JP2006002069A - Merocyanine dye copolymer and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having high sensitivity and excellent in stability by providing a new light-absorbing organic compound having broad absorption wavelength in a visible area and excellent in solubility to organic solvents and compatibility with other formulation components. <P>SOLUTION: A merocyanine dye copolymer has specific structure and properties and comprises a unit containing a merocyanine dye skeleton in the molecule and a unit composed of other monomer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a novel merocyanine dye copolymer and a photopolymerizable composition comprising the same.

With the advent of the information era, photochemical polymerization has been frequently used in a wide variety of fields. Now, its application goes beyond the field of synthetic resins to paints, printing plates, printed circuits, and integration. It has reached the field of information recording and electronic equipment such as circuits. Photochemical polymerization is a technique for polymerizing a polymerizable composition by irradiating with light. Broadly speaking, direct photopolymerization that initiates polymerization by directly irradiating and activating the polymerizable composition is called photopolymerization. There is photosensitization polymerization in which light is irradiated in the presence of a photosensitizer and the polymerizable composition is polymerized by utilizing active species of the photosensitizer. In any photochemical polymerization, the start and stop of the polymerization can be controlled by blinking of the exposure light source, and the degree of polymerization and the polymerization rate can be easily controlled by selecting the intensity and wavelength of the exposure light source. is doing. Moreover, the photochemical polymerization is generally low in polymerization initiation energy, and thus can be initiated even at a low temperature. In the field of information recording such as holograms and printing plates, such advantages of photochemical polymerization have been purchased, and visible light such as second harmonics of argon laser, helium neon laser, and Nd-YAG laser. The demand for photopolymerizable compositions that can be polymerized by irradiating is rapidly increasing.

Many of the polymerizable compounds and polymerization initiators to be blended in the photopolymerizable composition absorb only ultraviolet rays. Therefore, when the photopolymerizable composition is polymerized with visible light, it is a photointensifier that absorbs visible light. Sensitizer is an indispensable technical element. The characteristics of the light-absorbing organic compound that is the main component of the photosensitizer are as follows: a broad absorption wavelength region in the visible region, a large molecular extinction coefficient, a solubility between the solvent and other ingredients. Examples thereof include excellent solubility, excellent decoloring properties, and excellent stability.

Typical examples of the light-absorbing organic compound include merocyanine dyes, cyanine dyes, and styryl dyes (see Patent Documents 1 to 3). However, all of these have a narrow absorption wavelength region in the visible region. However, it is still insufficient in terms of photosensitive characteristics. Moreover, what expanded the absorption wavelength range by polymerizing a light-absorbing organic compound is described (refer patent documents 4 and 5). However, since these light-absorbing organic compounds are poor in solubility in a solvent and compatibility with other compounding components such as a polymerizable compound and a binder resin when preparing a photopolymerizable composition, etc. Further improvements are necessary in terms of characteristics.

Therefore, in a new application field of photochemical polymerization, for example, in the field of information recording and electronic equipment, a combination of materials other than a photosensitizer such as a polymerizable compound, a polymerization initiator, and a binder resin depending on the application. In the actual situation, the first is determined, and then, a variety of light-absorbing organic compounds are searched by trial and error for those that are suitable for those polymerizable compounds and polymerization initiators. Recently, as the use of photochemical polymerization has expanded, an organic compound having a wide absorption wavelength region in the visible region and excellent compatibility with other compounding components has been demanded.

JP-A-54-151024 Japanese Patent Laid-Open No. 58-29803 JP 59-56403 A JP 60-79014 A Japanese Patent Laid-Open No. 4-86653

In view of such a situation, the present invention has a high sensitivity by providing a novel light-absorbing organic compound having a wide absorption wavelength region in the visible region and excellent solubility in an organic solvent and compatibility with other compounding components. It is an object of the present invention to provide a photopolymerizable composition having excellent stability.

In order to solve this problem, the present inventor paid attention to the merocyanine dye copolymer, and intensively studied and searched. As a result, the structural unit represented by the general formula 1 and the structural unit represented by the general formula 2 were obtained. The included merocyanine dye copolymer has a significantly broad absorption wavelength region in the visible region, so that it can efficiently absorb visible light in the vicinity of 500 nm, which is widely used for photochemical polymerization, etc. It has been found that the color is excellent, and further, the solubility in an organic solvent and the compatibility with other components are excellent.

General formula 1:

(In General Formula 1, G ¹ represents a hydrogen atom or an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group may have a substituent. G ² represents an oxygen atom or a nitrogen atom, and nitrogen A hydrogen atom is bonded to the atom, L represents a linking group, and M represents a merocyanine dye.)

General formula 2:

(In General Formula 2, G ³ represents a hydrogen atom or an aliphatic hydrocarbon group, and G ⁴ represents a hydroxyl group or a linear or branched aliphatic hydrocarbon group, aromatic hydrocarbon group, ether group or amino group. To express.)

That is, this invention is a novel light-absorbing organic compound having a broad absorption wavelength region in the visible region, excellent solubility in organic solvents and compatibility with other compounding components, The above-mentioned problems are solved by providing a merocyanine dye copolymer comprising a structural unit represented by the general formula 2.

General formula 1:

(In General Formula 1, G ¹ represents a hydrogen atom or an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group may have a substituent. G ² represents an oxygen atom or a nitrogen atom, and nitrogen A hydrogen atom is bonded to the atom, L represents a linking group, and M represents a merocyanine dye.)

General formula 2:

(In General Formula 2, G ³ represents a hydrogen atom or an aliphatic hydrocarbon group, and G ⁴ represents a hydroxyl group or a linear or branched aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group or amino group. To express.)

The merocyanine dye copolymer of the present invention has a significantly broad absorption wavelength region in the visible region, so that it can efficiently absorb visible light in the vicinity of 500 nm, which is widely used for photochemical polymerization, etc. A photopolymerizable composition having high sensitivity and excellent stability can be provided because it is excellent in color, and further has excellent solubility in an organic solvent and compatibility with other components.

As described above, the present invention relates to a merocyanine dye copolymer comprising a structural unit represented by general formula 1 and a structural unit represented by general formula 2.

General formula 1

General formula 2:

In General Formula 1, G ¹ represents a hydrogen atom or an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group in G ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, 1- Propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 2-pentenyl group, 2-pentene-4-ynyl group, 1-methylpentyl group, 2-methylpentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl Group, dodecyl group, undecyl group, octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, Examples include a hexyl group, a cyclohexenyl group, a cycloheptyl group, and the like.

G ² represents an oxygen atom or a nitrogen atom, and a hydrogen atom is bonded to the nitrogen atom. L represents a linking group. Examples of the linking group include an aliphatic hydrocarbon group such as a methylene group, an ethylene group, a vinylene group, a trimethylene group, a propylene group, a propenylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. , Cyclopentylene group, cyclohexenylene group, cyclohexadienylene group and other alicyclic hydrocarbon groups, o-phenylene group, m-phenylene group, p-phenylene group, naphthylene group and other aromatic hydrocarbon groups, Furthermore, those combinations are mentioned. Among these, the number of constituent atoms of the chain length of the linking group is preferably less than 10 constituent atoms such as carbon atoms, specifically 2 to 8. M represents a merocyanine dye.

In General Formula 2, G ³ represents a hydrogen atom or an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group in G ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, 1- Propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 2-pentenyl group, 2-pentene-4-ynyl group, 1-methylpentyl group, 2-methylpentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl Group, dodecyl group, undecyl group, octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, Rohekishiru group, cyclohexenyl group, cycloheptyl groups.

G ⁴ represents a hydroxyl group or a linear or branched aliphatic hydrocarbon group, aromatic hydrocarbon group, ether group or amino group. Examples of the aliphatic hydrocarbon group in G ⁴ include a methyl group, ethyl group, and the like. Group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 2-pentenyl group, 2-penten-4-ynyl group, 1-methylpentyl group, 2-methylpentyl group, hexyl group, Isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, dodecyl group, 2-methylbutyl group, 3-methyl Til, 2-ethylbutyl, 1,3-dimethylbutyl, 2-ethylhexyl, 2-methylpentyl, cyclohexyl, adamantyl, isobornyl, dicyclopentanyl, tetrahydrofurfuryl, 2- Hydroxypropyl group, trimethylolpropyl group and the like, and aromatic hydrocarbon group includes phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, Examples include m-cumenyl group, p-cumenyl group, biphenylyl group, etc. As ether group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group , Pentyloxy group, phenoxy group, benzyloxy group, methylenedioxy group, ethyl Rangeoxy group, 3-hydroxy-2,2-bis (hydroxymethyl) propoxy group, 6-hydroxyhexanoxy group, 3-hydroxypropoxy group, 2,4-dihydroxybutoxy group, 4-hydroxycyclohexanoxy group, 5-hydroxypentoxy group, 4-butoxycarbonylphenoxy group, 4-tert-butylphenoxy group, benzyloxy group, 2- (4-phenyl) ethoxy group, 4-phenylylphenoxy group, ferrocenylmethoxy group, 2- Examples include ferrocenylethoxy group, trifluoroethoxy group, tetrafluoropropoxy group, octafluoropentoxy group, 2,3-dibromopropoxy group, trimethoxysilylpropoxy group and the like, and amino groups include methylamino group, dimethyl group Amino group, ethylamino group, diethylamino Group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, dibutylamino group, isobutylamino group, diisobutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group , Dipentylamino group, piperidino group, morpholino group and the like.

Further, the merocyanine dye bonded to the structural unit represented by the general formula 1 has a structure of any one of the general formulas 3 to 5, and is bonded to the copolymer via the linking group L.

General formula 3

Formula 4

Formula 5

In General Formulas 3 to 5, Z ^{1 to} Z ⁹ represent the same or different heterocycles. X ^{1 to} X ⁶ are each independently a carbon atom or a group 15 or group 16 in the periodic table such as a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, etc. Represents a hetero atom. Y ^{1 to} Y ⁹ represent the same or different heteroatoms, and examples of the individual heteroatoms include elements of Group 16 in the periodic table such as oxygen atoms, sulfur atoms, selenium atoms, and tellurium atoms. It is done. Therefore, specific examples of the heterocyclic ring in Z ^{1 to} Z ⁹ include, for example, acenaphthyreno [1,2-d] thiazole ring, isoxazole ring, isoquinoline ring, imidazole ring, 2,4-imidazolidinedione ring, 2, 4-imidazolidinedithione ring, imidazoline ring, imidazo [4,5-d] quinoxaline ring, imidazo [4,5-d] quinoline ring, imidazo [4,5-d] pyridine ring, indolenine ring, indole ring, Oxadiazole ring, 2,5-oxazolidinedione ring, 2,5-oxazolidinedithione ring, oxazole ring, quinoline ring, quinolino [2,3-d] thiazole ring, 2,4-thiazolidinecythione ring, 2,4 -Thiazolidinedione ring, thiadiazole ring, thiazoline ring, thiazole ring, 2-thioxo-4-imidazolidi Ring, 2-thioxo-5-oxazolidinone ring, 2-thioxo-4-thiazolidinone ring, 2-thioxo-5-pyrrolidinone ring, tetrazole ring, naphtho [2,3-d] imidazole ring, naphtho [1,2- d] thiazole ring, naphtho [2,3-d] thiazole ring, triazole ring, pyrazole ring, pyridine ring, 2,5-pyrrolidinedione ring, 2,5-pyrrolidinedithione ring, pyrrole ring, phenanthreno [9,10- d] thiazole ring, benzimidazole ring, benzoindolenine ring, benzoxazole ring, benzoselenazole ring, benzothiadiazole ring and the like.

R ^{1 to} R ²⁷ in General Formulas 3 to 5 each independently represent a hydrogen atom or a substituent. Examples of the substituent in R ^{1 to} R ²⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a 2-propynyl group, a butyl group, an isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 2-pentenyl group, 2-penten-4-ynyl group, 1-methylpentyl group, 2-methylpentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, aliphatic hydrocarbon group such as dodecyl group, undecyl group, octadecyl group, cyclo Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, Alicyclic hydrocarbon group such as loheptyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, Aromatic hydrocarbon groups such as biphenylyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, benzyloxy group, Ether groups such as methylenedioxy group and ethylenedioxy group, ester groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group, methylamino group, dimethylamino group, ethylamino group, diethylamino group Group, propylamino group, dipropylamino group, isopropyl Ruamino group, diisopropylamino group, butylamino group, dibutylamino group, isobutylamino group, diisobutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group, dipentylamino group, piperidino group, morpholino group, etc. Substituents composed of halogen groups such as amino group, fluoro group, chloro group, bromo group, iodo group, hydroxy group, carboxy group, sulfo group or salts thereof, cyano group, nitro group, and combinations thereof Can be mentioned. And any one of R ^{1 to} R ²⁷ becomes a divalent group, and is linked to the copolymer as L in the general formula 1 to bond the merocyanine dye and the copolymer. At this time, the substituents R ^{1 to} R ²⁷ linked as L represent the linking group L in the general formula 1. Note that when X ^{1 to} X ⁶ are divalent or trivalent heteroatoms, some or all of R ⁵ , R ⁶ , R ^{12 to} R ^15, and R ^{22 to} R ²⁷ do not exist. Further, Z ¹ , Z ³ and Z ⁶ in the general formulas 3 to 5 may have one or more substituents. Examples of the substituent include the substituents listed in R ^{1 to} R ²⁷ . m is an integer of 0 or more. When m is 0, R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ²⁰ and R ²¹ do not exist.

The merocyanine dye copolymer of the present invention is a copolymer comprising 1 to 50 mol%, preferably 10 to 40 mol%, of the structural unit represented by the general formula 1; The number average molecular weight (hereinafter sometimes abbreviated as “Mn”) is in the range of 1,000 to 100,000, preferably 2,000 to 10,000, and its weight average molecular weight (hereinafter “Mw”). Is a merocyanine dye copolymer in the range of 1,000 to 100,000, preferably 5,000 to 30,000.

Such a merocyanine dye copolymer can be synthesized by various methods. However, if importance is attached to economy, for example, the merocyanine dye monomer represented by the general formula 6 corresponding to the general formula 1 and the general formula 2 The merocyanine dye copolymer of the present invention can be synthesized by polymerizing the corresponding monomer represented by the general formula 7 in the presence of a free radical initiator.

General formula 6:

(In General Formula 6, G ¹ , G ² , L, and M represent the same as in General Formula 1 above.)

（一般式７において、Ｇ^３、Ｇ^４は上記一般式２と同じものを表す。） Formula 7

(In General Formula 7, G ³ and G ⁴ represent the same as in General Formula 2 above.)

Specific examples of the merocyanine dye monomer represented by the general formula 6 include those represented by the chemical formulas 1 to 11. By the way, these merocyanine dye monomers are, for example, the method described in Masaaki Hayami “Photosensitive Dye”, pages 11 to 31, 1997, published by Sangyo Tosho Co., Ltd., or in accordance with those methods. The quantity can be obtained.

Chemical formula 1:

Chemical formula 2:

Chemical formula 3:

Chemical formula 4:

Chemical formula 5:

Chemical formula 6:

Chemical formula 7:

Chemical formula 8:

Chemical formula 9:

Chemical formula 10:

Formula 11:

Examples of the monomer represented by the general formula 7 used for the synthesis of the merocyanine dye copolymer of the present invention include methyl vinyl ketone, phenyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, and cyclohexyl vinyl. Ketones, vinyl ketones such as isobutyl vinyl ketone, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, neopentyl acrylate, hexyl acrylate, heptyl acrylate, Octyl acrylate, nonyl acrylate, dodecyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, 2-ethylbutyl acrylate 1,3-dimethylbutyl acrylate, 2-ethylhexyl acrylate, 2-methylpentyl acrylate, cyclohexyl acrylate, adamantyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, tetrahydrofurfryl acrylate, 2-hydroxypropyl acrylate, Cyclohexyl acrylate, neopentyl glycol acrylate, pentaerythritol acrylate, 1,6-hexanediol acrylate, trimethylolpropane acrylate, tetraethylene glycol acrylate, 1,3-butylene glycol acrylate, ethylene glycol acrylate, glycerol acrylate, 1,3-propane Diol acrylate, 1,2,4-butanetriol Acrylate, 1,4-cyclohexanediol acrylate, 1,5-pentanediol acrylate, phenyl acrylate, 4-methoxycarbonylphenyl acrylate, 4-ethoxycarbonylphenyl acrylate, 4-butoxycarbonylphenyl acrylate, 4-tert-butylphenyl acrylate, Benzyl acrylate, 4-phenylethyl acrylate, 4-phenoxydiethylene glycol acrylate, 4-phenoxytetraethylene glycol acrylate, 4-phenoxyhexaethylene glycol acrylate, 4-biphenylyl acrylate, ferrocenylmethyl acrylate, ferrocenylethyl acrylate , Trifluoroethyl acrylate, tetrafluoropropyl acrylate, heptade Acrylic esters such as cafluorodecyl acrylate, octafluoropentyl acrylate, 2,3-dibromopropyl acrylate, trimethoxysilylpropyl acrylate, glycidyl acrylate, or methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl Methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, neopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, dodecyl methacrylate, 2-methylbutyl methacrylate, 3-methylbutyl methacrylate, 2-ethylbutyl Methacrylate, 1,3-dimethyl Butyl methacrylate, 2-ethylhexyl methacrylate, 2-methylpentyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, neopentyl glycol methacrylate , Pentaerythritol methacrylate, 1,6-hexanediol methacrylate, trimethylolpropyl methacrylate, tetraethylene glycol methacrylate, 1,3-butylene glycol methacrylate, ethylene glycol methacrylate, glycerol methacrylate, 1,3-propanediol methacrylate, 1,2, 4 Butanetriol methacrylate, 1,4-cyclohexanediol methacrylate, 1,5-pentanediol methacrylate, phenyl methacrylate, 4-methoxycarbonylphenyl methacrylate, 4-ethoxycarbonylphenyl methacrylate, 4-butoxycarbonylphenyl methacrylate, 4-tert-butylphenyl Methacrylate, benzyl methacrylate, 4-phenylethyl methacrylate, 4-phenoxydiethylene glycol methacrylate, 4-phenoxytetraethylene glycol methacrylate, 4-phenoxyhexaethylene glycol methacrylate, 4-biphenylyl methacrylate, ferrocenylmethyl methacrylate, ferrocenyl Ethyl methacrylate, trifluoroethyl methacrylate Methacrylic acid esters such as rate, tetrafluoropropyl methacrylate, heptadecafluorodecyl methacrylate, octafluoropentyl methacrylate, 2,3-dibromopropyl methacrylate, trimethoxysilylpropyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, N-methylolacrylamide N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, N, N-dimethylacrylamide, etc. And other monomers such as acrylamides and methacrylamides.

In addition, the merocyanine dye copolymer of the present invention may contain 1 to 30 mol% of a copolymer component other than the monomer. Examples of monomers that can be used as other copolymerization components include ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, vinyl ethers such as phenyl vinyl ether, vinyl acetate, vinyl chloroacetate, Vinyl esters such as vinyl butyrate, vinyl acetate, vinyl benzoate, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, vinylpyrrolidine, etc. And the like. In addition, these monomers may be ones in which one or more dyes such as a coumarin compound, a cyanine compound, a cyclopentanone compound, a stilbene dye, a pyran compound, a methylene blue compound, and a merocyanine dye are bonded. .

In the method for synthesizing the merocyanine dye copolymer of the present invention, the monomer represented by the general formula 6 and the monomer represented by the general formula 7 are contained in a reaction vessel in a molar ratio of 2: 1 to 1: 1, respectively. Mix in a ratio of 60, and if necessary, dissolve in a solvent as appropriate. For example, di- (tert-butyl) peroxide, 1,1-bis (tert-butyl-peroxy) 3,3,5-trimethylcyclohexane , Tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperoxybivalate, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2, 5-di (butylperoxy) hexane, benzoyl peroxide, decanoyl peroxide, propionyl peroxide, hydroxyheptyl peroxide, cyclohexyl peroxide Non-peroxides such as tert-butyl perbenzoate, dicumyl peroxide, lauroyl peroxide, azoisobisbutyronitrile, 2,2-azobis (2-methylpropionitrile), 2,2-azobis ( After adding a free radical initiator such as 2-methylvaleronitrile) or an azo compound such as 4,4′-azobis (4-cyanovaleric acid), the temperature is adjusted to ambient temperature or ambient temperature by heating and refluxing with stirring. React at a temperature above.

Examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, and chlorobenzene. , Halides such as bromobenzene, α-dichlorobenzene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2 Alcohols such as methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene glycol, glycerin And phenols, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, methyl carbitol, ethyl carbitol , Ethers such as methyl cellosolve, ethyl cellosolve, ketones such as furfural, acetone, ethyl methyl ketone, cyclohexanone, acetic acid, acetic anhydride, propionic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, Ethylene carbonate, propylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, N-methylacetamide, N, N -Acids and acid derivatives such as dimethylacetamide, hexamethylphosphoric triamide, trimethyl phosphate, nitriles such as acetonitrile, propionitrile, succinonitrile, benzonitrile, nitriles such as nitromethane, nitribenzene, benzonitrile, nitromethane, nitrobenzene, etc. Nitro compounds, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, water and the like, and these may be used in combination as appropriate.

In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. Conversely, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir the raw material compound, and a side reaction tends to occur. Therefore, it is desirable that the amount of the solvent is within a range of usually 5 to 50 times by weight ratio up to 100 times the whole raw material compound. Although depending on the type of raw material compound and reaction conditions, the reaction is completed within 10 hours, preferably 0.5 to 5 hours.

Although the merocyanine dye copolymer thus obtained may be used as it is depending on the application, it is usually prior to use, for example, dissolution, liquid separation, gradient, filtration, extraction, concentration, thin layer chromatography, It can refine | purify by the general purpose method for purifying related compounds, such as a gas chromatography, a high performance liquid chromatography, distillation, sublimation, crystallization, and these methods are applied in combination as needed.

The merocyanine dye copolymer of the present invention has an absorption maximum in the visible region longer than 490 nm, usually in the wavelength region near 505 to 550 nm, and has a wide absorption wavelength region in the visible region, with the absorption maximum wavelength being the center. Since the half-value width of the molecular extinction coefficient is wide, visible light having a wavelength of around 500 nm, which is widely used for photochemical polymerization, is efficiently absorbed. Moreover, the merocyanine dye-based copolymer of the present invention is widely used for photochemical polymerization, for example, hydrocarbon-based, alcohol-based, ether-based, ketone-based, nitrile-based, halogen-based, amide-based, esters, etc. Shows practically no hindrance in hydrophilic and hydrophobic solvents, especially when using alcoholic and ketone solvents such as ethyl cellosolve, methyl ethyl ketone, and methyl isobutyl ketone. It is excellent in compatibility with other compounding components such as a polymerizable compound and a binder resin. Because of these properties, the merocyanine dye copolymer of the present invention is, for example, information display devices such as holograms, photographs, copying machines, printers, facsimiles, flexographic plate making, printing such as gravure printing, printing circuits such as photoresist, integrated circuits, etc. It has a wide variety of uses including a photosensitizer in a circuit and a light absorber constituting a recording layer of a write-once or rewritable high-density optical recording medium.

Furthermore, the merocyanine dye copolymer of the present invention, in addition to the above-described uses, in particular, the merocyanine dye copolymer absorbs light in the ultraviolet region, visible region, or infrared region as necessary. One or more of these materials, and if necessary, other acrylic acid homopolymers and copolymers such as acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, nitrocellulose, methylcellulose, ethylcellulose, cellulose Cellulose polymer of acetate, polyethylene, polypropylene, polystyrene, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl pyrrolidone, polyvinyl alcohol vinyl polymer and vinyl compound copolymer, polyester, polyurethane, Polyamide, butadiene-steel Copolymer, epoxy polymer, melamine compound, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, oleic acid Plasticizers such as tetrahydrofurfuryl, sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether, alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl -N-carboxyethyl-N-hydroxyethylimidazolinium betaine surfactants, hindered amine compounds, acrylate compounds, metal complex compounds, oxy With one or more additives such as light stabilizers such as samide compounds and triazine compounds, phosphorus antioxidants, sulfur antioxidants, and antioxidants such as phenolic antioxidants, Other than clothing, for example, drape, lace, casement, print, venetian blind, roll screen, shutter, goodwill, blanket, futon, futon, duvet cover, duvet cotton, sheets, cushion, pillow, pillow cover, cushion, Mats, carpets, sleeping bags, tents, interior materials for vehicles including automobiles, bedding products such as window glass and window glass, disposable diapers, diaper covers, health supplies such as glasses, monocles, and hoods, insoles, shoes Linings, remote areas, furoshiki, umbrellas, parasols, stuffed animals, lighting devices, for example, cathode ray tube displays, liquid crystal displays -Optical filters for information display devices such as television receivers and personal computers using electroluminescent displays, plasma displays, panels and screens, sunglasses, sunroofs, sun visors, PET bottles, storage, plastic houses, When used as a cold chill, optical fiber, prepaid card, microwave oven, oven and other viewing windows, photoelectric conversion elements, and packaging materials, filling materials, containers, etc. In addition to preventing or reducing problems and inconveniences caused by environmental light such as natural light and artificial light, the color, color tone, texture, etc. of the article can be adjusted, and the light reflected or transmitted from the article can be of a desired color. There are real benefits that can be balanced.

Hereinafter, embodiments of the present invention will be described based on examples.

<Merocyanine Dye Monomer> An appropriate amount of dimethylacetamide is taken in a reaction vessel, and 1.8 g of merocyanine dye represented by Chemical Formula 12, 8 ml of triethylamine and 4- (N, N-dimethylamino) are cooled and stirred at 10 ° C. or lower. ) 10 mg of pyridine was added, and 2 ml of methacrylic acid chloride was added dropwise, followed by heating to 40 ° C. and reaction for 4 hours. Ethanol was added to the reaction mixture and cooled to room temperature. The precipitated crystals were collected and recrystallized with chloroform. As a result, 0.84 g of red crystals of the merocyanine dye monomer represented by Chemical Formula 1 was obtained.

Chemical formula 12:

When a part of the crystal was taken and the melting point was measured by a conventional method, the melting point of the merocyanine dye monomer represented by Chemical Formula 1 was 198 ° C. Further, when a visible absorption spectrum in a methanol solution was measured according to a conventional method, an absorption maximum (ε = 9.93 × 10 ⁴ ) was observed near a wavelength of 525 nm. Furthermore, when a ¹ H-nuclear magnetic resonance spectrum (hereinafter abbreviated as “ ¹ H-NMR spectrum”) in a chloroform-d solution was measured by a conventional method, the chemical shift δ (ppm, TMS) was 1 .4 (t, 3H), 1.9 (s, 3H), 4.0 (q, 2H), 4.4 (s, 4H), 5.3 (d, 1H), 5.6 (s, 1H), 6.1 (s, 1H), and 7.0 to 7.6 (m, 5H).

<Merocyanine Dye Copolymer> A reaction vessel was charged with 6 ml of dimethyl sulfoxide, 0.1 g of merocyanine dye monomer represented by Chemical Formula 1, 0.25 ml of methyl methacrylate, and 20 mg of azobisisobutyronitrile. The reaction was carried out at 80 ° C. for 5 hours. The reaction solution was poured into a large excess of methanol, and the filtered polymer was reprecipitated using chloroform as a good solvent and methanol as a poor solvent. As a result, a pale red color of the merocyanine dye copolymer of the present invention represented by Chemical Formula 13 was obtained. 40 mg of polymer was obtained.

Chemical formula 13:

A part of this polymer was taken, and the copolymer composition determined from ¹ H-NMR according to a conventional method had a merocyanine residue content of 31.3 mol%. Furthermore, the number average molecular weight in terms of polystyrene was 2,500, the weight average molecular weight was 6,000, the molecular weight distribution Mw / Mn was 2.4, and the average degree of polymerization was 4. Further, when a visible absorption spectrum in a methanol solution was measured according to a conventional method, an absorption maximum (ε = 9.93 × 10 ⁴ ) was observed near a wavelength of 525 nm. Then, centering on the absorption maximum wavelength, a wavelength at which the molecular extinction coefficient is halved on the short wavelength side of the absorption maximum wavelength (474 nm) and a wavelength at which the molecular extinction coefficient is halved on the long wavelength side of the absorption maximum wavelength (542 nm), respectively. The half-width was obtained by calculating 1/2 of the wavelength difference between the two, and it was 34 nm.

<Merocyanine Dye Copolymer> A reaction vessel was charged with 6 ml of dimethyl sulfoxide, 0.04 g of a merocyanine dye monomer represented by Chemical Formula 1, 0.5 ml of methyl methacrylate, and 20 mg of azobisisobutyronitrile. The reaction was carried out at 80 ° C. for 5 hours. The reaction solution was poured into a large excess of methanol, and the filtered polymer was reprecipitated using chloroform as a good solvent and methanol as a poor solvent. As a result, a pale red color of the merocyanine dye copolymer of the present invention represented by the chemical formula 14 was obtained. 40 mg of polymer was obtained.

Chemical formula 14:

A copolymer composition obtained by taking a part of this polymer and determined from ¹ H-NMR according to a conventional method had a merocyanine residue content of 1.8 mol%. Furthermore, the number average molecular weight in terms of polystyrene was 9,200, the weight average molecular weight was 20,000, the molecular weight distribution Mw / Mn was 2.2, and the average degree of polymerization was 1.5. Further, when a visible absorption spectrum in a methanol solution was measured according to a conventional method, an absorption maximum (ε = 9.93 × 10 ⁴ ) was observed near a wavelength of 525 nm. Then, centering on the absorption maximum wavelength, a wavelength at which the molecular extinction coefficient is halved on the short wavelength side of the absorption maximum wavelength (484 nm) and a wavelength at which the molecular extinction coefficient is halved on the long wavelength side of the absorption maximum wavelength (544 nm), respectively. The half-width was obtained by calculating 1/2 of the wavelength difference between the two, and it was 30 nm.

<Merocyanine Dye Monomer> An appropriate amount of dimethylacetamide was taken in a reaction vessel, and while cooling and stirring to 10 ° C. or lower, 0.7 g of merocyanine dye represented by Chemical Formula 15, 2 ml of triethylamine, and 4- (N, N-dimethylamino) ) 5 mg of pyridine was added, and 1.3 ml of methacrylic acid chloride was added dropwise, followed by reaction at the same temperature for 2 hours, and then 30 ml of pure water was added to the reaction mixture. The precipitated crystals were collected and purified by silica gel column chromatography (developing solvent; chloroform). As a result, 0.15 g of a red crystal of a merocyanine dye monomer represented by Chemical Formula 7 was obtained.

Chemical formula 15:

When a part of the crystal was taken and the melting point was measured by a conventional method, the melting point of the merocyanine dye monomer represented by Chemical Formula 7 was 253 ° C. Further, when a visible absorption spectrum in a methanol solution was measured according to a conventional method, an absorption maximum (ε = 1.33 × 10 ⁵ ) was observed near a wavelength of 511 nm. Furthermore, when the ¹ H-NMR spectrum in the chloroform-d solution was measured by a conventional method, the chemical shift δ (ppm, TMS) was 2.0 (s, 3H), 3.8 (s, 6H), Peaks were observed at 4.5 (s, 4H), 5.5 (s, 1H), 6.1 (s, 1H), and 7.3-8.0 (m, 5H).

<Merocyanine Dye Copolymer> Into a reaction vessel was charged 6 ml of dimethyl sulfoxide, 53 mg of merocyanine dye monomer represented by Chemical Formula 7, 0.11 ml of methyl methacrylate, 5.6 mg of azobisisobutyronitrile, and under a nitrogen stream, The reaction was carried out at 100 ° C. for 6 hours. The reaction solution was poured into a large excess of methanol, and the filtered polymer was reprecipitated with chloroform as a good solvent and methanol as a poor solvent. As a result, the light red color of the merocyanine dye copolymer of the present invention represented by the chemical formula 16 was obtained. 55 mg of polymer was obtained.

Chemical formula 16:

A portion of this polymer was taken and the copolymer composition determined from ¹ H-NMR according to a conventional method had a merocyanine residue content of 10 mol%. Furthermore, the number average molecular weight in terms of polystyrene was 3,700, the weight average molecular weight was 5,900, the molecular weight distribution Mw / Mn was 1.6, and the average degree of polymerization was 3. Further, when a visible absorption spectrum in a methanol solution was measured according to a conventional method, an absorption maximum (ε = 1.33 × 10 ⁵ ) was observed near a wavelength of 511 nm. Then, centering on the absorption maximum wavelength, a wavelength (479 nm) at which the molecular extinction coefficient is halved on the short wavelength side of the absorption maximum wavelength and a wavelength (527 nm) at which the molecular extinction coefficient is halved on the long wavelength side of the absorption maximum wavelength, respectively. The half value width was obtained by calculating 1/2 of the wavelength difference between the two, and it was 24 nm.

<Merocyanine Dye Monomer> An appropriate amount of dimethylacetamide was taken in a reaction vessel, and while cooling and stirring at 10 ° C. or lower, 0.8 g of merocyanine dye represented by Chemical Formula 17, 1.6 ml of triethylamine, and 4- (N, N— After adding 5 mg of (dimethylamino) pyridine and further adding 0.8 ml of methacrylic acid chloride dropwise, the mixture was heated to 50 ° C. and reacted for 30 minutes. After adding 8 ml of pure water to the reaction mixture and cooling to room temperature, the precipitated crystals were collected and purified by silica gel column chromatography (developing solvent: chloroform). As a result, the merocyanine dye monomer represented by Chemical Formula 5 was obtained. 0.22 g of red crystals was obtained.

Chemical formula 17:

When a part of the crystal was taken and the melting point was measured by a conventional method, the melting point of the merocyanine dye monomer represented by Chemical Formula 5 was 220 ° C. Further, when a visible absorption spectrum in a methanol solution was measured according to a conventional method, an absorption maximum (ε = 1.05 × 10 ⁵ ) was observed near a wavelength of 494 nm. Furthermore, when the ¹ H-NMR spectrum in the chloroform-d solution was measured by a conventional method, the chemical shift δ (ppm, TMS) was 1.3 (m, 3H), 1.5 (m, 3H), 1.9 (d, 3H), 4.3 (m, 2H), 4.5 (m, 2H), 4.6 (m, 2H), 4.9 (m, 2H), 5.5 (d , 1H), 6.1 (s, 1H), and 7.3-8.4 (m, 6H).

<Merocyanine Dye Copolymer> A reaction vessel was charged with 6 ml of dimethyl sulfoxide, 0.1 g of a merocyanine dye monomer represented by Chemical Formula 5, 0.23 ml of methyl methacrylate, and 10 mg of azobisisobutyronitrile. The reaction was performed at 100 ° C. for 6 hours. The reaction solution was poured into a large excess of methanol, and the filtered polymer was reprecipitated using chloroform as a good solvent and methanol as a poor solvent. As a result, a pale red color of the merocyanine dye copolymer of the present invention represented by Formula 18 was obtained. 38 mg of polymer was obtained.

Chemical formula 18:

A part of this polymer was taken, and the copolymer composition determined from ¹ H-NMR according to a conventional method had a merocyanine residue content of 7.1 mol%. Furthermore, the number average molecular weight in terms of polystyrene was 5,400, the weight average molecular weight was 9,000, the molecular weight distribution Mw / Mn was 1.7, and the average degree of polymerization was 6. Further, when a visible absorption spectrum in a methanol solution was measured according to a conventional method, an absorption maximum (ε = 1.05 × 10 ⁵ ) was observed near a wavelength of 494 nm. Then, centering on the absorption maximum wavelength, a wavelength at which the molecular extinction coefficient is halved on the short wavelength side of the absorption maximum wavelength (463 nm) and a wavelength at which the molecular extinction coefficient is halved on the long wavelength side of the absorption maximum wavelength (512 nm), respectively. It was 24.5 nm when it calculated | required, 1/2 of both wavelength difference was calculated, and the half value width was calculated | required. <Experimental example 1: sensitivity measurement>

Binder polymer (trade name “XPD2000” manufactured by Chugai Trading) 10% ethyl cellosolve solution, 10 parts by weight of monomer (trade name “A-TMM-3LM-N” manufactured by Shin-Nakamura Chemical Co., Ltd.), initiator (trade name) "Diphenyliodonium phosphate" manufactured by Avocado) 0.5 parts by weight of a solution was prepared, and any one of Chemical Formula 13, Chemical Formula 16, Chemical Formula 18, and Comparative Control Dye (Chemical Formula 12), which are merocyanine dye copolymers of the present invention 0.3 parts by weight of each was added to prepare a photopolymerization composition.

Next, according to a conventional method, this composition was uniformly applied to a surface-treated aluminum plate to form a photosensitive layer, and then a polyvinyl alcohol layer was formed to prevent polymerization due to oxygen. Then, a gray scale was brought into close contact with this photosensitive layer, and light from a 150 W xenon lamp was extracted with light having a desired wavelength (539 nm) using a sharp cut filter and an interference filter, and exposed for 60 seconds. Thereafter, development was performed with an alkaline developer to determine the number of photocured insolubilization steps, and the sensitivity was determined using the following equation. These results are shown in Table 1.

E (mJ / cm ² ) = Io (mJ / cm ² · s) × Tn × t (s)
E: total irradiation amount during photocuring, Tn: transmittance of step tablet nth stage, t: exposure time, Io: exposure intensity

The combination of various filters (sharp cut filter, interference filter, heat ray cut filter) is sharp cut filter (product name “Y52”; manufactured by Toshiba Glass), interference filter (product name “KL54”; manufactured by Toshiba Glass), heat ray cut filter. (Trade name “HA-30”; manufactured by HOYA) was used.

From the above results, merocyanine dyes copolymer of the present invention is a gray scale sensitivity 0.8~1.9mJ / cm ^2, compared to the gray scale sensitivity 8.6mJ / cm ² of comparative compound, the dye for the entire system In spite of the decrease in weight part, the sensitivity was increased by 4 times or more. In addition, the photopolymerization composition using the merocyanine dye copolymer has improved sensitivity as compared with the photopolymerization composition using the comparative compound, although the abundance of the dye itself is reduced. Since it is possible to easily eliminate the color, it is considered that the color erasability is dominant.

<Experimental Example 2: Hologram Evaluation> (1) Production of Volume Type Hologram A photosensitive composition for volume type hologram recording was obtained by mixing the following components. As the sensitizing dye, the merocyanine dye copolymer of the present invention (chemical formula 13) was used. A merocyanine dye monomer (Chemical Formula 12) was used as a comparative compound. <Composition> Bisphenol epoxy resin (made by Showa Polymer) 100 parts by weight Acrylate monomer (made by Avocado) 100 parts by weight Diphenyliodonium salt (made by Avocado) 5 parts by weight Methyl ethyl ketone (made by Wako Pure Chemical Industries) 100 parts by weight Sensitizing dye 0 .2 parts by weight

(2) Production of Photosensitive Medium for Volume Type Hologram Recording The photosensitive composition for volume type hologram recording is applied on a glass having a thickness of 10 mm with an applicator, and the hologram recording composition having a thickness of 15 μm when dried. A layer was formed to prepare a photosensitive medium for volume hologram recording. A polyethylene terephthalate (hereinafter abbreviated as “PET”) film was laminated as a protective film on the hologram recording composition side of the volume hologram recording photosensitive medium.

(3) Production of Volume Type Hologram A 488 nm argon laser beam was incident from the glass substrate side to perform interference exposure, and a volume type hologram was recorded. Subsequently, the interference light was fixed by irradiating a xenon lamp to produce a volume hologram. Table 2 shows the total exposure (mJ) required for producing the volume hologram.

The hologram sensitivity of the merocyanine dye copolymer (Chemical Formula 13) and the merocyanine dye monomer (Chemical Formula 12) are 27 mJ and 72 mJ, respectively. It can be seen that the dye copolymer has achieved a sensitivity increase of about 3 times compared to the comparative control compound. As with the grayscale evaluation results, the sensitivity was improved compared to the case of the monomer even though the amount of the dye itself was reduced. Since the color of itself can be easily eliminated, the decoloring property is also improved, and it can be advantageously used as a photosensitive material for hologram recording. Furthermore, the merocyanine dye copolymer of the present invention can be copolymerized to be more soluble in solvents commonly used for photochemical polymerization such as holograms than other dye monomers, and to be compatible with other compounding components. Improvement in solubility was confirmed.

In addition, for example, it can be advantageously used as a photosensitizer and an absorbent in various fields including information display devices, printing, printed circuits, integrated circuits, and optical recording media.

Claims (5)

A merocyanine dye copolymer comprising a structural unit represented by General Formula 1 and a structural unit represented by General Formula 2. General formula 1:

(In General Formula 1, G ¹ represents a hydrogen atom or an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group may have a substituent. G ² represents an oxygen atom or a nitrogen atom, and nitrogen A hydrogen atom is bonded to the atom, L represents a linking group, and M represents a merocyanine dye.)
General formula 2:

(In General Formula 2, G ³ represents a hydrogen atom or an aliphatic hydrocarbon group, and G ⁴ represents a hydroxyl group or a linear or branched aliphatic hydrocarbon group, aromatic hydrocarbon group, ether group or amino group. To express.) The merocyanine dye copolymer according to claim 1, wherein the merocyanine dye is any one of the general formulas 3 to 5.
General formula 3:

General formula 4:

General formula 5:

(In General Formulas 3 to 5, Z ^{1 to} Z ⁹ represent the same or different heterocyclic rings, and these heterocyclic rings may have a substituent. X ^{1 to} X ⁶ are each independently Y ^{1 to} Y ⁹ each represent the same or different hetero atom, R ^{1 to} R ²⁷ each independently represents a hydrogen atom or a substituent, and any one of them Are linked as L in formula 1. When X ^{1 to} X ⁶ are heteroatoms, R ⁵ , R ⁶ , R ^{12 to} R ¹⁵ and R ^{22 to} R ²⁷ may not exist. , M is an integer of 0 or more, and when m is 0, R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ²⁰ and R ²¹ do not exist.)   The merocyanine dye copolymer according to claim 1 or 2, which contains 1 to 50 mol% of the structural unit represented by general formula 1 and has a number average molecular weight of 1,000 to 100,000.   A photopolymerizable composition comprising the merocyanine dye copolymer according to any one of claims 1 to 3. A merocyanine dye monomer represented by general formula 6, which is a constituent unit of the merocyanine dye copolymer according to any one of claims 1 to 3.
General formula 6:

(In General Formula 6, G ¹ , G ² , L, and M represent the same as in General Formula 1 above.)