbing polymers.

Patent Document 2 discloses a triazine-based ultraviolet absorber that has excellent heat resistance and bleed resistance by linking triazine skeletons. Moreover, Patent Document 3 discloses a triazine-based ultraviolet absorber that absorbs ultraviolet rays in a long wavelength region and has excellent heat resistance. However, the UV absorption properties of these triazine-based UV absorbers in the short wavelength range of visible light are not fully satisfactory, and their bleed resistance is also insufficient, and since they do not have polymerizable groups, bleeding is suppressed by polymerization. I can't.

In addition, the greater the number of hydroxyl groups on the aromatic ring bonded to the triazine ring that can hydrogen bond with the nitrogen atom of the triazine ring, the higher the heat resistance of triazine-based UV absorbers, but the higher the coloring property. It tends to be higher. It cannot be said that the triazine-based ultraviolet absorbers disclosed in these patent documents have both sufficient heat resistance and colorability.

WO2018/216750 Japanese Patent Application Publication No. 2016-113445 JP2017-132948A

The object of the present invention is to provide an ultraviolet absorber that absorbs light in the ultraviolet wavelength region of less than 400 nm and visible light short wavelength region of 400 to 420 nm, and has excellent heat resistance, bleed resistance, and low coloring property.

The present invention relates to an ultraviolet absorber having a triazine ring directly bonded to a hydroxynaphthyl group, wherein the hydroxynaphthyl group is a group having a structure represented by the following general formula (1).
General formula (1) *-X-Y-Z
(In the formula, X represents -COO- or -CONH-, Y represents a divalent linking group, Z represents a polymerizable unsaturated group, and * represents a bond with a hydroxynaphthyl group. )

The present invention also relates to the ultraviolet absorber, wherein the polymerizable unsaturated group is one selected from the group consisting of a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.

The present invention also relates to an ultraviolet absorber that is a polymer of the ultraviolet absorber.

The present invention also relates to an ultraviolet absorber that is a copolymer of the ultraviolet absorber and other monomers.

The present invention also relates to an ultraviolet absorbing molding agent characterized by containing the ultraviolet absorber.

The present invention also relates to an ultraviolet absorbing coating agent characterized by containing the ultraviolet absorber.

According to the present invention, an ultraviolet absorber and an ultraviolet absorbing coating that absorb light in the ultraviolet region of less than 400 nm and in the short wavelength region of visible light from 400 to 420 nm and have excellent heat resistance, bleed resistance, and low coloring property. can provide drugs.

<Ultraviolet absorber>
The ultraviolet absorber of the present invention can absorb light in the visible light short wavelength region of about 400 to 420 nm in addition to the ultraviolet region of less than 400 nm due to the action of the naphthalene ring bonded to the triazine ring. Note that the naphthalene ring is preferably directly bonded to the triazine ring without a linking group. Moreover, it is more preferable that at least one of the 1, 2, or 3 naphthalene rings directly bonded to the triazine contains a hydroxy group at the 2-position. Furthermore, the number of naphthalene rings having a 2-position hydroxy group directly bonded to the triazine ring is more preferably one. As the number of naphthalene rings having a 2-position hydroxy group directly bonded to the triazine ring increases, heat resistance tends to improve, but coloration tends to increase.

The ultraviolet absorber of the present invention may be in monomer form or in polymer form. The monomer type ultraviolet absorber of the present invention is an ultraviolet absorber having a triazine ring directly bonded to a hydroxynaphthyl group, and wherein the hydroxynaphthyl group has a structure represented by the following general formula (1). These are ultraviolet absorbers represented by formula (2), general formula (3), and general formula (4).
General formula (1) *-X-Y-Z
(In the formula, X represents -COO- or -CONH-, Y represents a divalent linking group, Z represents a polymerizable unsaturated group, and * represents a bond with a hydroxynaphthyl group. )

In general formulas (2) to (4), R _1b to R _1g , R _2a to R _2g , and R _3a to R _3g each independently represent a hydrogen atom, a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, An atom, a nitrile group, a nitro group, a carboxyl group, a sulfo group, R ₇ , a substituted or unsubstituted aryl group, and a group represented by general formula (1).

X in general formula (1) is an ester group or an amide group represented by -COO- or -CONH-. * indicates a bond with a hydroxynaphthyl group. By directly bonding such an electron-withdrawing group to the hydroxynaphthalene ring, the heat resistance of the ultraviolet absorbent can be improved and the coloring property can be reduced.

The linking group Y in general formula (1) is an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. It may have a substituent of an aryl group, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and there is one carbon atom between the carbon atoms of the alkylene group having 1 to 20 carbon atoms. or a plurality of cycloalkylene groups having 6 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, carbonyl groups, ether bonds, ester bonds, carbonate bonds, amide bonds, urethane bonds, urea bonds, the following general formula (Y- 1) to (Y-6) may be connected.

Z in general formula (1) is a vinyl group, (meth)allyl group, or (meth)acryloyl group, and is represented by general formulas (Z-1) to (Z-5) below. From the viewpoint of versatility in polymerization, (meth)acryloyl groups represented by general formulas (Z-4) and (Z-5) are preferred.

R ₇ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyleneoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 1 to 20 carbon atoms; and may have a substituent such as a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group, and an alkyl group having 1 to 20 carbon atoms, a carbon Alkenyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkyleneoxy group having 1 to 20 carbon atoms, and alkenyloxy group having 1 to 20 carbon atoms have one or more carbon atoms between them. They may be linked by a carbonyl group, ether bond, ester bond, carbonate bond, amide bond, urethane bond, or urea bond.

Substituted or unsubstituted aryl groups include aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, biphenyl groups, hydroxy groups, alkyl groups having 1 to 20 carbon atoms, and aryl groups having 1 to 20 carbon atoms. Substituent for an alkenyl group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group. It may have.

Examples of the compound represented by the general formula (2) include the following compounds, but the ultraviolet absorber of the present invention is not limited to these compounds.

Examples of the compound represented by the general formula (4) include the following compounds, but the ultraviolet absorbent of the present invention is not limited to these compounds.
(A-11)

The method for synthesizing the triazine-based ultraviolet absorber is not particularly limited, and can be synthesized using a known synthesis method for compounds having a triazine structure. For example, there is a method in which cyanuric chloride or a cyanuric chloride derivative is subjected to a substitution reaction with naphthol or a naphthol derivative using aluminum trichloride. Other methods include, for example, a method in which methyl 2-hydroxy-1-naphthoate and benzamidine hydrochloride are subjected to a condensation cyclization reaction using sodium methoxide. The naphthalene ring connected to the triazine ring with a single bond and the substituents provided by R ₄ , R ₅ , and R ₆ may be introduced after forming the triazine structure, or may be introduced before forming the triazine structure.

The method for introducing the substituent represented by general formula (1) is not particularly limited, and any known method can be used. For example, introduction of an ester bond by addition reaction of carboxylic acid to an epoxy compound, introduction of an ester bond or amide bond by reaction of acid chloride with alcohol or amine, and introduction of ester bond by transesterification reaction of carboxylic acid or carboxylic acid ester with alcohol. Examples include methods such as introducing a bond. The substituent represented by general formula (1) may be introduced after forming the triazine structure, or may be introduced before forming the triazine structure.

The method for purifying these triazine-based ultraviolet absorbers is not particularly limited, and methods using distillation, recrystallization, reprecipitation, filtering materials, and adsorbents can be used.

<Ultraviolet absorbing polymer>
The UV absorbers of the present invention may be in polymeric form. Since the monomer-shaped ultraviolet absorber represented by general formula (1) has a polymerizable unsaturated group, it can be made into an ultraviolet absorbing polymer by polymerizing the polymerizable unsaturated group.
The ultraviolet absorbing polymer absorbs light in the ultraviolet region of less than 400 nm and the short wavelength region of visible light from 400 to 420 nm by containing the monomer-form ultraviolet absorber of the present invention as a monomer component. By polymerizing the UV absorber, it can be made into a UV absorber with excellent heat resistance and bleed resistance, making it a material more suitable for molding resin compositions and coating compositions.

The ultraviolet absorbing polymer of the present invention may be obtained by homopolymerizing the monomeric ultraviolet absorbent of the present invention, or may be obtained by copolymerizing with other monomers. When blending into a molding resin composition or a coating composition, it is preferable to copolymerize the ultraviolet absorber of the present invention with other monomers.

When the monomeric ultraviolet absorber of the present invention is copolymerized with other monomers, the monomeric ultraviolet absorber is It is preferably contained in the mass component in an amount of 20 to 80% by mass. When it is less than 20% by mass, the effect of absorbing ultraviolet rays is low, and when it is more than 80% by mass, the compatibility with the base resin to be blended tends to be poor.

Examples of other monomers include (meth)acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth)acrylamide, vinyl ether, vinyl alcohol ester, styrenes, Examples include (meth)acrylonitrile, acidic group-containing monomers, monomers having a hindered amine photostable structure, and ultraviolet absorbing unsaturated monomers other than those of the present invention.

(Meth)acrylic acid esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( isobutyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, (meth) 2-Hydroxyethyl acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy (meth)acrylate -2-Hydroxypropyl, benzyl (meth)acrylate, diethylene glycol monomethyl (meth)acrylate, diethylene glycol monoethyl (meth)acrylate, triethylene glycol monomethyl (meth)acrylate, triethylene (meth)acrylate Glycol monoethyl ether, (meth)acrylic acid polyethylene glycol monomethyl ether, (meth)acrylic acid polyethylene glycol monoethyl ether, (meth)acrylic acid β-phenoxyethoxyethyl ether, (meth)acrylic acid nonylphenoxy polyethylene glycol, (meth)acrylic acid polyethylene glycol monoethyl ether Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, (meth)acrylic acid Dicyclopentanyl, tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, glycidyl (meth)acrylate, 4-(2,3-epoxypropoxy)butyl (meth)acrylate, 1 , 4-cyclohexanedimethanol mono(meth)acrylate, and the like.

Examples of crotonate esters include n-butyl crotonate, isobutyl crotonate, sec-butyl crotonate, tert-butyl crotonate, and hexyl crotonate.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate.

Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of the itaconic acid diester include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth)acrylamide is, for example, (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl Acrylic (meth)amide, N-tert-butyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-(2-methoxyethyl) (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N -diethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-benzyl (meth)acrylamide, (meth)acryloylmorpholine, diacetone acrylamide and the like.

Examples of the vinyl ether include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (eg, t-Boc, etc.), methyl vinylbenzoate, and α-methylstyrene.

Acidic group-containing monomers include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and anhydride. Unsaturated dicarboxylic acids or their acid anhydrides such as itaconic acid, citraconic acid, citraconic anhydride, and mesaconic acid; Trivalent or higher unsaturated polycarboxylic acids or their acid anhydrides; Mono(2-acryloyloxyethyl succinate) ), mono(2-methacryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate, etc. (meth)acryloyloxyalkyl] ester; mono(meth)acrylates of carboxy polymers at both ends, such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate.

Monomers having a hindered amine photostable structure include, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetra Methylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano -4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6 , 6-tetramethylpiperidine, etc., and these may be used alone or in combination of two or more as necessary.

When these monomers having a hindered amine photostable structure are copolymerized, photostability can be further improved. More preferably, it is contained in the copolymer composition in an amount of 3 to 40% by mass. When it is less than 3% by mass, the effect of ensuring photostability is small, and when it is more than 40% by mass, hydrophilicity tends to be high and compatibility tends to be poor.

Examples of UV-absorbing unsaturated monomers other than those of the present invention include 4-acryloyloxybenzophenone, 4-methacryloyloxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, and 2-hydroxybenzophenone. Hydroxy-4-(2-acryloyloxy)ethoxybenzophenone, 2-hydroxy-4-(2-methacryloyloxy)ethoxybenzophenone, 2-hydroxy-4-(2-methyl-2-acryloyloxy)ethoxybenzophenone, 2,2 ' -Benzophenone unsaturated monomers such as dihydroxy-4-methacryloyloxybenzophenone; 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'- Hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy- 3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl-3'-(methacryloyloxyethyl)phenyl]-2H -benzotriazole,
Benzotriazole unsaturated monomers such as 2-[2'-hydroxy-5'-(β-methacryloyloxyethoxy)-3'-tert-butylphenyl]-4-tert-butyl-2H-benzotriazole, etc. can be mentioned.

(Ultraviolet absorbing molding agent)
Further, the ultraviolet absorbing polymer can be used as an ultraviolet absorbing molding agent. The ultraviolet absorbing molding agent may be used alone, or may be used as a molding resin composition consisting of a polyolefin and an ultraviolet absorbing polymer. When used alone or when mixed with a polyolefin, the ultraviolet absorbing polymer preferably contains an unsaturated monomer represented by general formula (5) and/or (6) in its copolymer composition.

General formula (5)

(In the formula, R ₈ represents a hydrogen atom or a methyl group. R ₉ represents a hydrocarbon group having 18 or less carbon atoms.)

General formula (6)

(In the formula, R ₁₀ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.)
The unsaturated monomer represented by the general formula (5) plays a role in ensuring compatibility with the polyolefin. When R ₉ is a hydrocarbon group having 18 or less carbon atoms, the crystallinity of the unsaturated monomer represented by the general formula (5) is relatively suppressed, and high compatibility with the polyolefin is ensured.
In general formula (5), R ₉ which is a hydrocarbon group having 18 or less carbon atoms is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -butyl group, n-pentyl group, sec-pentyl group, tert-pentyl group, 3-pentyl group, isopentyl group, neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2 -dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4- Dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, 2-ethylhexyl group, isooctyl group, tert-octyl group, n-nonyl group , isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. Straight chain or branched alkyl group; alicyclic carbonization such as cyclododecyl group Hydrogen group; examples include polycyclic hydrocarbon groups such as isobornyl group, dicyclopentanyl group, dicyclopentenyl group, and adamantyl group. Among these, a hydrocarbon group having 10 or less carbon atoms is preferred.

Specific examples of the unsaturated monomer represented by general formula (5) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, t-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, (meth)acrylate Acid stearyl, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylic acid Examples include dicyclopentenyl and adamantyl (meth)acrylate.

The unsaturated monomer represented by the general formula (6) also plays a role in ensuring compatibility with the polyolefin.

As specific examples of the unsaturated monomer represented by general formula (6), styrene, vinyltoluene, etc. are preferably used.

It is preferable that the unsaturated monomer represented by the general formula (5) and/or (6) is contained in the copolymer composition in an amount of 20% by weight or more. If it is less than 20% by weight, the effect of ensuring compatibility tends to be small.

Examples of the synthesis of ultraviolet absorbing polymers include anionic polymerization, cationic polymerization, free radical polymerization, living anionic polymerization, living cationic polymerization, and living radical polymerization. Among these, free radical polymerization and living radical polymerization are preferred.

Free radical polymerization preferably uses a polymerization initiator. The polymerization initiator is preferably, for example, an azo compound or a peroxide. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2 , 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate) , 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl) ) propane], etc. Peroxides include, for example, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate. , tert-butyl peroxyneodecanoate, tert-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide, and the like. Polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150°C, more preferably 50 to 110°C. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

In living radical polymerization, side reactions that occur in general radical polymerization are suppressed, and furthermore, polymerization growth occurs uniformly, so block polymers and resins with uniform molecular weight can be easily synthesized.

Living radical polymerization uses organic halides or halogenated sulfonyl compounds as initiators, and atom transfer radical polymerization uses transition metal complexes as catalysts, which can be applied to a wide range of monomers and can be adapted to existing equipment. This is preferable in that the polymerization temperature can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in References 1 to 8 below.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614
(Reference document 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) International Publication No. 96/030421 (Reference 6) International Publication No. 97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

It is preferable to use an organic solvent in the synthesis of the ultraviolet absorbing polymer. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene. Examples include glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. The organic solvents can be used alone or in combination of two or more.

The weight average molecular weight of the ultraviolet absorbing polymer measured by gel permeation chromatography (GPC) is preferably 5,000 to 200,000, more preferably 5,000 to 100,000.

UV absorbing polymers can be co-molded with polyolefins.

<Polyolefin>
Examples of polyolefins include polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene, and copolymers thereof.
Examples of polyethylene include low density polyethylene and high density polyethylene.
Examples of polypropylene include crystalline or amorphous polypropylene.
Copolymers using these include, for example, random, block or graft copolymers of ethylene and propylene, copolymers of α-olefin and ethylene or propylene, ethylene-vinyl acetate copolymers, and ethylene-methyl acrylate copolymers. Examples include polymers, ethylene-ethyl acrylate copolymers, and ethylene-acrylic acid copolymers.
Among these, crystalline or amorphous polypropylene, ethylene-propylene random, block or graft copolymers are preferred, and propylene-ethylene block copolymers are more preferred. Further, polypropylene resin is preferable from the viewpoint of being inexpensive and having a low specific gravity so that the weight of the molded product can be reduced.

The number average molecular weight of the polyolefin is about 30,000 to 500,000.

The melt flow rate (MFR) of the polyolefin is preferably 1 to 100 (g/10 minutes). Note that MFR is a value determined in accordance with JISK-7210.

The content of the ultraviolet absorbing polymer is preferably 0.01 to 10 parts by weight per 100 parts by weight of the polyolefin.

The ultraviolet absorbing molding agent of the present invention can contain wax.

Examples of the wax include polyethylene wax and polypropylene wax. The melting point of the wax is preferably 50 to 180°C, more preferably 80 to 170°C. Note that the melting point of the wax is measured in a nitrogen atmosphere using a differential scanning calorimeter. Note that polyolefin is a compound that does not have a melting point but has a softening point.

The number average molecular weight of the wax is preferably 500 to 25,000, more preferably 1,000 to 15,000. Note that the number average molecular weight is a value measured in accordance with JIS K2207:1996 (Japanese Industrial Standards).

The wax content is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polyolefin.

The molding resin composition of the present invention is preferably produced, for example, as a masterbatch containing a high concentration of ultraviolet absorbing polymer. A masterbatch can be produced, for example, by melt-kneading an ultraviolet absorbing polymer and a polyolefin and forming the mixture into pellets using a pelletizer. In order to prevent agglomeration of the ultraviolet absorbing polymer, it is preferable to prepare a dispersion by melting and kneading the ultraviolet absorbing polymer and wax in advance, and then melting and kneading the dispersion with the polyolefin to prepare a masterbatch. Here, it is preferable to use a blend mixer or a three-roll mill to prepare the dispersion.

Rather than blending a considerable amount of the UV-absorbing polymer at the time of molding, the UV-absorbing polymer is first pre-dispersed as a masterbatch and then blended (melted and kneaded) with the diluted thermoplastic resin to form the desired molded product. When manufactured, the UV-absorbing polymer can be easily dispersed uniformly within the molded body.
When producing a molding resin composition as a masterbatch, it is preferable to mix 1 to 30 parts by mass of an ultraviolet absorbing polymer with respect to 100 parts by mass of polyolefin. The mass ratio of the masterbatch (x) to the diluent resin (y) is preferably x/y=1/5 to 1/100. When the content is within this range, the molded product can easily obtain good optical properties.

The diluting resin is not limited to polyolefins, and thermoplastic resins having good compatibility with polyolefins can be appropriately selected and used.
For melt-kneading, it is preferable to use, for example, a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, or the like. The melting and kneading temperature varies depending on the type of polyolefin, but is usually about 150 to 250°C.

The molding resin composition of the present invention can contain an antioxidant, a light stabilizer, a dispersant, etc. in addition to the polyolefin and the ultraviolet absorbing polymer.

The molding resin composition of the present invention preferably contains an ultraviolet absorbing polymer and a thermoplastic resin other than polyolefin.
Examples of thermoplastic resins other than polyolefin include polycarbonate, polyacrylic, polyester, and cycloolefin resin.

<Polycarbonate>
Polycarbonate is a compound obtained by synthesizing divalent phenol and a carbonate precursor by a known method. Divalent phenols include, for example, hydroquinone, resorcinol, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3,5-dimethyl) phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)sulfide, and the like. Among these, bis(4-hydroxyphenyl) alkanes are preferred, and 2,2-bis(4-hydroxyphenyl)propane, also known as bisphenol A, is more preferred.
Examples of the carbonate precursor include phosgene, diphenyl carbonate, dihaloformate of divalent phenol, and the like. Among these, diphenyl carbonate is preferred.

The dihydric phenol and the carbonate precursor can be used alone or in combination of two or more types.

<Polyacrylic>
Polyacrylic is a compound obtained by polymerizing monomers such as methyl methacrylate and/or ethyl methacrylate by a known method. Examples include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-acrylic acid copolymer. In addition to the above-mentioned monomers, monomers such as butadiene, α-methylstyrene, maleic anhydride, etc. can also be added for polymerization, and heat resistance, fluidity, and impact resistance can be adjusted by adjusting the monomer amount and molecular weight.

<Polyester>
Polyester is a resin that has an ester bond in the main chain of the molecule, and is a polycondensate synthesized from dicarboxylic acid (including its derivatives) and diol (dihydric alcohol or dihydric phenol); ) and a cyclic ether compound; and a ring-opening polymer of a cyclic ether compound. Examples of the polyester include a homopolymer made of a dicarboxylic acid and a diol, a copolymer using a plurality of raw materials, and a polymer blend obtained by mixing these. Note that the dicarboxylic acid derivatives are acid anhydrides and esters. Although there are two types of dicarboxylic acids, aliphatic and aromatic, aromatic is more preferable because it improves heat resistance.

Aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxylphenylacetic acid, m-phenylenediglylic acid, p-phenylenediglycolic acid, diphenyldiacetic acid, diphenyl-p , p'-dicarboxylic acid, diphenyl-4,4'-diacetic acid, diphenylmethane-p,p'-dicarboxylic acid, diphenylethane-m,m'-dicarboxylic acid, stilbenzylcarboxylic acid, diphenylbutane-p,p' -dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyric acid, 1,2-diphenoxypropane-p,p'-dicarboxylic acid, 1,5-diphenoxypentane-p,p'-dicarboxylic acid, 1,6-dicarboxylic acid Phenoxyhexane-p,p'-dicarboxylic acid, p-(p-carboxyphenoxy)benzoic acid, 1,2-bis(2-methoxyphenoxy)-ethane-p,p'-dicarboxylic acid, 1,3-bis( 2-methoxyphenoxy)propane-p,p'-dicarboxylic acid, 1,4-bis(2-methoxyphenoxy)butane-p,p'-dicarboxylic acid, 1,5-bis(2-methoxyphenoxy)-3- Examples include oxypentane-p,p'-dicarboxylic acid.
Examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, adipic acid, corkic acid, mazelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, and fumaric acid.

Dihydric alcohols include, for example, ethylene glycol, trimethylene glycol, butane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,4-diol, cis-2-butene-1 , 4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, cyclohexanedimethanol and the like. Among these, ethylene glycol, butane-1,4-diol, and cyclohexanedimethanol are preferred.
Examples of dihydric phenols include hydroquinone, resorcinol, bisphenol A, and the like.
Examples of the cyclic ether compound include ethylene oxide and propylene oxide.

Dicarboxylic acids and dihydric alcohols can be used alone or in combination of two or more.

<Cycloolefin resin>
Cycloolefin resins are polymers of ethylene or α-olefins and cyclic olefins. α-olefins are monomers derived from C4 to C12 α-olefins, such as 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1- Examples include hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene. Cyclic olefins are monomers derived from norbornene, and include substituted hydrogen groups, halogen atoms, and monovalent or divalent hydrocarbon groups. Among these, unsubstituted norbornene is preferred.

The ultraviolet absorbing molding agent of the present invention is preferably made into a masterbatch even when a thermoplastic resin other than polyolefin is used, as in the case where polyolefin is used. Further, the method for preparing the masterbatch, optional ingredients, etc. are the same as above.

The ultraviolet absorbing molding agent of the present invention is preferably used, for example, in food packaging materials, pharmaceutical packaging materials, and display applications. For food packaging materials and pharmaceutical packaging materials, it is preferable to use, for example, polyester as the thermoplastic resin. These molded bodies have improved flexibility and visibility, and can suppress deterioration of the contents.
Furthermore, for display applications (for example, televisions, personal computers, smartphones, etc.), it is preferable to use, for example, polyacrylic or polycarbonate as the thermoplastic resin. These molded objects can suppress the harmful effects on the eyes by absorbing the ultraviolet rays contained in backlights and the short wavelength range of visible light contained in sunlight. By absorbing light in the wavelength range, it is possible to suppress deterioration of display elements of a display, and furthermore, it is possible to suppress a decrease in transparency due to migration.

The molded article of the present invention is produced by molding an ultraviolet absorbing molding agent.
Examples of the molding method include extrusion molding, injection molding, and blow molding. Examples of extrusion molding include compression molding, pipe extrusion molding, lamination molding, T-die molding, inflation molding, and melt spinning.

The molding temperature is usually 160 to 240°C, depending on the softening point of the diluted resin.

In the present invention, the molded article is obtained by putting an ultraviolet-absorbing molding agent into a mold. Moreover, the molded body includes an article obtained without using a mold such as a plastic film, and a molded body.

The molded article of the present invention can be used, for example, in medical drugs, cosmetics, food containers and packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, home appliances, building materials for housing, toiletries, etc. Can be used for a wide range of purposes such as supplies. Furthermore, it can be used in a wide range of applications such as display materials, sensor materials, and optical control materials.

(UV absorbing coating agent)
The ultraviolet absorbing agent of the present invention can be used as an ultraviolet absorbing coating agent. The external radiation absorbing coating agent may be used alone or may be mixed to form a coating composition.
Specifically, the ultraviolet absorbing coating agent is a pressure-sensitive adhesive or an adhesive for coating a pressure-sensitive adhesive layer or an adhesive layer on a base material as a pressure-sensitive adhesive sheet or adhesive sheet, or a pressure-sensitive adhesive or adhesive for coating a pressure-sensitive adhesive layer or an adhesive layer on a base material. It is sometimes used as a paint for coating layers.
The adhesive preferably contains the ultraviolet absorbing polymer of the present invention and a curing agent.
The ultraviolet absorbing polymer is a polymer synthesized by radical polymerization of an ultraviolet absorbing unsaturated monomer, (meth)acrylic acid ester, and an acidic group-containing monomer and/or a hydroxyl group-containing monomer.
Examples of the acidic group-containing monomer include acrylic acid and methacrylic acid.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate.

Examples of the curing agent include isocyanate curing agents, epoxy curing agents, aziridine curing agents, metal chelate curing agents, and the like.

The adhesive can be applied, for example, onto a release sheet and dried to form an adhesive layer, and a base material can be bonded onto the adhesive layer to produce an adhesive sheet.

The adhesive sheet is preferably used for display applications (for example, televisions, personal computers, smartphones, etc.) by being attached to a display.
By containing the ultraviolet absorbing material of the present invention, the adhesive sheet can absorb ultraviolet rays included in the backlight and light in the short wavelength range of visible light, thereby suppressing adverse effects on the eyes. Furthermore, by absorbing light in the short wavelength region of ultraviolet rays and visible light contained in sunlight, it is possible to suppress deterioration of display elements of a display, and furthermore, it is possible to suppress a decrease in transparency due to migration. Note that the terms sheet, film and tape are synonymous.

The coating agent, which is a paint, preferably contains a monomer-shaped ultraviolet absorber or ultraviolet absorbing polymer, and other resins, and further preferably contains an organic solvent. The other resin preferably has a glass transition temperature of 30° C. or higher. Examples include nitrocellulose and polyester. Additionally, thermosetting resins can be used for paint applications. In this case, it is preferable to include a curing agent. The thermosetting resin is a resin having a glass transition temperature of 10° C. or higher. Examples of the thermosetting resin include acrylic resin, polyester, and polyurethane. Moreover, it is preferable that the thermosetting resin has a functional group capable of reacting with a curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Examples of the curing agent include isocyanate curing agents, epoxy curing agents, aziridine curing agents, and amine curing agents.

When the ultraviolet absorber of the present invention is used as a coating material for a coating layer, it is preferable that the ultraviolet absorbent coating agent has photocurability. Therefore, it is preferable to include a photopolymerizable compound and a photopolymerization initiator. Moreover, it is more preferable that the ultraviolet absorber in the ultraviolet absorbing coating agent contains a photocurable site. The ultraviolet absorbing coating agent is preferably used as a hard coat layer, a top coat layer, or an intermediate layer of various laminates. In addition, known additives and organic solvents can be contained as needed.

Photopolymerizable compounds include monomers and oligomers. Examples of photopolymerizable compounds include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and β-carboxyethyl (meth)acrylate. ) acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxy Tetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid Acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, ester Acrylate, (meth)acrylic ester of methylolated melamine, various acrylic esters and methacrylic esters such as epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol di Examples include vinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like.

Examples of photopolymerization initiators include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime ester compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds, and imidazole. Examples include titanocene compounds, titanocene compounds, and the like. Among these, oxime ester compounds are preferred in terms of high sensitivity.

The ultraviolet absorbing coating agent of the present invention can be used as a coating layer, for example, in medical drugs, cosmetics, food containers and packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, and home appliances. It can be used in a wide range of applications, including products, building materials for housing, toiletries, etc. Furthermore, it can be used in a wide range of applications such as glass interlayer materials, lens materials, display materials, sensor materials, and optical control materials.

The present invention will be explained in more detail below. The invention is not limited to the examples. Note that "parts by mass" is written as "parts" and "% by mass" is written as "%".

(molecular weight)
The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8320GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was performed at a flow rate of 0.35 ml/min using a THF solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. All molecular weights are polystyrene equivalent values.

(Non-volatile content)
To determine the non-volatile content, weigh 0.5g of the sample into an aluminum container and heat it in an electric oven at 200°C for 1 hour.
It was calculated from the weight ratio before and after drying after 0 minutes.
Non-volatile content % = (weight after drying) / (weight before drying) x 100

<Example of monomer-shaped ultraviolet absorber>
(Example 1)
[Ultraviolet absorber (A-1)]
In a four-necked flask equipped with a thermometer, stirrer, and condenser, add 44.0 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 87.7 parts of aluminum chloride, and chlorobenzene. 660 parts were charged and stirred at room temperature to dissolve. Next, 49.9 parts of methyl 6-hydroxy-2-naphthoate was added little by little, and the mixture was heated to 90°C and stirred for 2 hours. After the reaction was completed, 2000 parts of methanol and 500 parts of water were placed in a separately prepared beaker, and the above reaction solution was added dropwise. The deposited precipitate was separated by filtration, and the resulting wet cake was returned to 1000 parts of methanol, reslurred at room temperature for 1 hour, and filtered. The obtained wet cake was dried at 80° C. overnight to obtain 62.8 parts of a methyl ester intermediate.
Next, 62.8 parts of the methyl ester intermediate, 630 parts of methanol, 314 parts of 25% aqueous sodium hydroxide solution, and 314 parts of water were placed in a four-necked flask equipped with a thermometer, stirrer, and cooling tube. , heated to 60° C. and stirred for 3 hours. After the reaction was completed, 1000 parts of 15% hydrochloric acid was placed in a separately prepared beaker, and the above reaction solution was added dropwise. The deposited precipitate was separated by filtration, and the resulting wet cake was reslurried with 1000 parts of water for 1 hour, and then filtered. The obtained wet cake was dried at 80° C. overnight to obtain 59.1 parts of a carboxylic acid intermediate.
Subsequently, 59.1 parts of carboxylic acid intermediate, 40.1 parts of glycidyl methacrylate, and 1.9 parts of N,N-dimethylbenzylamine were placed in a four-necked flask equipped with a thermometer, stirrer, and cooling tube. 0.06 parts of methylhydroquinone and 590 parts of N-methyl-2-pyrrolidone were added, heated to 100°C under an air atmosphere, and stirred for 4 hours. After the reaction was completed, 600 parts of methanol, 300 parts of water, and 300 parts of 35% hydrochloric acid were placed in a separately prepared beaker, and the above reaction solution was added dropwise. The deposited precipitate was separated by filtration, and the resulting wet cake was returned to 1000 parts of methanol, reslurred at room temperature for 1 hour, and filtered. The obtained wet cake was dried under reduced pressure at 60° C. overnight to obtain 63.3 parts of ultraviolet absorber (A-1).

As a result of NMR measurement of the ultraviolet absorber (A-1), results supporting the above structure were obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: BRUKER AVANCE400
Resonance frequency: 400MHz ( ^1H -NMR)
Solvent: dimethyl sulfoxide- _d6
Tetramethylsilane was used as an internal standard substance for ¹ H-NMR, the chemical shift value was expressed in δ value (ppm), and the coupling constant was expressed in Hertz. Further, s stands for singlet, d stands for double, dd stands for double-double, t stands for triplet, m stands for multiple, and br stands for broad. The contents of the obtained NMR spectrum are as follows.
δ=1.90 (s, 3H, -CH ₃ ), 4.16 (m, 1H, -CH-OH), 4.24 (m, 2H, -O-CH ₂ -), 4.34 (m , 2H, -O-CH ₂ -), 5.50 (br, 1H, -CH-OH), 5.70 (d, J=1.6Hz, 1H, C=CH ₂ ), 6.10 (d , J=1.6Hz, 1H, C=CH ₂ ), 7.40 (d, J=9.0Hz, 1H, naphthalene ring-H), 7.67 (t, J=7.3Hz, 4H, benzene ring-H), 7.70-7.80 (m, 2H, benzene ring-H), 7.70-7.80 (m, 1H, naphthalene ring-H), 8.03 (dd, J=9 .2, 2.0Hz, 1H, naphthalene ring-H), 8.24 (d, J=9.0Hz, 1H, naphthalene ring-H), 8.62 (d, J=7.3Hz, 4H, benzene ring-H), 8.64 (d, J=2.0Hz, 1H, naphthalene ring-H), 12.00-13.00 (br, 1H, naphthalene ring-OH)

As mentioned above, in this specification, the structure was identified by NMR using the ultraviolet absorbing agent (A-1) as an example. The structures of other ultraviolet absorbers were also identified by NMR in the same manner as above, but the data are omitted.

(Example 2)
[Ultraviolet absorber (A-2)]
A UV absorber (A-2) was obtained in the same manner as in Example 1 except that methyl 6-hydroxy-1-naphthoate was used instead of methyl 6-hydroxy-2-naphthoate.

(Example 3)
[Ultraviolet absorber (A-3)]
A UV absorber (A-3) was obtained in the same manner as in Example 1 except that methyl 7-hydroxy-2-naphthoate was used instead of methyl 6-hydroxy-2-naphthoate.

(Example 4)
[Ultraviolet absorber (A-4)]
A UV absorber (A-4) was obtained in the same manner as in Example 1 except that methyl 3-hydroxy-2-naphthoate was used instead of methyl 6-hydroxy-2-naphthoate.

(Example 5)
[Ultraviolet absorber (A-5)]
Into a four-necked flask equipped with a thermometer, stirrer, and cooling tube, 20.0 parts of the carboxylic acid intermediate of Example 1, 0.3 parts of N,N-dimethylformamide, and 200 parts of chlorobenzene were charged, and cooled. while stirring. Next, 11.4 parts of thionyl chloride was added dropwise little by little at 0°C, and the mixture was stirred at 60°C for 2 hours. Next, 9.3 parts of 2-hydroxyethyl methacrylate and 9.7 parts of triethylamine were added dropwise little by little, and the mixture was stirred at 60°C for 6 hours. After the reaction was completed, 300 parts of 10% hydrochloric acid was placed in a separately prepared beaker, and the above reaction solution was added dropwise. The deposited precipitate was separated by filtration, and the obtained wet cake was returned to 300 parts of methanol, reslurred for 1 hour at room temperature, and then filtered. The obtained wet cake was dried under reduced pressure at 60° C. overnight to obtain 20.3 parts of ultraviolet absorber (A-5).

(Example 6)
[Ultraviolet absorber (A-6)]
A UV absorber (A-6) was obtained in the same manner as in Example 5 except that 2-aminoethyl methacrylate was used instead of 2-hydroxyethyl methacrylate.

(Example 7)
[Ultraviolet absorber (A-7)]
A UV absorber (A-7) was obtained in the same manner as in Example 5 except that allyl alcohol was used instead of 2-hydroxyethyl methacrylate.

(Example 8)
[Ultraviolet absorber (A-8)]
In a four-neck flask equipped with a thermometer, stirrer, and cooling tube, add 20.0 parts of ultraviolet absorber (A-1), 0.05 parts of dioctyltin dilaurate, 0.0006 parts of dibutylhydroxytoluene, and chlorobenzene. 200 parts of were added and stirred at room temperature. Next, after heating the reaction solution to 70°C, 5.5 parts of 2-isocyanatoethyl methacrylate was added dropwise little by little, and the mixture was stirred for 5 hours. After the reaction was completed, 300 parts of water was placed in a separately prepared beaker, and the above reaction solution was added dropwise. The deposited precipitate was separated by filtration, and the obtained wet cake was returned to 300 parts of methanol, reslurred for 1 hour at room temperature, and then filtered. The obtained wet cake was dried under reduced pressure at 60° C. overnight to obtain 22.9 parts of ultraviolet absorber (A-8).

(Example 9)
[Ultraviolet absorber (A-9)]
A UV absorber (A-9) was obtained in the same manner as in Example 5 except that glycerol dimethacrylate was used instead of 2-hydroxyethyl methacrylate.

(Example 10)
[Ultraviolet absorber (A-10)]
A UV absorber (A-10) was obtained in the same manner as in Example 5, except that pentaerythritol triacrylate was used instead of 2-hydroxyethyl methacrylate.

(Example 11)
[Ultraviolet absorber (A-11)]
A UV absorber (A-11) was obtained in the same manner as in Example 1 except that cyanuric chloride was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. .

(Comparative example 1)
[Ultraviolet absorber (A-12)]
The known compound 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol was used as it was for evaluation.

(Comparative example 2)
[Ultraviolet absorber (A-13)]

The above intermediate was synthesized using cyanuric chloride, 2-methylresorcinol, and 1-bromohexane as raw materials according to the synthesis method of Examples such as JP-A-11-71356 and JP-A-2018-504479.
Subsequently, 20.0 parts of the above intermediate and 100 parts of tetrahydrofuran were charged into a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and the mixture was stirred at room temperature. Then, 5.7 parts of acryloyl chloride was added dropwise little by little. Thereafter, 8.6 parts of triethylamine was added dropwise little by little, and the mixture was stirred at room temperature for 1 hour. On the other hand, 300 parts of water was placed in a beaker, and the above reaction solution was added dropwise, heated and stirred to evaporate tetrahydrofuran until the ultraviolet absorber was precipitated, and filtered. The obtained wet cake was returned to 300 parts of water, reslurred at room temperature for 1 hour, and filtered. The obtained wet cake was dried under reduced pressure at 60°C to obtain the following ultraviolet absorber (A-13).

(A-13)

[Heat-resistant]
Table 1 shows the evaluation results of the ultraviolet absorbers of Examples 1 to 11 and the ultraviolet absorbers of Comparative Examples 1 to 2 using a thermogravimetric differential thermal analyzer. Moreover, the measurement conditions are as follows.
<Measurement conditions>
Device: TG-DTA8122 (manufactured by RIGAKU)
Measurement atmosphere: Nitrogen Temperature rising conditions: 10°C/min
Measurement range: 40-500℃

The evaluation criteria for heat resistance are as follows.
○: 50% weight loss temperature is 420°C or higher △: 50% weight loss temperature is 370°C or higher and lower than 420°C ×: 50% weight loss temperature is lower than 370°C. Impractical

[Light absorption]
Table 1 shows the results of measuring the ultraviolet and visible absorption spectra of the ultraviolet absorbers of Examples 1 to 11 and the ultraviolet absorbers of Comparative Examples 1 and 2. Moreover, the preparation method of the measurement container and the measurement conditions are as follows. In addition, all of these ultraviolet absorbers were evaluated for visible light absorption, etc., after confirming that the transmittance was less than 10% in the wavelength range of 320 nm or more and less than 400 nm.

<Method for preparing solution>
1 part of ultraviolet absorber and 1000 parts of chloroform were mixed and completely dissolved. Subsequently, 1 part of the above solution and 99 parts of chloroform were uniformly mixed to prepare a measurement solution having a concentration of 10 ppm.

<Measurement conditions>
Equipment: U-3500 (manufactured by Hitachi, Ltd.)
Measurement wavelength: 260-700nm

The evaluation criteria for ultraviolet/visible absorption spectra are as follows.
○: Absorbs light in the visible light region of 400 to 420 nm, and absorbs only light in the ultraviolet region with a maximum absorption wavelength of 360 nm or more in the 340 to 420 nm region ×: less than 400 nm. Impractical

[purity]
Purity was assessed by high performance liquid chromatography measurements equipped with a UV detector. ACQUITY UPLC H-Class (manufactured by Waters) was used as the device, ACQUITY UPLC BEH C18 was used as the column, the temperature was 40 degrees, the eluent was 50 mM ammonium acetate aqueous solution and DMF, and the flow rate was 0.4 ml/min. The gradient was measured. The measurement sample was dissolved in DMF and 1 μL was injected.

The evaluation criteria for purity are as follows.
○: No peak of excess reactant, purity 95% or more Δ: No peak of excess reactant, purity 85% or more and less than 95% ×: Excess reactant peak present. Not practical. Note that the term "excess reactant" means one in which the reaction has proceeded excessively and the ultraviolet absorber has been polysubstituted with polymerizable sites.

[Colorability]
The color of the obtained ultraviolet absorber was visually evaluated. The evaluation criteria are as follows.
○: Pale yellow. Good △: Yellow. Practical range: Dark yellow. Impractical

<Example of ultraviolet absorbing polymer>
(Example 12)
[Ultraviolet absorbing polymer (B-1)]
In a four-necked separable flask equipped with a thermometer, stirrer, cooling tube, and dropping funnel, 40.0 parts of ultraviolet absorber (A-1), 0.4 parts of 2-ethylhexyl thioglycolate, and 56.9 parts of cyclohexanone were added. The temperature was raised to 100° C. under a nitrogen stream. Separately, 0.4 parts of 2,2'-azobis(dimethyl isobutyrate) and 2.3 parts of cyclohexanone were mixed and completely dissolved to prepare a polymerization initiator solution, which was then charged into a dropping funnel. A polymerization initiator solution was added dropwise over 6 hours to carry out a polymerization reaction. Two hours after the dropwise addition was completed, it was confirmed that the conversion rate from the solid content was 98% or more, and the polymerization reaction was completed by cooling. The obtained ultraviolet absorbing polymer (B-1) had a nonvolatile content of 40.8%, a weight average molecular weight (Mw) of 30,000, a number average molecular weight (Mn) of 15,000, and a molecular weight distribution (Mw/Mn). ) was 2.00.

The ultraviolet absorbing polymers of Examples 13 to 27 and Comparative Examples 3 to 4 were produced in the same manner as in Example 12 using the polymer compositions shown in Table 2. Note that the ultraviolet absorbing polymer (B-17) of Comparative Example 3 gelled during polymerization.

[Heat-resistant]
Table 2 shows the evaluation results of the ultraviolet absorbing polymers of Examples 12 to 27 and Comparative Example 4 using a thermogravimetric differential thermal analyzer. Moreover, the measurement conditions are as follows.
<Measurement conditions>
Device: TG-DTA8122 (manufactured by RIGAKU)
Measurement atmosphere: Nitrogen Temperature rising conditions: 10°C/min
Measurement range: 40-500℃

The evaluation criteria for heat resistance are as follows.
○: 50% weight loss temperature is 360°C or higher ×: 50% weight loss temperature is less than 360°C. Impractical

[Light absorption]
Table 2 shows the results of measuring the ultraviolet and visible absorption spectra of the ultraviolet absorbing polymers of Examples 12 to 27 and Comparative Example 4. Moreover, the preparation method of the measurement container and the measurement conditions are as follows. Note that all of these ultraviolet absorbing polymers were evaluated for visible light absorption, etc., after confirming that the transmittance was less than 10% in the wavelength range of 320 nm or more and less than 400 nm.

<Method for preparing solution>
1 part of ultraviolet absorber and 1000 parts of chloroform were mixed and completely dissolved. Subsequently, 5 parts of the above solution and 95 parts of chloroform were uniformly mixed to prepare a measurement solution with a concentration of 10 ppm.

<Measurement conditions>
Equipment: U-3500 (manufactured by Hitachi, Ltd.)
Measurement wavelength: 260-700nm

The evaluation criteria for ultraviolet/visible absorption spectra are as follows.
○: Absorbs light in the visible light region of 400-420 nm, and maximum absorption wavelength in the 340-420 nm region is 360 nm or more ×: Absorbs only light in the ultraviolet region of less than 400 nm

The abbreviations used in Table 2 are as follows.
MMA: Methyl methacrylate LA: Lauryl acrylate ISTA: Isostearyl acrylate CHMA: Cyclohexyl methacrylate DCPMA: Dicyclopentanyl methacrylate BzMA: Benzyl methacrylate MAnh: Maleic anhydride AA: Acrylic acid HEMA: 2-hydroxyethyl methacrylate Comparative monomer: 2-[ 2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole

(Example 28)
<Manufacture of masterbatch>
100 parts of wax (C-1) and 100 parts of dried ultraviolet absorbing polymer (B-1) were mixed and kneaded at 160°C using a three-roll mill to obtain ultraviolet absorbing polymer (B-1). A dispersion of was obtained. Next, 12.2 parts of the above-obtained dispersion were mixed with 97.8 parts of polyolefin (D-1) using a Henschel mixer. Next, the mixture was melt-kneaded at 180° C. using a single-screw extruder with a screw diameter of 30 mm, and then cut into pellets using a pelletizer to obtain a masterbatch. The dried product of the ultraviolet absorbing polymer was obtained by performing reprecipitation purification by a known method and vacuum drying at 60° C. for 24 hours.
<Film molding>
10 parts of the obtained masterbatch were mixed with 100 parts of polyolefin (D-1) as a diluent resin. Next, using a T-die molding machine (manufactured by Toyo Seiki), the mixture was melt-mixed and molded at a temperature of 180° C. to obtain a film with a thickness of 1 mm.

(Examples 29 to 43, Comparative Example 5)
A masterbatch was produced in the same manner as in Example 28, except that the materials in Example 28 were changed to the materials and blending amounts shown in Table 3, and then the films of Examples 29 to 43 and Comparative Example 5 were produced, respectively. . The blending amounts of the ultraviolet absorbing polymer and diluent resin in the masterbatch were adjusted so that the ultraviolet absorber concentration (UVA concentration) in the film was the same as in Example 28.

(Example 44)
<Manufacture of masterbatch, which is an ultraviolet absorbing molding agent>
100 parts of polycarbonate (E-1) and 20 parts of dried ultraviolet absorbing polymer (B-8) were charged into a twin screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm through the same supply port, and heated at 280°C. After melting and kneading, the mixture was cut into pellets using a pelletizer to prepare a masterbatch. The dried product of the ultraviolet absorbing polymer was obtained by performing reprecipitation purification by a known method and vacuum drying at 60° C. for 24 hours.
<Film molding>
6.6 parts of the obtained masterbatch was mixed with 103.4 parts of diluted resin polycarbonate (E-1), and melt-mixed at a temperature of 280°C using a T-die molding machine (manufactured by Toyo Seiki). Then, a film with a thickness of 1 mm was formed.

(Examples 45-47, Comparative Examples 6-9)
A masterbatch was produced in the same manner as in Example 44, except that the material in Example 44 was changed to the material shown in Table 4, and then films of Examples 45 to 47 and Comparative Examples 6 to 9 were produced, respectively. The blending amounts of the ultraviolet absorbing polymer and diluent resin in the masterbatch were adjusted so that the ultraviolet absorber concentration (UVA concentration) in the film was the same as in Example 44.

[optical properties]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The transmittance was determined by measuring the spectral transmittance against a white standard plate.
It was evaluated whether the following conditions were satisfied.
○: Light transmittance in the wavelength range of 380 to 400 nm is less than 2% over the entire region ×: Light transmittance in the wavelength range of 380 to 400 nm is 2% or more over the entire region. Impractical

[transparency]
The transparency of the obtained film was visually evaluated. The evaluation criteria are as follows.
◎: No turbidity observed at all. Very good: Almost no turbidity observed. Good △: Some turbidity is observed. Practical range ×: Turbidity is clearly observed. Impractical

[Quality over time]
The obtained film was exposed with a xenon weather meter at an illuminance of 60 W/m ² from 300 to 400 nm for 1500 hours.
○: No yellowing observed at all.
Δ: Slight yellowing is observed.
×: Yellowing is clearly observed. Impractical

[Migration evaluation]
The obtained film was sandwiched between soft vinyl chloride sheets and heat-pressed using a heat press under conditions of a pressure of 100 g/cm ² and a temperature of 170° C. for 30 seconds. Next, the film was immediately removed and migration to the soft vinyl chloride sheet was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation was performed by selecting five points on the soft vinyl chloride sheet that had undergone the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
○: Absorbance at less than 400 nm and from 400 to 420 nm is less than 0.05 Δ: Absorbance at less than 400 nm and from 400 to 420 nm is 0.05 or more and less than 0.2 ×: Absorbance at less than 400 nm and from 400 to 420 nm is 0.2 or more. Impractical

[Thermal change in light absorption over time]
The resulting film was evaluated for changes in light absorption over time.
<Evaluation method>
After placing the obtained film in an oven with an internal temperature of 80° C. for one week, the change in shape of the ultraviolet/visible absorption spectrum was evaluated. The evaluation criteria are as follows.
○: No change is observed in the spectral shape before and after applying thermal history. ×: The spectral shape changes before and after applying thermal history. Impractical

The waxes used in the examples are shown below.
(C-1) Polyethylene wax (Sunwax 131-P, average molecular weight 3500, melting point 105°C, manufactured by Sanyo Chemical Industries, Ltd.)

Moreover, the polyolefins (number average molecular weight 30,000 or more) used in the examples are shown below.
(D-1) Polyethylene (Suntec LD M2270, MFR=7g/10min, manufactured by Asahi Kasei Chemicals)

Furthermore, thermoplastic resins other than polyolefin used in Examples are shown below.
(E-1) Polycarbonate (Iupilon S3000, MFR=15g/10min, manufactured by Mitsubishi Engineering Plastics)
(E-2) Polymethacrylic resin (Acrypet MF, MFR=14g/10min, manufactured by Mitsubishi Rayon Co., Ltd.)
(E-3) Polyester (Mitsui Pet SA135, manufactured by Mitsui Chemicals)
(E-4) Cycloolefin resin (TOPAS5013L-10, manufactured by Mitsui Chemicals)

(Production example F-1 of adhesive resin)
Using a reaction apparatus equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 96.0 parts of n-butyl acrylate and 4.0 parts of 2-hydroxylethyl acrylate were added under a nitrogen atmosphere. 50% of the total amount, 0.2 parts of 2,2'-azobisisobutylnitrile as a polymerization initiator, and 150 parts of ethyl acetate as a solvent were charged into a reaction tank, and the remaining 50% of the above total amount An appropriate amount of ethyl acetate was charged into the dropping tank. Next, after starting heating and confirming the start of the reaction in the reaction tank, the contents of the dropping tube and 0.01 part of 2,2'-azobisisobutylnitrile diluted with ethyl acetate were added under reflux. dripped. After the dropwise addition was completed, the reaction was carried out for 5 hours while maintaining the reflux state. After the reaction was completed, it was cooled and an appropriate amount of ethyl acetate was added to obtain Production Example F-1 of adhesive resin, which is an acrylic resin. The resulting adhesive resin of Production Example F-1 had a weight average molecular weight of 500,000, a nonvolatile content of 40%, and a viscosity of 3,200 mPa·s.

(Example 50)
As an adhesive resin, 2 parts of ultraviolet absorbing polymer (B-1) was mixed with 100 parts of non-volatile content of the adhesive resin of Production Example F-1, and as a silane coupling agent, KBM-403 (Shin-Etsu Chemical Co., Ltd.) was mixed. Added 0.1 part of trimethylolpropane adduct of tolylene diisocyanate (abbreviation: TDI-TMP, NCO value = 13.2, nonvolatile content = 75%) as a curing agent (D), The mixture was thoroughly stirred to obtain an adhesive. Thereafter, this adhesive was applied onto a polyethylene terephthalate base release film having a thickness of 38 μm so that the thickness after drying would be 50 μm, and was dried in a hot air oven at 100° C. for 2 minutes. Then, a 25 μm polyethylene terephthalate film was attached to the adhesive layer side and aged in this state at room temperature for 7 days to obtain an adhesive sheet.

(Examples 51 to 65, Comparative Example 10)
As shown in Table 5, adhesive sheets of Examples 51 to 65 and Comparative Example 10 were obtained by adjusting in the same manner as in Example 50. The amount of the ultraviolet absorbing polymer was adjusted so that the ultraviolet absorber concentration (UVA concentration) in the dried coating film was the same as in Example 50.

(Evaluation of adhesive sheet)
[Adhesive force]
The obtained pressure-sensitive adhesive sheet was prepared in a size of 25 mm in width and 150 mm in length. The release film was peeled off from the pressure-sensitive adhesive sheet at 23° C. and in an atmosphere with a relative humidity of 50%, and the exposed pressure-sensitive adhesive layer was attached to a glass plate, and pressure-bonded once with a 2 kg roll. After being left for 24 hours, the adhesive strength was measured in a 180° peel test in which the film was peeled off at a rate of 300 mm/min in a 180° direction using a tensile testing machine, and evaluated based on the following evaluation criteria. (Based on JIS Z0237:2000)
◎: Adhesive strength is 15N or more, very good.
○: Adhesive force is 10N or more and less than 15N, good.
×: Adhesive force is less than 10N, impractical.

[Holding power]
The obtained pressure-sensitive adhesive sheet was prepared in a size of 25 mm in width and 150 mm in length. In accordance with JIS Z0237:2000, the releasable sheet was peeled off from the adhesive sheet, and the adhesive layer was pasted on the lower end portion of a polished stainless steel plate measuring 30 mm in width and 150 mm in length, measuring 25 mm in width and 25 mm in width, and then rolled in a 2 kg roll. After crimping once back and forth, a load of 1 kg was applied in an atmosphere of 40° C., and the holding force was measured by leaving it for 70,000 seconds. For evaluation, the length of the downward shift of the upper end of the adhesive sheet pasting surface was measured.
Evaluation criteria ○: The length of deviation is less than 0.5 mm. Good.
x: The deviated length is 0.5 mm or more. Not practical.

[transparency]
The releasable sheet was peeled off from the resulting pressure-sensitive adhesive sheet, and the transparency of the pressure-sensitive adhesive layer was visually evaluated. The appearance of the adhesive layer was evaluated based on the following three-level evaluation criteria.
○: Adhesive layer is transparent and good △: Adhesive layer is slightly whitened, but in practical use ×: Adhesive layer is whitened and cannot be put to practical use

[Migration evaluation]
The resulting pressure-sensitive adhesive sheet was prepared to have a size of 100 mm in width and 100 mm in length. The release film was peeled off from the pressure-sensitive adhesive sheet at 23° C. and in an atmosphere with a relative humidity of 50%, and the exposed pressure-sensitive adhesive layer was attached to a glass plate, and pressure-bonded once with a 2 kg roll. Then, it was left in the same environment for 48 hours, and then the adhesive sheet was peeled off, and the migration property of the ultraviolet absorbing material to the glass was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation was performed by selecting 5 points on the glass that had undergone the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
○: Absorbance at less than 400 nm and from 400 to 420 nm is less than 0.05 Δ: Absorbance at less than 400 nm and from 400 to 420 nm is 0.05 or more and less than 0.2 ×: Absorbance at less than 400 nm and from 400 to 420 nm is 0.2 or more. Impractical

[Thermal change in light absorption over time]
The adhesive sheet was evaluated for changes in light absorption over time.
<Evaluation method>
After placing the adhesive sheet in an oven with an internal temperature of 80° C. for one week, changes in the shape of the ultraviolet and visible absorption spectra were evaluated. The evaluation criteria are as follows.
○: No change is observed in the spectral shape before and after applying thermal history. ×: The spectral shape changes before and after applying thermal history. Impractical

<Paint>
(Example 66)
A paint with the following composition was prepared by stirring and mixing.
Ultraviolet absorbing polymer (B-1) 1.0 parts Polyester (Vylon GK250, manufactured by Toyobo Co., Ltd.) 9.0 parts Methyl ethyl ketone 90.0 parts

(Examples 67 to 81, Comparative Example 11)
As shown in Table 6, the coatings of Examples 67 to 81 and Comparative Example 11 were obtained by preparing in the same manner as in Example 66. The amount of the ultraviolet absorbing polymer was adjusted so that the ultraviolet absorber concentration (UVA concentration) in the dried coating film was the same as in Example 66.

(Preparation of coated product)
The obtained coating material was applied to a glass substrate having a thickness of 1000 μm using a bar coater so as to have a dry film thickness of 6 μm, and was dried at 100° C. for 2 minutes to form a coating film.
(Evaluation of coated product)
The obtained coated product was evaluated by the following method.

[Transparency evaluation]
The transparency of the obtained substrate was visually evaluated.
○: No turbidity observed at all. Good ×: Turbidity is observed. Impractical

[Migration evaluation]
A soft vinyl chloride sheet was placed on the coating surface of the obtained coating, and heat-pressed using a heat press under conditions of a pressure of 100 g/cm ² and a temperature of 170° C. for 30 seconds. Next, the film was immediately removed and migration to the soft vinyl chloride sheet was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation was performed by selecting five points on the soft vinyl chloride sheet that had undergone the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
○: Absorbance at less than 400 nm and from 400 to 420 nm is less than 0.05 Δ: Absorbance at less than 400 nm and from 400 to 420 nm is 0.05 or more and less than 0.2 ×: Absorbance at less than 400 nm and from 400 to 420 nm is 0.2 or more. Impractical

[Thermal change in light absorption over time]
The resulting coated product was evaluated for changes in light absorption over time with heat.
<Evaluation method>
After the obtained coated product was placed in an oven with an internal temperature of 80° C. for one week, changes in the shape of the ultraviolet/visible absorption spectrum were evaluated. The evaluation criteria are as follows.
○: No change is observed in the spectral shape before and after applying thermal history. ×: The spectral shape changes before and after applying thermal history. Impractical

<Photocurable composition>
(Example 82)
Each raw material was mixed and stirred to prepare a photocurable composition with the following composition.
Ultraviolet absorber (A-1) 10.0 parts Photopolymerizable compound (polyfunctional acrylate "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)
9.0 parts Photopolymerization initiator (IGM ResinBV "Omnirad184") 1.0 parts Propylene glycol monomethyl ether 80.0 parts

(Examples 83-88, Comparative Examples 12-13)
As shown in Table 7, photocurable compositions of Examples 83 to 88 and Comparative Examples 12 to 13 were obtained by preparing in the same manner as in Example 82. The amount of the ultraviolet absorber or ultraviolet absorbing polymer was adjusted so that the ultraviolet absorber concentration (UVA concentration) in the dried coating film was the same as in Example 82.

(Preparation of coated product)
The above photocurable composition was coated onto a 1 mm thick glass substrate using a bar coater so that the dry film thickness was 6 μm. The obtained coating layer was dried at 100° C. for 1 minute, and then cured by irradiating ultraviolet rays of 400 mJ/cm ² with a high-pressure mercury lamp to prepare a coated article.
(Evaluation of coated product)
The obtained coated product was evaluated by the following method.

[Scratch resistance]
The coated product was set in a Gakushin tester and subjected to Gakushin testing 10 times at a load of 250 g using steel wool. The degree of scratching on the removed coated product was judged according to the following five-level visual evaluation. The larger the value, the better the scratch resistance of the cured film.
5: No scratches at all.
4: Slight scratches.
3: There are scratches, but the base material is not visible.
2: There are scratches and some of the cured film has peeled off.
1: The cured film has peeled off and the base material is exposed. Impractical

[Pencil hardness]
In accordance with JIS-K5600, using a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON), the hardness of the pencil lead was varied and the cured film of the coating was tested 5 times under a load of 500 g. I took the test. The hardness of the lead when it was not scratched once or scratched only once out of 5 times was defined as the pencil hardness of the cured film. The evaluation criteria are as follows.
A: 2H or more.
B:H.
C: Lower than H. Impractical

[transparency]
The transparency of the obtained coating was visually evaluated.
○: No turbidity observed at all. Good △: Slight turbidity is observed. Practical range ×: Much turbidity is observed. Impractical

[Migration evaluation]
The obtained coated product was sandwiched between two soft vinyl chloride sheets and heat-pressed using a heat press under conditions of a pressure of 100 g/cm ² and a temperature of 170° C. for 30 seconds. Next, the film was immediately removed and migration to the soft vinyl chloride sheet was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation was performed by selecting five points on the soft vinyl chloride sheet that had undergone the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
○: Absorbance at less than 400 nm and from 400 to 420 nm is less than 0.05 Δ: Absorbance at less than 400 nm and from 400 to 420 nm is 0.05 or more and less than 0.2 ×: Absorbance at less than 400 nm and from 400 to 420 nm is 0.2 or more. Impractical

[Thermal change in light absorption over time]
The resulting coated product was evaluated for changes in light absorption over time with heat.
<Evaluation method>
After the obtained coated product was placed in an oven with an internal temperature of 80° C. for one week, changes in the shape of the ultraviolet/visible absorption spectrum were evaluated. The evaluation criteria are as follows.
○: No change is observed in the spectral shape before and after applying thermal history. ×: The spectral shape changes before and after applying thermal history. Impractical

As shown in Tables 1 to 7, the ultraviolet absorbers and ultraviolet absorbing polymers of the present invention absorb light in the ultraviolet region below 400 nm and in the short wavelength region of visible light from 400 to 420 nm, and have excellent heat resistance, bleed resistance, and low It was found to have excellent coloring properties.

Claims (6)

An ultraviolet absorbent having a triazine ring directly bonded to a hydroxynaphthyl group, wherein the hydroxynaphthyl group is a group having a structure represented by the following general formula (1).
General formula (1) *-X-Y-Z
(In the formula, X represents -COO- or -CONH-, Y represents a divalent linking group, Z represents a polymerizable unsaturated group, and * represents a bond with a hydroxynaphthyl group. ) The ultraviolet absorber according to claim 1, wherein the polymerizable unsaturated group is one selected from the group consisting of a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. An ultraviolet absorber which is a polymer of the ultraviolet absorber according to claim 1 or 2. An ultraviolet absorber which is a copolymer of the ultraviolet absorber according to claim 1 or 2 and other monomers. An ultraviolet absorbing molding agent characterized by containing the ultraviolet absorber according to any one of claims 1 to 4. An ultraviolet absorbing coating agent comprising the ultraviolet absorber according to any one of claims 1 to 4.