JP6729776B1 - Ultraviolet absorbing material and composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet absorbing material capable of suppressing the migration of an ultraviolet absorbent and at the same time the migration of a coloring agent while suppressing the transmission of ultraviolet rays and visible light in a short wavelength region. An ultraviolet absorbing material which is a salt-forming product of an anionic dye (A) represented by any one of formulas (1) to (3) and a resin (B) having a cationic group in a side chain. The resin (B) having a cationic group in its side chain preferably contains the unit represented by the general formula (4). [Selection diagram] None

Description

The present invention relates to an ultraviolet absorbing material and its use.

The coating material, the pressure-sensitive adhesive, and the resin molded product (hereinafter referred to as a molded product) contain an ultraviolet absorber in order to prevent deterioration due to ultraviolet rays. However, the ultraviolet absorber often causes aggregation within the coating film, deposition on the surface, or migration to the contents due to migration.
In addition, paints, pressure-sensitive adhesives, molded products, and the like may be colored depending on the application so that visible light can be transmitted while suppressing transmission of ultraviolet light. For example, a molded article for cosmetics can be colored as necessary to prevent visible light deterioration while suppressing ultraviolet deterioration of the content, so that the filling amount of the content can be confirmed. Further, in the medical drug application, the color of the packaging material is changed according to the type of the contents, and the medication error can be prevented while grasping the remaining amount of the contents.

A film coated with a paint, a pressure-sensitive adhesive sheet coated with a pressure-sensitive adhesive, and a molded product have been used as packaging materials for detergents, beverages, pharmaceutical agents, cosmetics and the like. Especially in applications such as beverages, pharmaceutical agents, and cosmetics, it is necessary to prevent the ultraviolet deterioration of the contents while visually recognizing the contents, but migration of the ultraviolet absorber affects the quality of the contents. In addition, blue light generated from a liquid crystal display of a computer adversely affects the eyes, so blue light suppressing glasses are also used. However, migration of the ultraviolet absorber from the lenses of the glasses may adversely affect the human body.

Patent Documents 1 and 2 disclose a resin composition containing a polymer obtained by polymerizing a benzotriazole-based compound having an ethylenically unsaturated bond, as a means for suppressing migration of an ultraviolet absorbing compound.

JP 2001-72722 A JP, 2001-114842, A

However, the conventional resin composition can suppress the transmission of ultraviolet rays near 360 nm, which is close to visible light, but cannot suppress the light in the longer wavelength region. In addition, there is also a problem in that the coloring agent is agglomerated when the molded product is colored.

It is an object of the present invention to provide an ultraviolet absorbing material capable of suppressing the migration of the ultraviolet absorbent and the migration of the colorant while suppressing the transmission of ultraviolet rays and visible light in the short wavelength region.

The ultraviolet absorbing material of the present invention is a salt-forming product of an anionic dye (A) represented by any of the following general formulas (1) to (3) and a resin (B) having a cationic group in a side chain.

In formula (1), 1 to 3 of R _{61 to} R ₇₁ are X ⁻ Y ⁺ , and the others are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X ⁻ is , SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation.
In the general formula (2), one of R ₂₉ and R ₃₀ is an alkyl group having 1 to 20 carbon atoms, and the other is a hydroxyl group. R ₂₁ to R _28, and _R 31 _{to R 35} ^{is X} - ^{Y +} a has ^{1-3, X} - ^{Y +} than are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, , X ⁻ represents SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation.
In the general formula (3), R ₄₆ is an alkyl group having 1 to 20 carbon atoms, and R _{41 to} R ₄₅ and R _{47 to} R ₅₁ each have 1 to 3 X ⁻ Y ⁺ , and X ⁻ Except for Y ⁺ , each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, X ⁻ represents SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation.

According to the present invention described above, it is possible to provide an ultraviolet absorbing material capable of suppressing the migration of the ultraviolet absorbent and the migration of the coloring agent while suppressing the transmission of ultraviolet rays and visible light in the short wavelength region.

The terms used in this specification are defined. In the present specification, “(meth)acryl”, “(meth)acrylate” “(meth)acryloyl” and the like mean “acryl or methacryl”, “acrylate or methacrylate” “acryloyl or methacryloyl” and the like, For example, “(meth)acrylic acid” means “acrylic acid or methacrylic acid”. Unsaturated monomers, monomers and monomers are ethylenically unsaturated group-containing compounds.

The ultraviolet absorbing material of the present invention comprises an anionic dye (A) represented by any of the general formulas (1) to (3) (hereinafter also referred to as an anionic dye) and a resin (B) (having a cationic group in the side chain) ( Hereinafter, it is an ultraviolet absorbing material which is a salt-forming reaction product with a resin (B).
The ultraviolet absorbing material of the present invention can be used without limitation in applications for coloring while suppressing the transmission of ultraviolet rays such as paints, molded articles, pressure-sensitive adhesive sheets, and hard coats. Needless to say, the ultraviolet absorbing material can be used for other purposes.

In formula (1), 1 to 3 of R _{61 to} R ₇₁ are X ⁻ Y ⁺ , and the others are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X ⁻ is , SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation.
In formula (2), one of R ₂₉ and R ₃₀ is an alkyl group having 1 to 20 carbon atoms, and the other is a hydroxyl group. R ₂₁ to R _28, and _R 31 _{to R 35} ^{is X} - ^{Y +} a has ^{1-3, X} - ^{Y +} than are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, , X ⁻ represents SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation.
In the general formula (3), R ₄₆ is an alkyl group having 1 to 20 carbon atoms, and R _{41 to} R ₄₅ and R _{47 to} R ₅₁ each have 1 to 3 X ⁻ Y ⁺ , and X ⁻ Except for Y ⁺ , each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, X ⁻ represents SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation.

<Anionic dye (A)>
Examples of the anionic dye (A) represented by the general formula (1) include Acid Yellow 3 represented by the following chemical formula.

(A-11)

Examples of the anionic dye (A) represented by the general formula (2) include Direct Yellow 8 represented by the following chemical formula.
(A-21)

Further, the following compounds may also be mentioned as the anionic dye (A) represented by the general formula (2).

Examples of the anionic dye (A) represented by the general formula (3) include the following chemical formulas.

The Y ⁺ unit in the anionic dye (A) is not limited as long as it is a cation that does not interfere with the formation of a salt-forming product with the resin (B) having a cationic group in the side chain. Absent.

<Resin (B) having a cationic group in the side chain>
The resin (B) preferably contains a unit represented by the following general formula (4).

General formula (4)

In general formula (4), R ₁ represents a hydrogen atom or an alkyl group. R _{2 to} R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and _two of R _{2 to} R ₄ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. P ⁻ represents an inorganic or organic anion. In addition, in this specification, the alkyl group, the alkenyl group, and the aryl group may have a substituent.

Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group and a cyclohexyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

R ₁ is particularly preferably a hydrogen atom or a methyl group.

In formula (4), R _{2 to} R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

The alkyl group in R _{2 to} R ₄ is, for example, a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n. -Hexadecyl and n-octadecyl), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl) Etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

The alkenyl group in R _{2 to} R ₄ is, for example, a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-). Examples thereof include propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl), and cycloalkenyl groups (2-cyclohexenyl and 3-cyclohexenyl). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

The aryl group in R _{2 to} R ₄ is, for example, a monocyclic aryl group (phenyl or the like), a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl and naphthoquinolyl) and an aromatic heterocyclic hydrocarbon group. (Thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (derived from xanthone) Group) and 9-oxothioxanthenyl (a group derived from thioxanthone) and the like).

When the alkyl group, alkenyl group or aryl group represented by R _{2 to} R ₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group and an alkoxycarbonyl. A substituent selected from a group, a carboxyl group, a phenyl group and the like can be mentioned. The substituent is preferably a halogen atom, a hydroxyl group, an alkoxyl group or a phenyl group.

As R _{2 to} R ₄ , an alkyl group is preferable, and an unsubstituted alkyl group is more preferable, from the viewpoint of storage stability.

In addition, two parts of R _{2 to} R ₄ may be bonded to each other to form a ring.

In the general formula (5), the Q site connecting the C—C main chain site and the ammonium salt group represents an alkylene group, an arylene group, —CONH—R ₅ —, and —COO—R ₅ —, and R ₅ is an alkylene group. Are listed. Among these, -CONH-R< ₁₅ >- and -COO-R< ₅ >- are preferable for the reasons of polymerizability and availability. Further, R ₅ is preferably a methylene group, an ethylene group, a propylene group or a butylene group, more preferably an ethylene group.

In the general formula (4), the P ⁻ unit is preferably an inorganic or organic anion. Needless to say, the P ⁻ unit is not limited as long as it is an anion that does not interfere with the formation of a salt-forming product with the anionic dye (A).

Examples of the inorganic anion include hydroxide ion; halogen ion such as chloride ion, bromide ion, iodide ion and the like.
Organic anions include, for example, carboxylate ions such as formate ion and acetate ion; carbonate ion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, and peroxide ion. Manganese ion ions; complex ions such as hexacyanoferrate (III) ion. Among these, halogen ions and carboxylate ions are preferable, and halogen ions are more preferable, in terms of reactivity and stability. When the anion is an organic anion such as a carboxylate ion, the organic anion in the resin may be covalently bonded to form an inner salt.

The resin (B) is synthesized, for example, by a method of copolymerizing a monomer having a quaternary ammonium salt group as a monomer component, or a resin having an amino group obtained by copolymerizing a monomer having an amino group as a monomer component. , A method of reacting an onium chlorinating agent to form an ammonium salt, and the like. In the present specification, the monomers exemplified below that can form a cationic group are collectively referred to as an amino monomer.

Examples of the monomer having a quaternary ammonium salt group include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride and (meth)acryloyloxyethylmethylmorpholinoammonium. Alkyl (meth)acrylyl quaternary ammonium salts such as chloride, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, alkyl (meth)acryloylaminoethyldimethylbenzylammonium chloride ) Acryloylamide-based quaternary ammonium salt, dimethyldiallylammonium methylsulfate, trimethylvinylphenylammonium chloride and the like can be mentioned.

Examples of the monomer having an amino group include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, diisobutyl. Aminoethyl(meth)acrylate, di-t-butylaminoethyl(meth)acrylate, dimethylaminopropyl(meth)acrylamide, diethylaminopropyl(meth)acrylamide, dipropylaminopropyl(meth)acrylamide, diisopropylaminopropyl(meth)acrylamide, Examples thereof include (meth)acrylic acid ester having a dialkylamino group such as dibutylaminopropyl(meth)acrylamide, diisobutylaminopropyl(meth)acrylamide, and di-t-butylaminopropyl(meth)acrylamide, or (meth)acrylamide.
Styrene having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylamine compounds such as diallylmethylamine and diallylamine,
Examples thereof include amino group-containing aromatic monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone, and N-vinylcarbazole.

Examples of the onium chlorinating agent include alkyl sulfuric acid such as dimethyl sulfuric acid, diethyl sulfuric acid, or dipropyl sulfuric acid, sulfonic acid ester such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or octyl. Examples thereof include alkyl chlorides such as chloride, methyl bromide, ethyl bromide, propyl bromide, alkyl bromides such as octyl chlorobromide, benzyl chloride, benzyl bromide, and the like.

The reaction of the onium chlorinating agent with the amino group is preferably carried out by, for example, dropping an equimolar amount or less of the onium chlorinating agent with respect to the amino group to the solution of the compound having an amino group. The temperature during the ammonium salt forming reaction is about 90° C. or lower, and particularly preferably about 30° C. or lower when ammonium chloride of a monomer having an amino group is carried out. The reaction time is about 1 to 4 hours.

Other onium chlorinating agents include alkoxycarbonyl alkyl halides. The alkoxycarbonylalkyl halide is a compound represented by the following general formula (51).
Formula _{(51) Z-R 6 -COOR} 7
In the general formula (51), Z is halogen such as chlorine or bromine, preferably bromine, and R ₆ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. And R ₇ is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. ). Examples of the compound represented by the general formula (51) include chloroacetic acid.

In the unit represented by the general formula (4), at least one of R _{2 to} R ₄ may be a group substituted with an anionic group. In this case, the resin (B) having a cationic group in its side chain is a resin having a cationic group and an anionic group in its side chain (a resin having a betaine structure). Monomers necessary for synthesizing a resin having a cationic group and an anionic group in a side chain include a monomer having an amino group and a compound represented by the general formula (12), for example, equimolar to an amino group. after the compound represented by the following general formula (12) was reacted in the same manner as in the above onium chloride agent, the -COOR ₇ hydrolyzing carboxylate ion - obtained by converting the ^(-COO). Thus, a monomer having a carboxybetaine structure and an ammonium base can be synthesized.

The resin (B) is preferably copolymerized with other monomers in addition to the amino monomer. Other monomers include, for example, (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, styrene compound, (meth) ) Acrylonitrile, an acid group-containing monomer, and a hydroxyl group-containing monomer.

Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( Isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, T-octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth ) 2-Methoxyethyl acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, (meth) Benzyl acrylate, (meth)acrylic acid diethylene glycol monomethyl ether, (meth)acrylic acid diethylene glycol monoethyl ether, (meth)acrylic acid triethylene glycol monomethyl ether, (meth)acrylic acid triethylene glycol monoethyl ether, (meth)acrylic Acid polyethylene glycol monomethyl ether, (meth)acrylic acid polyethylene glycol monoethyl ether, (meth)acrylic acid β-phenoxyethoxyethyl, (meth)acrylic acid nonylphenoxy polyethylene glycol, (meth)acrylic acid dicyclopentenyl, (meth) Dicyclopentenyloxyethyl acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylic Examples thereof include tribromophenyl acid and tribromophenyloxyethyl (meth)acrylate.

Examples of the crotonic acid ester include butyl crotonic acid and hexyl crotonic acid.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumarate diester 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, Nt-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, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Styrene compounds include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples thereof include styrene, hydroxystyrene protected with a group capable of being deprotected by an acidic substance (eg, t-Boc, etc.), methyl vinylbenzoate, and the like.

Examples of the acid group-containing monomer include 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 itaconic anhydride. Unsaturated carboxylic acids such as citraconic acid, citraconic anhydride, and mesaconic acid or their acid anhydrides; trivalent or higher polyvalent unsaturated carboxylic acids or their acid anhydrides; succinic acid mono(2-acryloyloxyethyl), Mono[(meta) of divalent or higher polyvalent carboxylic acids such as mono(2-methacryloyloxyethyl) succinate, mono(2-acryloyloxyethyl) phthalate, and mono(2-methacryloyloxyethyl) phthalate. ) Acryloyloxyalkyl]ester; mono(meth)acrylates of carboxy polymers at both terminals such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2(or 3)-hydroxypropyl(meth)acrylate, 2(or 3 or 4)-hydroxybutyl(meth)acrylate and cyclohexanedimethanol mono(meth). ) Hydroxyalkyl (meth)acrylates such as acrylates, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth)acrylamide-based monomers having a hydroxyl group, such as N-(2-hydroxy). Having N-(hydroxyalkyl)(meth)acrylamide such as ethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, or a hydroxyl group Vinyl ether type monomer, for example, hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, 2-(or 3- or 4-)hydroxybutyl vinyl ether, or allyl ether having a hydroxyl group. Examples of such monomers include hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, and 2-(or 3- or 4-) hydroxybutyl allyl ether.

Further, it is obtained by adding alkylene oxide and/or lactone to the above-mentioned hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether. The obtained ethylenically unsaturated monomer can also be used as the (meth)acrylate (a2) having a hydroxy group in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more of these are used. When two or more kinds of alkylene oxides are used in combination, the bond form may be random and/or block. As the lactone to be added, δ-valerolacton, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms and a combination system of two or more of these are used. It is also possible to add both alkylene oxide and lactone.

Other monomers may be used alone or in combination of two or more.

When the ultraviolet absorbing material of the present specification is used for producing a composition containing a polyolefin, the other monomer used for the synthesis of the resin (B) is a monomer represented by the following general formula (52) in the above examples, and It is preferable to use at least one of the monomers represented by the following general formula (53). When these are used, the property of the ultraviolet absorbing material shifts to hydrophobic, so that the compatibility with the highly hydrophobic polyolefin is improved and, for example, the transparency of the molded product is further improved. In this case, the total amount of the unsaturated monomer represented by the general formula (52) and the unsaturated monomer represented by the general formula (53) is 100% by mass of the monomer unit used for the synthesis of the resin (B). , 30 to 97 mass% is preferable, and 50 to 90 mass% is more preferable. If it is contained in an appropriate amount, compatibility and transparency will be further improved.

General formula (52)

In formula (52), R ₅₆ represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 10 or more carbon atoms.

General formula (53)

In formula (53), R ₅₇ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.

Examples of the unsaturated monomer represented by the general formula (52) include lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, isobornyl (meth)acrylate and dicyclopenta. Nyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, etc. are mentioned. Among these, isostearyl (meth)acrylate and dicyclopentanyl (meth)acrylate are preferable, and dicyclopentanyl (meth)acrylate is more preferable.

Examples of the unsaturated monomer represented by the general formula (53) include styrene, vinyltoluene, 4-ethylstyrene, 4-n-butylstyrene, 4-tert-butylstyrene and 4-n-octylstyrene.

The resin (B) can be synthesized by, for example, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, living radical polymerization, or the like. Among these, free radical polymerization and living radical polymerization are preferable.

Free radical polymerization preferably uses a polymerization initiator. The polymerization initiator is preferably, for example, an azo compound or a peroxide. Azo compounds include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane1-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] and the like. Examples of the peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate. , T-butyl peroxy neodecanoate, t-butyl peroxy vivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

The polymerization initiator may be used alone or in combination of two or more kinds.

The polymerization reaction temperature is preferably about 40 to 150°C, more preferably 50 to 110°C. The reaction time is preferably about 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 further, the growth of polymerization occurs uniformly, so that block polymers and resins with uniform molecular weights (resins with a narrow molecular weight distribution) can be easily synthesized. ..

Living radical polymerization uses an organic halide or a sulfonyl halide compound as an initiator, and the atom transfer radical polymerization method using a transition metal complex as a catalyst can be applied to a wide range of monomers and can be applied to existing facilities. It is preferable in that the polymerization temperature can be adopted. The atom transfer radical polymerization method is preferably performed by the method described in the following references 1 to 8 and the like.
(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. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866.
(Reference 5) International Publication No. 96/030421 pamphlet (Reference 6) International Publication No. 97/018247 pamphlet (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

It is preferable to use an organic solvent for the synthesis of the resin (B). Examples of the organic solvent 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, ethylene. Examples thereof include glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

The organic solvent may be used alone or in combination of two or more kinds.

The resin (B) can also have a (meth)acryloyl group. When the ultraviolet absorbing material is used in, for example, a photocurable composition, it has a (meth)acryloyl group, whereby the photosensitivity is improved and a coating film having high hardness can be formed.

Examples of the method of introducing a (meth)acryloyl group into the resin (B) include the following methods.
(Method 1)
A resin having a cationic group and a hydroxyl group in its side chain is synthesized. In the synthesis method, for example, a resin having a cationic group and a hydroxyl group in its side chain can be synthesized by polymerizing a monomer containing a hydroxyl group with a monomer containing an ammonium salt. Alternatively, a resin containing a monomer having a hydroxyl group is polymerized together with a monomer having an amino group to synthesize a resin having an amino group and a hydroxyl group in a side chain. Next, an onium chlorinating agent can be used to synthesize a resin having a cationic group and a hydroxyl group in the side chain.
Next, a monomer having an isocyanate group is added and reacted with the hydroxyl group. This makes it possible to introduce a (meth)acryloyl group into a resin having a cationic group in its side chain.
Examples of the monomer having an isocyanate group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.
The reaction temperature between the isocyanate group and the hydroxyl group is preferably 50°C to 150°C, more preferably 70°C to 120°C. Urethane bonds are easily formed when the reaction is performed at an appropriate temperature.

(Method 2)
A resin having a cationic group and a carboxyl group on its side chain is synthesized. For example, a resin containing a monomer having a carboxyl group and a monomer containing a carboxyl group can be polymerized together with a monomer having an ammonium salt to synthesize a resin having a cationic group and a carboxyl group in a side chain. Alternatively, a resin having an amino group and a carboxyl group in its side chain is synthesized by polymerizing a monomer containing a monomer having a carboxyl group together with a monomer having an amino group. Then, an onium chlorinating agent can be used to synthesize a resin having a cationic group and a carboxyl group in the side chain.
Next, a monomer having an epoxy group is added and reacted to introduce a (meth)acryloyl group into the resin having a cationic group in its side chain.
Examples of the monomer having an epoxy group include glycidyl methacrylate and the like.
The reaction temperature of the epoxy group and the carboxyl group is preferably 70°C to 150°C, more preferably 80°C to 120°C. The reaction can be completed promptly by reacting at an appropriate temperature.

(Method 3)
A resin having a cationic group and an epoxy group in its side chain is synthesized. For example, a resin containing a monomer having an epoxy group and a monomer containing an epoxy group can be polymerized to synthesize a resin having a cationic group and an epoxy group in a side chain. Alternatively, a monomer having an amino group and an epoxy group-containing monomer are polymerized to synthesize a resin having an amino group and an epoxy group in a side chain. Next, a resin having a cationic group and an epoxy group in the side chain can be synthesized using an onium chlorinating agent. Next, a monomer having a carboxyl group is added and reacted to have a cationic group in the side chain. A (meth)acryloyl group can be introduced into the resin.
The reaction conditions for the carboxyl group and the epoxy group are the same as above.

The content of the unit represented by the general formula (4) is preferably 4 to 74 mass% and more preferably 8 to 48 mass% in 100 mass% of the monomer unit constituting the resin (B). When contained in an appropriate amount, the solubility and the coloring power are further improved.

The weight average molecular weight (Mw) of the resin (B) is preferably 1,000 to 500,000, more preferably 3,000 to 15,000. The Mw is measured by gel permeation chromatography (GPC).

(Salt formation reaction)
The salt-forming reaction between the anionic dye (A) and the resin (B) is performed, for example, by stirring or vibrating an aqueous solution in which both are dissolved. In the aqueous solution, the cationic group of the resin (B) and the anionic group of the anionic dye (A) are ionized, and these are ion-bonded to each other, so that the ion-bonded portion becomes water-insoluble and a salt-forming material (ultraviolet absorbing material). Is deposited. On the other hand, since the salt of the counter anion of the resin (B) and the counter cation of the anionic dye (A) is water-soluble, it can be removed by washing with water or the like.

The anionic dye (A) and the resin (B) can be used alone or in combination of two or more in the salt formation reaction.

The aqueous solution used for the salt formation reaction may be a mixed solution of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2-(methoxymethoxy)ethanol, 2 -Butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, Diacetone alcohol, aniline, pyridine, N,N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2 , 4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4 methylpentanone and the like.

The ratio of the resin (B) and the anionic dye (A) is a molar ratio of all the cationic groups of the resin (B) to all the anionic groups (B) of the anionic dye, and is 10/1 to 1/ An amount corresponding to 4 is preferable, and 2/1 to 1/2 is more preferable.

In addition, the content of the portion derived from the anionic dye (A) in the entire salt-forming product is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. When it is contained in an appropriate amount, the ultraviolet absorptivity and the affinity with other components are further improved.

The content of the anionic dye (A) can be calculated by the following method. That is, it can be calculated by measuring the absorbance of the maximum absorption wavelength at the same concentration of the salt-forming substance and the anionic dye (A). The absorbance at the maximum absorption wavelength of the salt-forming substance at a certain concentration is r, the absorbance at the maximum absorption wavelength of the anionic dye (A) at the same concentration is a, and the molecular weight of the anionic dye (A) is Ma, of which When the total molecular weight of the counter cation is Mc, the structural site derived from the anionic dye (A) in the entire salt-forming product can be calculated by the following mathematical formula (1).
Formula (1) r×(Ma−Mc)/(ax×Ma)

<Paint>
It is preferable to include the ultraviolet absorbing material of the present specification, and it is more preferable to further include a resin.
The resin is a resin having a glass transition temperature of about 0 to 100° C., and examples thereof include epoxy resin, polyurethane, polyester, polyacrylic and the like.
A hardener may be used in combination with the resin, if necessary. Examples of the curing agent include isocyanate curing agents, amino resins and epoxy curing agents.

The coated article of the present specification preferably includes a coating film formed from a paint, and further preferably includes a base material. Examples of the method for forming the coating film include coating with a CED coater, a die coater, a gravure coater, or the like. The thickness of the coating film is about 1 to 100 μm. Examples of the substrate include glass, plastic film, paper and the like. The thickness of the base material is about 50 to 2000 μm.
When the coating material of the present specification is used for a display application, for example, it is preferably used as a coating agent used for a film laminated on the display. By including the ultraviolet absorbing material of the present invention in the coating agent used for the film, it is possible to absorb light in the short wavelength region of ultraviolet light or visible light contained in the backlight, and suppress adverse effects on the eyes. Further, by absorbing light in the short wavelength region of ultraviolet rays or visible light contained in sunlight, deterioration of the display element of the display can be suppressed, and further deterioration of transparency due to migration over time can be suppressed.

<Molding composition>
The molding composition of the present specification preferably contains an ultraviolet absorbing material and a thermoplastic resin. The molding composition is preferably used as a molded body by molding.
Examples of the thermoplastic resin include polyolefin, polycarbonate, polyacryl, polyester, cycloolefin resin and the like.

Examples of uses of the molded article include food packaging materials, pharmaceutical packaging materials, and display applications. The food packaging material and the pharmaceutical packaging material are preferably, for example, polyolefin or polyester. These molded products can be colored while improving flexibility and visibility, and suppressing deterioration of the content.
For display applications (for example, liquid crystal televisions, personal computer displays, smartphones, blue light suppressing glasses, etc.), for example, polyacryl, polycarbonate, etc. are preferable. These molded products can suppress adverse effects on the eyes by absorbing light in the short wavelength region such as ultraviolet rays and visible light contained in the backlight. Further, by absorbing light in the short wavelength region of ultraviolet rays or visible light contained in sunlight, deterioration of the display element of the display can be suppressed, and further deterioration of transparency with time due to migration can be suppressed.

<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 the polypropylene include crystalline or amorphous polypropylene.
Examples of copolymers using these include ethylene-propylene random, block or graft copolymers, α-olefin and ethylene or propylene copolymers, ethylene-vinyl acetate copolymers, and the like.
Among these, crystalline or amorphous polypropylene and ethylene-propylene random, block or graft copolymers are preferable, and propylene-ethylene block copolymers are more preferable. Further, polypropylene resin is preferable from the viewpoint of being inexpensive and having a small specific gravity, so that a molded product can be lightened.

The melt flow rate (MFR) of the polyolefin is preferably 1 to 100 (g/10 minutes). The MFR is a numerical value determined according to JIS K-7210.

<Polycarbonate>
Polycarbonate is a compound obtained by synthesizing a divalent phenol and a carbonate precursor by a known method. Examples of the divalent phenol include hydroquinone, resorcinol, 2,2-bis(4-hydroxyphenyl)propane, bis(4-vidroxyphenyl)methane, and 2,2-bis(4-hydroxy-3,5-dimethyl). Phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-vidroxyphenyl)sulfide and the like can be mentioned. Of these, bis(4-vidroxyphenyl)alkane-based compounds are preferable, and 2,2-bis(4-hydroxyphenyl)propane called bisphenol A is more preferable.
Examples of the carbonate precursor include phosgene, diphenyl carbonate, and dihaloformate of divalent phenol. Among these, diphenyl carbonate is preferable.

<Polyacrylic>
Polyacryl is a compound obtained by polymerizing a methyl methacrylate monomer or an ethyl methacrylate monomer by a known method, and examples thereof include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer and ethylene-acrylic acid copolymer. Examples include coalescence. In addition to the above monomers, a monomer such as butadiene, α-methylstyrene, maleic anhydride can also be added and polymerized, and heat resistance, fluidity and impact resistance can be adjusted depending on the amount and molecular weight of the monomer.

<Polyester>
Polyester is a resin having an ester bond in the main chain of the molecule, and is a polycondensate synthesized from dicarboxylic acid (including its derivative) and diol (dihydric alcohol or dihydric phenol); dicarboxylic acid (its derivative) And a cyclic ether compound; and a ring-opening polymerization product of the cyclic ether compound. Examples of the polyester include a homopolymer of a polymer of a dicarboxylic acid and a diol, a copolymer using a plurality of raw materials, and a polymer blend obtained by mixing these. The dicarboxylic acid derivative is an acid anhydride or an esterified product. As for the dicarboxylic acid, where there are two kinds of dicarboxylic acids, aliphatic and aromatic, aromatic is more preferable because heat resistance is improved.

Aromatic dicarboxylic acids are, for example, terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxylphenylacetic acid, m-phenylenediglygolic 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- Oxypentane-p,p'-dicarboxylic acid and the like can be mentioned.
Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, adipic acid, corkic acid, mazelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid and fumaric acid.

Examples of the dihydric alcohol include ethylene glycol, trimethylene glycol, butane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,4-diol and 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 preferable.
Examples of the dihydric phenol include hydroquinone, resorcinol, and bisphenol A.
Examples of the cyclic ether compound include ethylene oxide and propylene oxide.

<Cycloolefin resin>
The cycloolefin resin is a polymer of ethylene or α-olefin and a cyclic olefin. The α-olefin is a monomer derived from a C4 to C12 α olefin, and examples thereof include 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 -Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. The cyclic olefin is a monomer derived from norbornene, and examples thereof include a substituent of a hydrogen group, a halogen atom, a monovalent or divalent hydrocarbon group. Of these, unsubstituted norbornene is preferable.

The thermoplastic resins may be used alone or in combination of two or more.

(Method for producing molding composition)
In the method for producing the molding composition, for example, it is preferable to produce the ultraviolet absorbing material of the present invention as a masterbatch containing a high concentration. In the masterbatch, it is preferable that the ultraviolet absorbing material and the thermoplastic resin are melt-kneaded and then molded into an arbitrary shape. Then, the masterbatch and the dilute resin (thermoplastic resin) are melt-kneaded to form a molded product having a desired shape. In the ultraviolet absorbing material of the present invention, it is possible to disperse the ultraviolet absorbing material in a higher degree by once preparing the master batch and then forming the molded body, rather than preparing the molded body by melt-kneading the materials at once. it can.

Examples of the shape of the masterbatch include pellets, powders, and plates. For the melt-kneading, it is preferable to use, for example, a single-screw kneading extruder, a twin-screw kneading extruder, or a tandem twin-screw kneading extruder. The melt-kneading temperature varies depending on the type of thermoplastic resin, but is usually about 150 to 250°C.
Further, from the viewpoint of suppressing the aggregation of the ultraviolet absorbing material of the present invention, after preliminarily preparing a preliminary dispersion by melting and kneading the ultraviolet absorbing material and the wax, then, together with the thermoplastic resin, melt kneading for molding. It is preferred to make the composition. It should be noted that it is preferable to use, for example, a blend mixer or a three-roll mill to prepare the preliminary dispersion.

When producing the masterbatch, the amount of the ultraviolet absorbing material of the present invention used is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin. The mass ratio of the masterbatch and the diluted resin is preferably 1/5 to 1/100. When used in an appropriate ratio, the degree of coloring and mechanical strength of the molded product can be highly compatible. The diluting resin is not limited to the thermoplastic resin used for the masterbatch, and may be any thermoplastic resin having a good compatibility with the resin.

The molding composition using the ultraviolet absorbing material of the present invention may contain an antioxidant, a light stabilizer, a dispersant and the like as optional components other than the ultraviolet absorbing resin and the thermoplastic resin.

A molded product obtained by using the ultraviolet absorbing material of the present invention is produced by molding a molding composition. Examples of the molding method include extrusion molding, injection molding, blow molding and the like. Examples of the extrusion molding include compression molding, pipe extrusion molding, laminate molding, T-die molding, inflation molding, melt spinning and the like.

The thickness of the molded body is about 0.5 mm to 50 mm, although it depends on the application.

The molding temperature of the molded body depends on the type of thermoplastic resin, but is usually about 160 to 240°C.

0.1-20 mass% is preferable in a molded object, and, as for content of an ultraviolet absorbing material, 0.3-10 mass% is more preferable.

The molded product obtained by using the ultraviolet absorbing material of the present invention is produced by high-speed extrusion molding (molding machine screw rotation speed: about 150 rpm) having a faster molding speed than ordinary extrusion molding or compression molding having a long shear-free region. Even if you do, color unevenness and color separation are less likely to occur. In particular, even in high-speed compression molding (production speed of 500 pieces/minute or more, and in some cases 700 to 900 pieces/minute), which is about 10 times faster than injection molding, excellent effect that color unevenness and discoloration do not easily occur on the molded product. Is obtained.

Compression molding will be described as an example of the method for manufacturing the molded body of the present specification. First, a molding product including a step of melt-mixing the molding composition of the present invention, charging it into a compression molding machine, and applying a pushing force by compression without applying a shearing force in the compression molding machine, Is a manufacturing method. Here, when a pushing force by compression is applied without applying a shearing force, the molding composition exists in a state where no mixing force is applied to the molding composition, that is, in the shear-free region. The molded product is preferably a PET bottle plastic cap or the like. In this specification, a molded product is a product obtained by adding resin to a mold. Molded articles include articles obtained without using a mold, such as plastic films, and molded articles.

Molded articles obtained using the ultraviolet absorbing material of the present invention include, for example, medical agents, cosmetics, food containers and packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, It can be widely used for home appliances, building materials such as houses, toiletries, display materials, sensor materials, and optical control materials.

<Adhesive>
The adhesive of the present specification preferably contains an ultraviolet absorbing material, and more preferably contains an adhesive resin.
The adhesive resin is a resin having a glass transition temperature of about -60 to 0°C, more preferably -50 to -20°C. Examples of the adhesive resin include polyacryl, polyurethane, polysilicone, polyester, and rubber. Among these, polyacrylic which is inexpensive and has both adhesive strength and high transparency is preferable.
The adhesive resin is preferably used in combination with a curing agent, whereby both cohesive force and adhesive force can be achieved. Examples of the curing agent include an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, a metal chelate curing agent, and a carbodiimide curing agent.

The pressure-sensitive adhesive sheet of the present specification preferably includes a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive, and further preferably includes a base material. The base material is preferably paper or a plastic film. The base material can be appropriately selected and used from a base material having a release treatment and a base material having no release treatment. The pressure-sensitive adhesive layer can be formed using a known coating device. The thickness of the base material is usually about 1 to 500 μm. The thickness of the pressure-sensitive adhesive layer is usually about 1 to 500 μm.

Examples of applications of the pressure-sensitive adhesive sheet include label applications, window film applications, vehicle applications, and display applications. Among these, display applications are more preferable.
When the pressure-sensitive adhesive sheet is used for a display application, by containing the ultraviolet absorbing material of the present invention, it is possible to absorb light in the short wavelength region of ultraviolet light or visible light contained in the backlight, and suppress adverse effects on the eyes. Further, by absorbing light in the short wavelength region of ultraviolet rays or visible light contained in sunlight, deterioration of the display element of the display can be suppressed, and further deterioration of transparency due to migration over time can be suppressed. ..

<Photocurable composition>
In the photocurable composition of the present specification, the ultraviolet absorbing material preferably contains a photopolymerizable compound and a photopolymerizable initiator.
The content of the ultraviolet absorbing material is preferably 2 to 80% by mass in the photocurable composition.

The photopolymerizable compound is a known monomer or oligomer, is a compound having one or more ethylenically unsaturated groups (for example, a (meth)acryloyl group), and is preferably a compound having two or more. The content of the photopolymerizable compound is preferably 10 to 70% by mass in the photocurable composition.
The photopolymerizable initiator is a known compound. The content of the photopolymerizable compound is preferably 0.1 to 20% by mass in the photocurable composition.

The cured film of the present specification preferably includes a film formed from the photocurable composition. The cured film is a film that is cured by irradiating the photocurable composition with light (for example, ultraviolet rays). The cured film is preferably used as a hard coat, for example.
Examples of applications of the cured film include glass applications, in-vehicle applications, eyeglass lens applications, and display applications. By containing the ultraviolet absorbing material of the present specification in the cured film for display use, it is possible to absorb light in the short wavelength region of ultraviolet light or visible light contained in the backlight, and suppress adverse effects on the eyes. Further, by absorbing light in the short wavelength region of ultraviolet rays or visible light contained in sunlight, deterioration of the display element of the display can be suppressed, and further deterioration of transparency due to migration over time can be suppressed.

Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the examples. Unless otherwise specified, "parts by mass" will be referred to as "parts" and "% by mass" will be simply referred to as "%".

<Anionic dye (A)>
The compounds shown in (A-11), (A-22) to (A-23), and (A-31) to (A-33) as exemplified above were used.

<Production Example of Resin (B)>
(Resin (B-1) having a cationic group in its side chain)
100.0 parts of isopropyl alcohol was charged into a 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 60.0 parts of methyl methacrylate (MMA), 25.0 parts of butyl acrylate (BA), 15.0 parts of dimethylaminoethyl methacrylate methyl chloride salt (DMCMA), and 2.2′-azobis(methyl isobutyrate) were added. After uniformly mixing 10.0 parts and 40.0 parts of isopropyl alcohol, the mixture was placed in a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of dropping, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50°C. Thus, a resin (B-1) having a cationic group in the side chain having a nonvolatile content of 40% was obtained. The ammonium salt value of the obtained resin was 41 mgKOH/g.

(Resin (B-2) to (B-5), (B-7) having a cationic group in the side chain))
As shown in Table 1, in the same manner as the resin (B-1) having a cationic group in the side chain, the resins (B-2) to (B-5) and (B- 7) was produced. In Table 1, DCPMA is dicyclopentanyl methacrylate and St is styrene.

(Resin having cationic group in side chain (B-6))
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 100.0 parts of methoxypropyl acetate and heated to 75° C. under a nitrogen stream. Separately, 45.0 parts of methyl methacrylate, 25.0 parts of butyl acrylate, 15.0 parts of 2-hydroxyethyl methacrylate (HEMA), 15.0 parts of 2-(dimethylamino)methacrylate (DM) and 2.2'- After uniformly mixing 10.0 parts of azobis(methyl isobutyrate) and 40.0 parts of methoxypropyl acetate, the mixture was placed in a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of dropping, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50°C.
Next, 11.7 parts of propyl bromide (BP) was added and reacted at 100° C. for 4 hours. After confirming that the amine value was 2 or less, the mixture was cooled to 50°C.
Further, 17.9 parts of 2-methacryloyloxyethyl isocyanate (MOI) was added in the atmosphere of air, and 0.05 part of methylhydroquinone was further added as a polymerization inhibitor, and the reaction was carried out at 80° C. for 4 hours. After confirming that the isocyanate equivalent was 1 or less, the reaction was terminated.
Further, methoxypropyl acetate was added to adjust the nonvolatile content to 40% to obtain a resin (B-6) having a cationic group in the side chain. The ammonium salt value of the obtained resin was 41 mgKOH/g.

<Resin having cationic group in side chain (B-8)>
A 4-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser was charged with 15.4 parts of isopropyl alcohol, and 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentane was added under a nitrogen stream. 1.0 part of methyl acid and 50.0 parts of dimethylaminoethyl methacrylate methyl chloride salt were charged and the temperature was raised to 75° C. under a nitrogen stream. Then, 0.12 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) and 10.0 parts of isopropyl alcohol were added dropwise over 8 hours to synthesize an A block. Then, 25.0 parts of styrene, 25.0 parts of dicyclopentanyl methacrylate (DCPMA), and 104.0 parts of isopropyl alcohol were charged, and 2,2′-azobis(2,4-dimethylvaleronitrile) was added to 0. 12 parts and 10.0 parts of isopropyl alcohol were added dropwise over 8 hours to synthesize B block. After the dropping was completed, the reaction was continued for 24 hours. After that, sampling was performed, and it was confirmed that the polymerization yield was 99% or more, and a resin solution b-8 was obtained. The resin solution b-8 was dried at 50° C. for 12 hours with a vacuum dryer to obtain an AB block polymer (B-8).

(Resin having cationic group in side chain (B-9))
In a 4-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser, 21.6 parts of isopropyl alcohol, 3.5 parts of bis(dodecylsulfanylthiocarbonyl)disulfide, 2,2'-azobis(2 , 4-dimethylvaleronitrile) was charged to the reaction system, and the temperature was raised to 70° C. under a nitrogen stream and the reaction was carried out for 2 hours. 50.0 parts of methacrylic acid dimethylaminoethylmethyl chloride salt was charged therein, and the temperature was raised to 75° C. under a nitrogen stream. Then, 0.31 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) and 10.0 parts of isopropyl alcohol were added dropwise over 8 hours to synthesize an A block. Thereafter, 35.0 parts of methyl methacrylate (MMA), 15.0 parts of butyl acrylate (BA) and 34.2 parts of isopropyl alcohol were charged, and 2,2′-azobis(2,4-dimethylvaleronitrile) was added to 0. .31 parts and 10.0 parts of isopropyl alcohol were added dropwise over 8 hours to synthesize a B block. After the dropping was completed, the reaction was continued for 24 hours. After that, sampling was performed, and it was confirmed that the polymerization yield was 99% or more, and a resin solution b-9 was obtained. The resin solution b-9 was dried in a vacuum dryer at 50° C. for 12 hours to obtain an AB block polymer (B-9).

<Production Example of Comparative Ultraviolet Absorbing Material (RR-1)>
100.0 parts of isopropyl alcohol was charged into a 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 60.0 parts of methyl methacrylate, 25.0 parts of butyl acrylate, 15.0 parts of RUVA-93 (manufactured by Otsuka Chemical, methacrylic monomer having a benzotriazole group), and 10 parts of 2.2'-azobis(methyl isobutyrate). After uniformly mixing 0.0 parts and 40.0 parts of isopropyl alcohol, the mixture was charged into a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of dropping, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50°C. Thus, a comparative ultraviolet absorbing material (RR-1) was obtained.

Table 1 shows the monomers used for the synthesis of the resin (B) having a cationic group in the side chain.

<Manufacture of UV absorbing material>
(Ultraviolet absorbing material (R-1))
An ultraviolet absorbing material (R-1) comprising Acid Yellow 3 and a resin (B-1) having a cationic group in its side chain was produced by the following procedure.
10 parts of Acid Yellow 3 was added to 2000 parts of water and 400 parts of N-methylpyrrolidone, and they were sufficiently stirred and mixed. On the other hand, 2000 parts of water and 400 parts of N-methylpyrrolidone were mixed with 72.3 parts of the resin (B-1) having a cationic group in the side chain to obtain a cloudy solution. This solution was dropped little by little into the previously prepared aqueous solution containing Acid Yellow 3. After completion of the dropping, the reaction was carried out with sufficient stirring. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution onto a filter paper and deciding the end point when the bleeding disappeared. Then, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a drier to obtain Acid Yellow 3 and a resin (B-1) having a cationic group in a side chain. Thus, 80.0 parts of an ultraviolet absorbing material (R-1) which is a salt-forming product of

(Ultraviolet absorbing materials (R-2) to (R-18))
As shown in Table 2, ultraviolet absorbing materials (R-2) to (R-18) were produced in the same manner as the ultraviolet absorbing material (R-1).

<Absorbance measurement>
(Ultraviolet absorbing material (R-1))
A 10 ppm N-methylpyrrolidone solution of Acid Yellow 3 and the ultraviolet absorbing material (R-1) was prepared, and the absorbance at the maximum absorption wavelength was measured.
The maximum absorption wavelength of Acid Yellow 3 was 423 nm, the absorbance at this wavelength was 0.97, the maximum absorption wavelength of the ultraviolet absorbing material (R-1) was 418 nm, and the absorbance at this wavelength was 0.25. Since Acid Yellow 3 has a molecular weight of 477 and the total molecular weight of the counter cation is 23, the ratio of structural sites derived from the anionic dye (A) in the ultraviolet absorbing material was 25.7%.

(Ultraviolet absorbing materials (R-2) to (R-18))
The absorbance is measured in the same manner as the absorbance measurement of the ultraviolet absorbing material (R-1), and the ratio of the sites derived from the anionic dye (A) in the ultraviolet absorbing materials (R-2) to (R-18) is determined. It was calculated. This is shown in Table 2.

<Molding composition>
The thermoplastic resins used in the examples are shown below.
(C-1) Polyethylene (Suntech LDM2270, MFR=7g/10min, manufactured by Asahi Kasei Chemicals Corporation)
(C-2) Polyethylene (Novatech UJ790, MFR=50g/10min, manufactured by Nippon Polyethylene Co., Ltd.)
(C-3) Polypropylene (Novatech PPFA3EB, MFR=10.5g/10min, manufactured by Nippon Polypro)
(C-4) Polypropylene (Prime Polypro J226T, MFR=20G/10MIN, manufactured by Prime Polymer Co., Ltd.)
(C-5) Polycarbonate (Iupilon S3000, MFR=15g/10min, manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
(C-6) Polyacrylic (Acrypet MF, MFR=14 g/10 min, manufactured by Mitsubishi Rayon Co., Ltd.)
(C-7) Polyester (Mitsui Pet SA135, manufactured by Mitsui Chemicals, Inc.)
(C-8) cycloolefin resin (TOPAS5013L-10, manufactured by Mitsui Chemicals, Inc.)

The waxes used in the examples are shown below.
(D-1) Polyethylene wax (Sun wax 131-P, number average molecular weight 3500, melting point 105° C., manufactured by Sanyo Chemical Industries)
(D-2) Polyethylene wax (high wax 405MP, number average molecular weight 4500, melting point 120°C, manufactured by Mitsui Chemicals, Inc.)
(D-3) Polypropylene wax (high wax NP056, number average molecular weight 7200, melting point 130° C., manufactured by Mitsui Chemicals, Inc.)

(Example 1)
(Manufacture of masterbatch)
20 parts of the ultraviolet absorbing material (R-1) was mixed with 100 parts of the wax (D-1), and the mixture was heated and kneaded at 160° C. with a three-roll mill to obtain a dispersion of the ultraviolet absorbing material (R-1). Obtained. Then, 10 parts of the obtained dispersion was mixed with 100 parts of polyolefin (C-1) by a Henschel mixer, melt-kneaded at 180° C. by a single-screw extruder having a screw diameter of 30 mm, and a pelletizer was used. A pelletizing composition was cut to prepare a molding composition (masterbatch).
(Film forming)
10 parts of the obtained molding composition was mixed with 100 parts of the diluted resin polyolefin (C-1), and melt-mixed at a temperature of 180° C. using a T-die molding machine (manufactured by Toyo Seiki), A film having a thickness of 250 μm was formed.

(Examples 2 to 19, Comparative Examples 1 to 5)
Examples 2 to 19 and Comparative Examples 1 to 5 were performed in the same manner as in Example 1 except that the materials of Example 1 were changed as described in Table 3, to prepare masterbatches, and then to form films. Was produced.

(Examples 20 to 22, Comparative Examples 6 to 9)
(Manufacture of masterbatch)
100 parts of the thermoplastic resin (C-5) and 2 parts of the ultraviolet absorbing material shown in Table 4 were charged into the twin-screw extruder (manufactured by Japan Steel Works Ltd.) having a screw diameter of 30 mm from the same supply port, and melted at 280°C. After kneading, it was cut into pellets using a pelletizer to prepare a molding composition (masterbatch).
(Film forming)
10 parts of the obtained molding composition was mixed with 100 parts of the diluted resin thermoplastic resin (C-5), and melt-mixed at a temperature of 280° C. using a T-die molding machine (manufactured by Toyo Seiki). Then, a film having a thickness of 250 μm was formed.

(Examples 23 to 25, Comparative example 10)
(Manufacture of masterbatch)
100 parts of the thermoplastic resin (C-6) and 2 parts of the ultraviolet absorbing material shown in Table 4 were charged into the twin screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw diameter of 30 mm from the same supply port, and melted at 240°C. After kneading, it was cut into pellets using a pelletizer to prepare a molding composition (masterbatch).
(Film forming)
10 parts of the obtained molding composition was mixed with 100 parts of the diluted resin thermoplastic resin (C-6), and melt-mixed at a temperature of 280° C. using a T-die molding machine (manufactured by Toyo Seiki). Then, a film having a thickness of 250 μm was formed.

(Examples 26 to 28, Comparative Example 11)
(Manufacture of masterbatch)
100 parts of the thermoplastic resin (C-7) and 2 parts of the ultraviolet absorbing material shown in Table 4 were charged into the twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw diameter of 30 mm from the same supply port and melted at 280°C. After kneading, it was cut into pellets using a pelletizer to prepare a molding composition (masterbatch).
(Film forming)
10 parts of the obtained molding composition was mixed with 100 parts of the diluted resin thermoplastic resin (C-7), and melt-mixed at a temperature of 280° C. using a T-die molding machine (manufactured by Toyo Seiki). Then, a film having a thickness of 250 μm was formed.

(Examples 29 to 33, Comparative Example 12)
(Manufacture of masterbatch)
100 parts of the thermoplastic resin (C-8) and 2 parts of the ultraviolet absorbing material shown in Table 4 were charged from the same supply port into a twin-screw extruder (manufactured by Japan Steel Works Ltd.) having a screw diameter of 30 mm and melted at 240°C. After kneading, it was cut into pellets using a pelletizer to prepare a molding composition (masterbatch).
(Film forming)
10 parts of the obtained molding composition was mixed with 100 parts of the thermoplastic resin (C-8) as a diluted resin, and melt-mixed at a temperature of 280° C. using a T-die molding machine (manufactured by Toyo Seiki). Then, a film having a thickness of 250 μm was formed.

The obtained film was evaluated as follows.

[optical properties]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). As the transmittance, the spectral transmittance with respect to a white standard plate was measured.
It was evaluated whether the following conditions were satisfied.
◯: Light transmittance in the wavelength range of 380 to 420 nm is 2% or less over all areas: Good Δ: Light transmittance in the wavelength of 380 to 420 nm exceeds 2% in part and 10% or less: Practical range ×: Light in wavelength of 380 to 420 nm Transmittance is 10% or more in part or more than 2% in all areas: not practical

[Transparency evaluation]
The transparency of the obtained film was visually evaluated.
○: No turbidity is observed. Good Δ: Some turbidity is observed. Practical range x: Many turbidity is observed. Impractical

[Migration evaluation]
The obtained film was sandwiched between two soft vinyl chloride sheets, and thermocompression-bonded using a heat press machine under the conditions of a pressure of 100 g/cm ² and a temperature of 170° C. for 30 seconds. Then, 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 carried out by selecting 5 points on the soft vinyl chloride sheet that had been subjected to the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
◯: Absorbance at 280 to 400 nm is not detected (0.05 or less). Good Δ: Absorbance at 280 to 400 nm is more than 0.05 and 0.2 or less. Practical range x: Absorbance at 280 to 400 nm is higher than 0.2. Impractical

[Evaluation of extractability]
The obtained film was cut into 2×2 cm, put in 50 g of ion-exchanged water, extracted at 80° C. for 24 hours, and then the absorbance of the ion-exchanged water was measured and evaluated according to the following criteria. It should be noted that elution into ion-exchanged water can be suppressed in the sample having no absorbance.
◯: No absorbance. Good Δ: Absorbance is 0.2 or less. Practical range x: Absorbance above 0.2. Impractical

<Paint>
(Example 34)
The following materials were stirred and mixed to prepare a paint.
Ultraviolet absorbing material (R-1) 1.0 part Polyester (Vylon GK250, Toyobo Co., Ltd.) 9.0 parts Methyl ethyl ketone 90.0 parts

(Examples 35 to 41, Comparative Examples 13 to 15)
As shown in Table 5, the same adjustment as in Example 34 was performed.

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

[optical properties]
The transmittance of the obtained coating material was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). As the transmittance, the spectral transmittance with respect to a white standard plate was measured.
It was evaluated whether the following conditions were satisfied.
◯: Light transmittance in the wavelength range of 380 to 420 nm is 2% or less over all areas: Good Δ: Light transmittance in the wavelength of 380 to 420 nm exceeds 2% in part and 10% or less: Practical range ×: Light in wavelength of 380 to 420 nm Transmittance is 10% or more in part or more than 2% in all areas: not practical

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

[Migration evaluation]
One soft vinyl chloride sheet was placed on the coating surface of the obtained substrate, and thermocompression bonding was performed using a heat press machine under the conditions of a pressure of 100 g/cm ² and a temperature of 170° C. for 30 seconds. Then, 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 carried out by selecting 5 points on the soft vinyl chloride sheet that had been subjected to the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
◯: Absorbance at 280 to 400 nm is not detected (0.05 or less). Good Δ: Absorbance at 280 to 400 nm is more than 0.05 and 0.2 or less. Practical range x: Absorbance at 280 to 400 nm is higher than 0.2. Impractical

<Adhesive>
(Production Example of Adhesive Resin E-1)
Using a reactor equipped with a stirrer, a reflux condenser, a nitrogen introducing pipe, a thermometer, and a dropping pipe, 96.0 parts of n-butyl acrylate and 4.0 parts of 2-hydroxyl ethyl acrylate were prepared under a nitrogen atmosphere. 50% of the total amount, 0.22 parts of 2,2′-azobisisobutylnitrile as a polymerization initiator and 150 parts of ethyl acetate as a solvent were charged in a reaction tank, and the remaining 50% of the total amount was added. An appropriate amount of ethyl acetate was placed in the dropping tank. Then, after heating is started to confirm the start of the reaction in the reaction tank, the contents of the dropping tube and 0.01 part of a 2,2′-azobisisobutylnitrile diluted with ethyl acetate are refluxed. It dripped over 1 hour. After completion of the dropping, the reaction was carried out for 5 hours while maintaining the reflux state. After completion of the reaction, the mixture was cooled and an appropriate amount of ethyl acetate was added to obtain a tacky resin E-1 which was polyacrylic. The obtained adhesive resin E-1 had a weight average molecular weight of 500,000, a nonvolatile content of 40%, and a viscosity of 3,200 mPa·s.

(Production Example of Adhesive Resin E-2)
Using a reactor equipped with a stirrer, a reflux condenser, a nitrogen introducing pipe, a thermometer, and a dropping pipe, 96.0 parts of n-butyl acrylate and 4.0 parts of acrylic acid were added under a nitrogen atmosphere. 50% of the above, 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 total amount and an appropriate amount of ethyl acetate were charged. Was charged into the dropping tank. Then, after heating is started to confirm the start of the reaction in the reaction tank, the contents of the dropping tube and 0.01 part of a 2,2′-azobisisobutylnitrile diluted with ethyl acetate are refluxed. It dripped over 1 hour. After completion of the dropping, the reaction was carried out for 5 hours while maintaining the reflux state. After completion of the reaction, the mixture was cooled and an appropriate amount of ethyl acetate was added to obtain a polyacrylic adhesive resin E-2. The obtained adhesive resin E-2 had a weight average molecular weight of 600,000, a nonvolatile content of 40%, and a viscosity of 4,000 mPa·s.

(Example 42)
As the adhesive resin, 2 parts of the ultraviolet absorbing material (R-2) was mixed with 100 parts of the nonvolatile content of the adhesive resin of Production Example E-1, and KBM-403 (Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. 0.1 part), and 0.4 part of a trimethylolpropane adduct of tolylene diisocyanate (abbreviation: TDI-TMP, NCO value=13.2, nonvolatile content=75%) as a curing agent (D), After thorough stirring, an adhesive was obtained. Then, this adhesive was applied onto a release film of a polyethylene terephthalate substrate having a thickness of 38 μm so that the thickness after drying would be 50 μm, and dried in a hot air oven at 100° C. for 2 minutes. Then, a 25 μm polyethylene terephthalate film was attached to the pressure-sensitive adhesive layer side, and in this state, it was aged at room temperature for 7 days to obtain a pressure-sensitive adhesive sheet.

(Examples 43 to 46, Comparative Examples 16 to 17)
As shown in Table 6, it adjusted like Example 42.

(Evaluation of adhesive sheet)
[optical properties]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). As the transmittance, the spectral transmittance with respect to a white standard plate was measured. The evaluation criteria are as follows.
◯: Light transmittance in the wavelength range of 380 to 420 nm is 2% or less in all areas: Good Δ: Light transmittance in the wavelength of 380 to 420 nm exceeds 2% and 10% or less: Practical range ×: Light transmittance in the wavelength of 380 to 420 nm Is over 10% in part or over 2% over the whole area: not practical

[Adhesive force]
The obtained pressure-sensitive adhesive sheet was prepared in a size of 25 mm in width and 150 mm in length. The peelable film was peeled from the pressure-sensitive adhesive sheet in an atmosphere of 23° C. and a relative humidity of 50%, and the exposed pressure-sensitive adhesive layer was attached to a glass plate and pressure-bonded back and forth once with a 2 kg roll. The adhesive strength was measured by a 180° peel test in which the film was left for 24 hours and then peeled off in a 180° direction at a speed of 300 mm/min using a tensile tester. The evaluation criteria are as follows. (Based on JISZ0237:2000)
A: "Adhesive strength is 15N or more"
B: "Adhesive strength is 10 N or more and less than 15 N"
C: "Adhesive strength is less than 10N"

[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, a peelable sheet is peeled from the pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive layer is adhered to a 25 mm wide/25 mm wide lower end portion of a polished stainless steel plate having a width of 30 mm and a length of 150 mm, and a 2 kg roll. Then, the holding force was measured by applying a load of 1 kg in a 40° C. atmosphere and leaving it for 70,000 seconds. The evaluation was performed by measuring the length in which the upper end of the surface on which the pressure-sensitive adhesive sheet was attached was displaced downward. The evaluation criteria are as follows.
A: "The displaced length is less than 0.5 mm"
B: "The displaced length is 0.5 mm or more"

[transparency]
The release sheet was peeled off from the obtained pressure-sensitive adhesive sheet, and the transparency of the pressure-sensitive adhesive layer was visually evaluated. The evaluation criteria are as follows.
○: "The adhesive layer is transparent and has no practical problem"
Δ: “The adhesive layer is slightly whitened, which is a problem in practical use”
X: "Adhesive layer is whitened and is not practical"

[Migration evaluation]
The obtained pressure-sensitive adhesive sheet was prepared in a size of width 100 mm and length 100 mm. The peelable film was peeled from the pressure-sensitive adhesive sheet in an atmosphere of 23° C. and a relative humidity of 50%, and the exposed pressure-sensitive adhesive layer was attached to a glass plate and pressure-bonded back and forth once with a 2 kg roll. Then, it was left in the same environment for 48 hours, then the adhesive sheet was peeled off, and the migration property of the ultraviolet absorbing material to glass was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation was performed by selecting five points on the glass that had been subjected to the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof. The price standard is as follows.
◯: Absorbance at 280 to 400 nm is not detected (0.05 or less). Good Δ: Absorbance at 280 to 400 nm is more than 0.05 and 0.2 or less. Practical range x: Absorbance at 280 to 400 nm is higher than 0.2. Impractical

<Photocurable composition>
(Example 47)
With the following composition, each raw material was mixed and stirred to prepare a photocurable composition.
Ultraviolet absorbing material (R-2) 10.0 parts Photopolymerizable compound (polyfunctional acrylate "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)
9.0 parts photopolymerization initiator (IGM Resin BV "Omnirad 184") 1.0 part
Propylene glycol monomethyl ether 80.0 parts

(Examples 48 to 51, Comparative Examples 18 to 19)
As shown in Table 7, it adjusted like Example 47.

(Preparation of coating)
The above photocurable composition was applied to a glass substrate having a thickness of 1 mm using a bar coater so that the dry film thickness would be 6 μm. The obtained coating layer was dried at 100° C. for 1 minute and then irradiated with ultraviolet rays of 400 mJ/cm ² with a high pressure mercury lamp to form a cured film.
(Evaluation of coated products)
The obtained coated product was evaluated by the following methods.

[optical properties]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). For the transmittance, the spectral transmittance was measured with respect to a white standard plate.
It was evaluated whether the following conditions were satisfied.
◯: Light transmittance in the wavelength range of 380 to 420 nm is 2% or less in all areas: Good Δ: Light transmittance in the wavelength of 380 to 420 nm exceeds 2% and 10% or less: Practical range ×: Light transmittance in the wavelength of 380 to 420 nm Is over 10% in part or over 2% over the whole area: not practical

[Scratch resistance]
The cured film was set in a scholarship tester, and steel wool was shaken 10 times under a load of 250 g. With respect to the taken out coating, the degree of scratches was judged according to the following five-level visual evaluation. The larger the value, the better the scratch resistance of the cured film.
5: There are no scratches.
4: Slightly scratched.
3: There are scratches, but the base material is not visible.
2: Scratched and partially cured film peeled off.
1: The state where the cured film is peeled off and the base material is exposed.

[Pencil hardness]
Based on JIS-K5600, a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON) was used, and the hardness of the core of the pencil was variously changed, and a test was conducted 5 times under a load of 500 g. The pencil hardness of the cured film was defined as the hardness of the core when scratches were not made even once in five times, or when scratches were made only once. The evaluation criteria are as follows.
A: 2H or more.
B: H.
C: Lower than H.

[transparency]
The transparency of the obtained coating product was visually evaluated.
○: No turbidity is observed. Good Δ: Slight turbidity is observed. Practical range x: Many turbidity is observed. Impractical

[Migration evaluation]
The obtained coated product was sandwiched between two soft vinyl chloride sheets, and thermocompression bonded under the conditions of a pressure of 100 g/cm ² and a temperature of 170° C. for 30 seconds using a hot press machine. Then, 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 carried out by selecting 5 points on the soft vinyl chloride sheet that had been subjected to the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
◯: Absorbance at 280 to 400 nm is not detected (0.05 or less). Good Δ: Absorbance at 280 to 400 nm is 0.05 to 0.2 or less. Practical range x: Absorbance at 280 to 400 nm is higher than 0.2. Impractical

From the results of Tables 3 to 7, it is understood that the ultraviolet absorbing material of the present invention can suppress the migration of the ultraviolet absorbent and the migration of the colorant at the same time as suppressing the migration of the ultraviolet absorbent and the visible light in the short wavelength region. .. The ultraviolet absorbing material of the present invention can be used without limitation in applications requiring the solution of the above problems, including coatings, compositions for moldings, adhesives, and photocurable compositions.

Claims (10)

Salt formation was der the following general formula (1) to (3) an anionic dye represented by either (A) a resin having a cationic group in the side chain (B) is,
The resin (B) having a cationic group in its side chain has a unit represented by the following general formula (4) and is selected from the group consisting of (meth)acrylic acid ester, a styrene compound, and a hydroxyl group-containing monomer. Which is a resin obtained by copolymerizing one or more of the following monomers, and contains 4 to 74% by mass of the unit represented by the general formula (4) in 100% by mass of the monomer unit constituting the resin (B):
The ultraviolet absorbing material in which the portion derived from the anionic dye (A) is 3.7 to 56.2 mass% of the entire salt-forming product .
General formula (1) General formula (2)
(In the general formula _{(1), R} 61 ~R ₇₁ is 1 to 3 is ^X - is ^{Y +,} others are each water atom, X ^- is SO ₃ ^- represents, ^{Y +} is , Represents an inorganic or organic cation.
In the general formula _{(2), R 29} is an alkyl group having 1 to 20 carbon _{atoms, R 30} is a hydroxyl _group, R 21 _{to R 28,} and _R 31 _{to R 35} ^{is X} - 1 pieces of ^{Y +} Except for X ⁻ Y ⁺ , they are each independently a hydrogen atom or a methyl group, X ⁻ represents SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation.
In the general formula _{(3), R 46} is an alkyl group having 1 to 20 carbon _atoms, R 41 _{to R 45,} and _R 47 _{to R 51} ^{is X} - ^{Y +} a has ^{1, X} - ^{Y +} With the exception of each independently a hydrogen atom or a methyl group, X ⁻ represents SO ₃ ⁻ , and Y ⁺ represents an inorganic or organic cation. )
General formula (4)

(In the general formula (4), _{R 1} is, _.R 2 to R ₄ represents a hydrogen atom or a methyl group, each independently represent a methyl group or an ethyl group, Q is, _{-COO-R 5} - and represents, .P _{R 5} is representative of the ethylene group ^- represents an inorganic anion). Site derived from anionic dye (A) is 5 to 50% by weight of the total salt formation was UV-absorbing material of claim 1 Symbol placement. Paint containing the ultraviolet absorbing material according to claim 1 or 2. A molding composition comprising the ultraviolet absorbing material according to claim 1 or 2 and a thermoplastic resin. Adhesive containing an ultraviolet absorbing material according to claim 1 or 2. A photocurable composition comprising the ultraviolet absorbing material according to claim 1 or 2 , a photopolymerizable compound, and a photopolymerizable initiator. A coated article comprising a coating film formed from the coating material according to claim 3 . A molded article comprising the molding composition according to claim 4 . A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive according to claim 5 . A cured film comprising a film formed from the photocurable composition according to claim 6 .