JP2001209176A - Photopolymerizable composition and recording material using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having high sensitivity to light in the region from visible light to infrared light as well as to ultraviolet light. SOLUTION: The photopolymerizable composition contains a polymerizable compound having an ethylenically unsaturated bond, a compound of formula 1 (where Q1-Q3 are each O or S; R1 and R2 are each H, an aliphatic group, an aromatic group or a heterocyclic group; and Z1 and Z2 are each a substituent required to allow the compound of the formula 1 to become a dye) and an organoboron compound of formula A (where Ra1-Ra3 are each an aliphatic group, an aromatic group, a heterocyclic group or -SiRa5Ra6Ra7; Ra5-Ra7 are each an aliphatic group or an aromatic group; Ra4 is an aliphatic group; and Y+ is a group capable of forming a cation).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can easily perform recording using not only ultraviolet light but also visible light to infrared light, and can use inks, color filters, holograms, proofs, sealants and adhesives. The use of a photopolymerizable composition that can be suitably used in a wide range of fields, including lithographic printing, resin letterpress, photoresist, etc., and the use of a developing solution, etc. are unnecessary, and unnecessary waste is not generated, and clear and high contrast is obtained. The present invention relates to a recording material capable of easily forming a high black-and-white or color completely dry image.

[0002]

2. Description of the Related Art A photopolymerizable composition basically comprises a photopolymerization initiator and an addition-polymerizable compound having two or more ethylenically unsaturated bonds in a molecule ("polyfunctional monomer"). Includes, cures when irradiated with light, changes in tackiness,
Insoluble in solvents. Utilizing these properties, the photopolymerizable composition has been conventionally used for photography, printing, metal surface treatment,
Widely used in fields such as ink.

In recent years, research on image formation using a photopolymerizable composition has been actively conducted. For example, an image forming system using photosensitive microcapsules in which the photopolymerizable composition is encapsulated in microcapsules has been proposed. ing. In recent years, attempts have been made to spectrally sensitize the photopolymerizable composition to a visible light region and form a digital image using a laser as a light source (Journal of the Photographic Society of Japan 49: 5, 210 (1986)).
), And application to full-color photosensitive materials (Japanese Patent Application Laid-Open No. 59-189340). Further, a novel photopolymerizable composition using an organic boron anion salt of an organic cationic dye has been proposed (European Patent No. 22).
3,587 A1, etc.). The photosensitive and heat-sensitive recording material using such a photopolymerizable composition is very environmentally preferable because it can record an image in a completely dry system without using a developing solution or the like and does not generate waste. Things.

When an image is recorded on a photosensitive recording material, it is advantageous to use not only UV light and short-wave visible light, but also an inexpensive infrared laser and green to red light. However, in a recording material using a photopolymerizable composition,
Many are sensitive to ultraviolet light, but are insensitive to visible light to infrared light or, even if exposed, have insufficient sensitivity. As a result, the formed image may be unclear or the contrast between the image portion and the non-image portion may be insufficient, and further improvement is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention is not limited to ultraviolet light, visible light ~
Photopolymerized with high sensitivity to infrared light and suitable for use in a wide range of fields including inks, color filters, holograms, proofs, sealants, adhesives, lithographic printing, resin letterpress, photoresist, etc. It is intended to provide a neutral composition. Further, the present invention provides a recording material capable of recording images in a completely dry system by using the photopolymerizable composition, and capable of easily forming a clear, high-contrast black-and-white or color image. The purpose is to provide. In particular, an object of the present invention is to provide a recording material in which the covering of the background portion is reduced.

[0006]

Means for Solving the Problems To solve the above problems, a photopolymerizable composition according to a first aspect of the present invention comprises a polymerizable compound having an ethylenically unsaturated bond and a compound represented by the following general formula (1): And a organoboron compound represented by the following general formula (A).

[0007]

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In the general formula (1), Q¹~ Q^ThreeAre each independently
Represents an oxygen atom or a sulfur atom; ¹And R^TwoIs German
And a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group
And Z¹And Z^TwoAre each independently represented by the general formula (1)
Lists the substituents required for the compound represented by the compound to become a dye.
You.

[0009]

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In the general formula (A), R _a ¹ , R _a ² and R _a ³
Each independently represent an aliphatic group, an aromatic group, a heterocyclic group or ^{_{-SiR a 5 R a 6 R a}} 7,, R a 5, R a 6 , and R _a ^7,
Each independently represents an aliphatic group or an aromatic group;
_a ⁴ represents an aliphatic group, and Y ⁺ represents a group capable of forming a cation.

In the photopolymerizable composition of the first embodiment, the compound represented by the general formula (1) is represented by the following general formula (4)
Preferably, the compound is represented by

[0012]

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In the general formula (4), L ¹ and L ² each independently represent a methine group which may be substituted;
And G ¹ and G ² each independently represent an electron-withdrawing group, or form an aromatic ring or a heterocyclic ring by bonding with G ¹ and G ² .

In order to solve the above problems, a photopolymerizable composition according to a second aspect of the present invention comprises a polymerizable compound having an ethylenically unsaturated bond and a compound represented by the following general formula (2). And a compound capable of generating a radical by interacting with a compound represented by the following general formula (2).

[0015]

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In the general formula (2), X ¹ represents NR ¹² , a sulfur atom, a selenium atom or an oxygen atom, and R ⁴ , R ⁵ and R ¹² each independently represent a hydrogen atom, an aliphatic group, Represents an aromatic group or a heterocyclic group, R ⁶ , R ⁷ , R ⁸ , R ⁹ ,
R ¹⁰ and R ¹¹ are each independently a hydrogen atom or 1
Represents a substituent having a valence of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
And two or more selected from R ¹² may combine to form a ring.

In order to solve the above problems, a photopolymerizable composition according to a third aspect of the present invention comprises a polymerizable compound having an ethylenically unsaturated bond and a compound represented by the following general formula (3). And a compound capable of generating a radical by interacting with a compound represented by the following general formula (3).

[0018]

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In the general formula (3), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent, and Z ³ and Z ⁴ each independently represent a group represented by the general formula (3). Represents a substituent necessary for the compound to be converted into a dye.

In the photopolymerizable composition of the third embodiment, the compound represented by the general formula (3) is represented by the following general formula (5)
Preferably, the compound is represented by

[0021]

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In the general formula (5), L ¹ and L ² each independently represent a methine group which may be substituted, and m represents 0 to 3
And G ¹ and G ² each independently represent an electron-withdrawing group, or form an aromatic ring or a heterocyclic ring by bonding with G ¹ and G ² .

In the photopolymerizable compositions of the second and third embodiments, each of the compounds represented by the general formula (2) and the compound represented by the general formula (3) interacts to generate a radical. The obtained compound is preferably an organic boron compound represented by the following general formula (A).

[0024]

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In the general formula (A), R _a ¹ , R _a ² and R _a ³
Each independently represent an aliphatic group, an aromatic group, a heterocyclic group or ^{_{-SiR a 5 R a 6 R a}} 7,, R a 5, R a 6 , and R _a ^7,
Each independently represents an aliphatic group or an aromatic group;
_a ⁴ represents an aliphatic group, and Y ⁺ represents a group capable of forming a cation.

In order to solve the above-mentioned problems, the recording material according to the first aspect of the present invention has a recording layer on a support, and the recording layer comprises a microcapsule containing a color-forming component, The polymerizable compound having at least the photopolymerizable composition according to any one of the third to third aspects, and having an ethylenically unsaturated bond, having a site that reacts with the color-forming component to form the color-forming component. It is a compound.

In order to solve the above-mentioned problems, a recording material according to a second aspect of the present invention has a recording layer on a support, and the recording layer includes a microcapsule containing a color-forming component, A color-forming compound that reacts with a component to form a color;
At least the photopolymerizable composition according to the third embodiment, wherein the polymerizable compound having an ethylenically unsaturated bond has a site for suppressing a reaction between the color-forming component and the color-forming compound. It is a compound.

When the recording material according to the first or second embodiment is used as a recording material for forming a multicolor image, the first recording layer sensitive to light having a center wavelength λ1 and the first recording layer sensitive to light having a center wavelength λ2. 1
, A second recording layer that develops a color different from the recording layer
Have a multilayer structure in which the first, second,..., And i-th recording layers that are sensitive to light having the center wavelength λi and are colored in a different color from the i-th recording layer are stacked in this order. Can be.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION (Photopolymerizable composition) In a first embodiment of the photopolymerizable composition of the present invention, a polymerizable compound having an ethylenically unsaturated bond is represented by the following general formula (1). And a organopolymerizable compound represented by the formula (A). A second embodiment of the photopolymerizable composition of the present invention is a polymerizable compound having an ethylenically unsaturated bond, a compound represented by the general formula (2), and a compound represented by the general formula (2). Compounds that generate radicals by interacting with
A "radical generator"). A third embodiment of the photopolymerizable composition of the present invention includes:
A polymerizable compound having an ethylenically unsaturated bond,
Photopolymerization containing a compound represented by the general formula (3) and a compound that generates a radical by interacting with the compound represented by the general formula (3) (hereinafter, referred to as “radical generator”). The composition is an acidic composition.

When the photopolymerizable compositions of the first to third embodiments are irradiated with light, each of the compounds represented by the general formulas (1) to (3) absorbs light, In the embodiment, the organic boron compound represented by the general formula (A) interacts with the compound represented by the general formula (1), and
In the embodiment, the radical generator interacts with each of the compound represented by the general formula (2) and the compound represented by the general formula (3) to generate a radical, which is polymerizable by the radical. The compound undergoes radical polymerization. Hereinafter, each component contained in the photopolymerizable composition of the first to third aspects will be described in detail.

Polymerizable Compound Having Ethylenic Unsaturated Bond The photopolymerizable composition according to the first to third aspects is a polymerizable compound having an ethylenically unsaturated bond (polymerizable compound).
It contains. The polymerizable compound is a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule, and the polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose. For example, acrylic acid derivatives such as acrylic acid esters and acrylamides, acrylic acid and its salts, methacrylic acid esters and methacrylic acid derivatives such as methacrylamides, methacrylic acid and its salts, maleic anhydride, and maleic acid Esters, itaconic acid, itaconic esters,
Styrenes, vinyl ethers, vinyl esters, N
-Vinyl heterocycles, allyl ethers, allyl esters, and the like.

The polymerizable compound contains one or two or more olefinic double bonds, and may be either low molecular weight (monomer) or high molecular weight (oligomer). Examples of the monomer containing a double bond include, for example, alkyl or hydroxyalkyl acrylate or methacrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate or ethyl methacrylate. And the like. Silicon acrylates are also advantageous. Other examples include acrylonitrile,
Acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl- and halostyrene, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride and the like. Can be

Examples of monomers containing two or more double bonds include diacrylates such as ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenol A,
And 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triaryl Allyl isocyanurate or tris (2-acryloylethyl) isocyanurate is exemplified.

Examples of relatively unsaturated (oligomeric) polyunsaturated compounds include epoxy resins having a (meth) acrylic group, polyesters having a (meth) acrylic group, polyesters containing vinyl ether or epoxy group, polyurethanes and polyurethanes. And polyethers. In addition, examples of unsaturated oligomers are unsaturated polyester resins, typically made from maleic acid, phthalic acid and one or more diols, from about 500 to 3000
Having a molecular weight of In addition, it is also possible to use vinyl ether monomers and oligomers, and maleate terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy backbones. Particularly suitable are combinations of oligomers having vinyl ether groups with the polymers described in WO 90/01512. Also suitable are copolymers of vinyl ether and maleic acid functionalized monomers. Such unsaturated oligomers can also belong as prepolymers.

Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids and esters of polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the main or side chains, such as unsaturated polyesters, polyamides and polyurethanes and their derivatives. Copolymers, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth) acrylic groups in the side chain, and mixtures of one or more such polymers.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linoleic acid or oleic acid. Among them, acrylic acid and methacrylic acid are preferred.

Suitable polyols include aromatic and
In particular, aliphatic and cycloaliphatic polyols. Examples of aromatic polyols include hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) propane, novolak and resorcin. Examples of polyepoxides are those based on the abovementioned polyols, especially aromatic polyols, and epichlorohydrin. Other suitable polyols are polymers and copolymers containing hydroxyl groups in the polymer chains or side chains, for example polyvinyl alcohol and their copolymers or polyhydroxyalkyl methacrylates or their copolymers. Further suitable polyols are oligoesters having hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols include alkylene diols having preferably 2 to 12 carbon atoms, such as ethylene glycol, 1,2-
Or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol; preferably a molecular weight of 200 to 1500 Polyethylene glycol having 1,3,3-cyclopentanediol, 1,2
-, 1,3- or 1,4-cyclohexanediol,
1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.

The polyol can be partially or completely esterified with one carboxylic acid or with a different unsaturated carboxylic acid, and in the partial ester the free hydroxyl groups can be modified, eg Can be etherified or esterified with a carboxylic acid.

Examples of the ester include the following. That is, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate , Pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate,

Tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol triitaconate, dipentaerythritol pentitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-
Butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate,
Sorbitol tetraacrylate, pentaerythritol-modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylate and methacrylate, glycerol diacrylate and triacrylate, 1,4-cyclohexanediacrylate, and a molecular weight of 200 to 1500 Bisacrylates and bismethacrylates of polyethylene glycol, or mixtures thereof.

Also suitable as the polymerizable compound are the same or different unsaturated carboxylic acids and aromatic or cycloaliphatic aliphatic compounds having preferably 2 to 6, especially 2 to 4 amino groups. And amides with aliphatic polyamines. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,
2-, 1,3- or 1,4-butylenediamine, 1,5
-Pentylenediamine, 1,6-hexylenediamine,
Octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (β-aminoethoxy)-or Di (β
-Aminopropoxy) ethane. In addition, polymers and copolymers preferably having an additional amino group in the side chain, and oligoamides having an amino terminal group are suitable. Examples of such unsaturated amides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis (methacrylamidopropoxy) ethane, β-
Methacrylamidoethyl methacrylate and N-[(β
-Hydroxyethoxy) ethyl] acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and from diols or diamines. Some of the maleic acid can be replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, for example styrene. Polyesters and polyamides can be derived from dicarboxylic acids, from ethylenically unsaturated diols or diamines, especially from those having a relatively long chain, for example, from 6 to 20 carbon atoms. Examples of polyurethanes include those composed of saturated or unsaturated diisocyanates and unsaturated or, respectively, saturated diols.

Polybutadienes and polyisoprenes and their copolymers are known. Examples of suitable comonomers are olefins such as ethylene, propene, butene and hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride. Polymers having (meth) acrylate groups in the side chains are likewise known. For example, it can be obtained as a reaction product of a novolak-based epoxy resin with (meth) acrylic acid, or a homo- or copolymer of vinyl alcohol or (meth) acrylic acid with its hydroxyalkyl derivative esterified with Or a homo- or copolymer of (meth) acrylate esterified with hydroxyalkyl (meth) acrylate.

The polymerizable compound may be a compound having a site exhibiting another function in its structure, depending on the use of the first and second photopolymerizable compositions. When the photopolymerizable composition according to the first or second embodiment is used for a recording material, it may have a portion that promotes a color-forming reaction of a color-forming component constituting an image portion or a portion that suppresses color formation. Good. These will be described later.

The content of the polymerizable compound having an ethylenically unsaturated bond is usually 10 to 99% by mass, and 30 to 95% by mass based on the total mass of the photopolymerizable composition.
Is preferred.

Compounds Represented by General Formulas (1) to (3) The compounds represented by the general formulas (1) to (3) contained in the photopolymerizable compositions of the first to third embodiments, respectively. The resulting compound is a neutral organic dye having no counter anion in the structure. In the photopolymerizable composition according to the first aspect, the compound represented by the general formula (1) has a function of spectrally sensitizing radical generation from the organic boron compound represented by the general formula (A). In the photopolymerizable compositions of the second and third embodiments, the compounds represented by the general formulas (2) and (3) have a function of spectrally sensitizing the radical generator. That is, when a compound represented by the above general formulas (1) to (3) is contained, irradiation with visible to infrared light corresponding to the absorption of the compound results in an organic boron compound having no absorption in this region or Even when a radical generator is contained, radical generation from an organic boron compound or a radical generator can be promoted. The compounds represented by the general formulas (1) to (3)
Since a high decoloring property is exhibited by irradiation with light of 50 nm or more, the recording material or the like using the photopolymerizable composition according to the first to third aspects can prevent the background portion from being covered and can improve the contrast. High clear images can be formed.

-1 Compound represented by the general formula (1)

[0049]

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In the general formula (1), Q ^{1 to} Q ³ each independently represent an oxygen atom or a sulfur atom. Among them, Q ¹ and Q ² are preferably oxygen atoms, and Q ³ is preferably a sulfur atom.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. When R ¹ and R ² represent an aliphatic group, examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group,
Substituted alkynyl groups, aralkyl groups, or substituted aralkyl groups, and the like, among which alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aralkyl groups,
Alternatively, a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable. Further, the aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

Examples of the alkyl group include linear, branched and cyclic alkyl groups. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkyl portion of the substituted alkyl group is the same as in the case of the alkyl group. The alkyl group may be a substituted alkyl group or an unsubstituted alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group,
Examples thereof include a 2-ethylhexyl group, a decyl group, a dodecyl group, an octadecyl group, a cyclohexyl group, a cyclopentyl group, a neopentyl group, an isopropyl group, and an isobutyl group.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, , A methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group), an alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylaminosulfonyl group having 30 or less carbon atoms, An alkoxy group having 30 or less carbon atoms (for example, a methoxy group, an ethoxy group, a benzyloxy group, a phenoxyethoxy group, a phenethyloxy group, etc.), an alkylthio group having 30 or less carbon atoms (for example, a methylthio group, an ethylthio group,
A methylthioethylthioethyl group or the like), an aryloxy group having 30 or less carbon atoms (for example, a phenoxy group, a p-tolyloxy group, a 1-naphthoxy group, a 2-naphthoxy group or the like);
Nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryloxycarbonyloxy group,

An acyloxy group having 30 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, etc.), a carbamoyl group (eg, carbamoyl group) Group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group,
An N, N-dimethylsulfamoyl group, a morpholinosulfonyl group, a piperidinosulfonyl group, etc., an aryl group having 30 or less carbon atoms (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) And the like, a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acylamino group, etc.), a substituted ureido group, a substituted phosphono group, a heterocyclic group and the like. Here, the carboxyl group, sulfo group, hydroxy group, and phosphono group may be in a salt state. At that time, examples of the cation forming a salt include Y ⁺ described below.

Examples of the alkenyl group include linear, branched and cyclic alkenyl groups. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkenyl portion of the substituted alkenyl group is the same as in the case of the alkenyl group. The alkenyl group may be a substituted alkenyl group or an unsubstituted alkenyl group. Examples of the substituent of the substituted alkenyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the alkynyl group include linear, branched and cyclic alkynyl groups. The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkynyl portion of the substituted alkynyl group is the same as in the case of the alkynyl group. Further, the alkynyl group may be either an alkynyl group having a substituent or an unsubstituted alkynyl group. Examples of the substituent of the substituted alkynyl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

Examples of the aralkyl group include linear, branched and cyclic aralkyl groups, and the aralkyl group preferably has 7 to 35 carbon atoms, more preferably 7 to 25 carbon atoms. The preferred range of the number of carbon atoms in the aralkyl portion of the substituted aralkyl group is the same as in the case of the aralkyl group. Further, the aralkyl group may be either an aralkyl group having a substituent or an unsubstituted aralkyl group. Examples of the substituent of the substituted aralkyl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

When R ¹ and R ² represent an aromatic group, examples of the aromatic group include an aryl group and a substituted aryl group. The number of carbon atoms in the aryl group is 6
To 30 are preferable, and 6 to 20 are more preferable. The preferred range of the number of carbon atoms in the aryl portion of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, and a β-naphthyl group. Examples of the substituent of the substituted aryl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

When R ¹ and R ² represent a heterocyclic group, the heterocyclic group includes a substituted heterocyclic group and an unsubstituted heterocyclic group. The heterocyclic group represented by R ¹ and R ² is preferably a heterocyclic group having 4 to 13 carbon atoms. Examples of such a heterocyclic group include a nitrogen-containing atom, an oxygen-containing atom, and a sulfur-containing heterocyclic ring, and more specifically, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyridazone ring, a quinoline ring, and an isoquinoline. Ring, quinoxaline ring, acridine ring, furan ring, oxazole ring, thiazole ring, oxadiazole ring, thiazoline ring, thiophene ring, indole ring and the like. When R ¹ and R ² represent a heterocyclic group having a substituent, examples of the substituent include the aforementioned R ¹
And the same substituents as those in the case where R ² has a substituent.

In particular, R ¹ and R ² represent an unsubstituted alkyl group (for example, a methyl group, an ethyl group, an n-propyl group,
-Butyl group, n-pentyl group, n-hexyl group, octyl group, octadecyl group, etc.) or a substituted alkyl group. Preferred examples of the substituted alkyl group include an alkoxyalkyl group (eg, methoxyethyl group, phenoxyethyl group, etc.) and an alkoxycarbonylalkyl group (eg, butoxycarbonylmethyl group, phenoxyethoxycarbonylmethyl group, etc.). R ¹ and R ² may be bonded to each other with an adjacent substituent to form a ring. Examples of the ring include a 5- or 6-membered hetero ring.

In the general formula (1), Z ¹ and Z ² each independently represent a substituent necessary for the compound represented by the general formula (1) to be a dye. Examples of the substituent include a group capable of forming a conjugated chain.

Among the compounds represented by the general formula (1), a compound represented by the following general formula (4) is preferable.

[0063]

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In the general formula (4), L ¹ and L ² each independently represent a methine group which may be substituted. When L ¹ and L ² represent a methine group, the methine group includes a methine group having a substituent and an unsubstituted methine group.
When L ¹ and L ² represent a methine group having a substituent, examples of the substituent include the same substituents as described above when R ¹ and R ² have a substituent.
It may form a ring (eg, a 5- or 6-membered carbon ring) with another methine group, or may form a ring with an auxochrome.

In the general formula (4), G ¹ and G ² each independently represent an electron-withdrawing group, or form an aromatic ring or a heterocyclic ring by bonding G ¹ and G ² . G ¹ and G ²
The electron withdrawing group represented by represents a substituent having a positive Hammett σ value. Examples of the electron-withdrawing group represented by G ¹ and G ² include an acetyl group, a propionyl group, a pivaloyl group, a chloroacetyl group, a trifluoroacetyl group,
Methylcyclopropylcarbonyl group, 1-ethylcyclopropylcarbonyl group, 1-benzylcyclopropylcarbonyl group, benzoyl group, 4-methoxybenzoyl group, acyl group such as tenoyl group, methoxycarbonyl group,
An oxycarbonyl group such as an ethoxycarbonyl group, a 2-methoxyethoxycarbonyl group, a 4-methoxyphenoxycarbonyl group, a carbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-diethylcarbamoyl group, an N-phenylcarbamoyl group; Carbamoyl groups such as 2,4-bis (pentyloxy) phenylcarbamoyl group, N-2,4-bis (octyloxy) phenylcarbamoyl group, morpholinocarbonyl group, cyano group, methanesulfonyl group, benzenesulfonyl group, and toluenesulfonyl group A phosphono group such as a diethylphosphono group, a benzoxazol-2-yl, a benzothiazol-2-yl group, a 3,4-dihydroquinazolin-4-one-2-yl group, and a 3,4-dihydro group. Quinazolin-4-sulfon-2-yl group Preferred heterocyclic groups are.

When G ¹ and G ² are bonded to form an aromatic ring, examples of the aromatic ring include benzene, naphthalene, and anthracene.

When G ¹ and G ² are combined to form a heterocyclic ring, the heterocyclic ring includes a 5- or 6-membered heterocyclic ring. As the 5- or 6-membered heterocyclic nucleus formed by G ¹ and G ² , a thiazole nucleus ゾ ー ル thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dichlorothiazole), benzo Thiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole,
5-methylbenzothiazole, 5-phenylbenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenoxybenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5-chloro-6 -Methylbenzothiazole, tetrahydrobenzothiazole,
4-phenylbenzothiazole, 5,6-bismethylthiobenzothiazole),

Naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] Thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2
3-d] thiazole), 8-methylthionaphtho [2,1
-D] thiazole｝, a thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline),
Oxazole nucleus ｛Oxazole nucleus (eg, oxazole, 4-methyloxazole, 4-nitrooxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (eg, benzoxazole, 5-chloro) Benzoxazole, 5-methylbenzoxazole, 5
-Fluorobenzoxazole, 5-phenylbenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-acetylbenzoxazole), naphthooxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [ 1,2-
d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-d] oxazole)},

Oxazoline nucleus (for example, 4,4-dimethyloxazoline), selenazole nucleus selenazole nucleus (for example, 4-methyl selenazole, 4-nitro selenazole, 4-phenyl selenazole), benzo selenazole nucleus (for example, Benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 6-
Nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1
-D] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-
Methyl selenazoline), a tellurazole nucleus and a tellurazole nucleus (for example, tellurazole, 4-methyltellurazole,
4-phenyltellurazole), benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5,6-dimethylbenzotellurazole, 6-methoxybenzotellurazole), naphtho Tellurazole nucleus (for example, naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole)},

The tellurazoline nucleus (for example, tellurazoline,
4-methyltellrazoline), 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine,
3,3-diethylindolenine, 3,3-dimethyl-5
-Cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine,
3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine),

Imidazole nucleus: imidazole nucleus (eg, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (eg, 1-alkylbenzimidazole, 1-alkyl-5-chloro) Benzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1
-Alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole,
1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-arylbenzimidazole), naphtho Imidazole nucleus (for example, 1-alkylnaphtho [1,2-d] imidazole)}. In the examples of the imidazole nucleus, examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl, and a hydroxyalkyl group (for example, 2-hydroxyethyl, 3
-Hydroxypropyl) is preferred, and a methyl group and an ethyl group are particularly preferred. In the examples of the imidazole nucleus, examples of the aryl group include phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, and alkoxy (eg, methoxy) substituted phenyl.

Further, 5 formed by G ¹ and G ²
The 6- or 6-membered heterocyclic nucleus includes a dithiol nucleus and a dithiol nucleus (eg, 1,3-dithiol, 4-chloro-
1,3-dithiol, 4,5-dialkoxycarbonyl-1,3-dithiol), 4,5-benzo-1,3-dithiol nucleus, 4,5-naphth-1,3-dithiol nucleus｝, dithiolane nucleus (For example, 1,3-dithiolane,
4-fluoro-1,3-dithiolane), dioxysole nucleus ｛dioxole nucleus (for example, 1,3-dioxole,
4-methyl-1,3-dioxole), 4,5-benzo-1,3-dioxole nucleus, 4,5-naphth-1,3-
Dioxol nucleus｝, dioxolane nucleus (eg, 1,3-
Dioxolane, 4-trifluoromethyl-1,3-dioxolane). In the examples of the dithiol nucleus, the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 9 carbon atoms, for example, an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like.

Further, the 5- or 6-membered heterocyclic nucleus formed by G ¹ and G ² includes a pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl -4-pyridine), quinoline nucleus ｛quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-
Quinoline, 6-nitro-2-quinoline, 8-fluoro-
2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline,
-Quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-
Methoxy-4-quinoline, 6-methyl-4-quinoline,
6-methoxy-4-quinoline, 6-chloro-4-quinoline, 5,6-dimethyl-4-quinoline), isoquinoline nucleus (for example, 6-nitro-1-isoquinoline, 3,4-
Dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (for example, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1, 3-diallylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-dibenzylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diphenylimidazo [4,5-b] Quinoxalin, 6-nitro-1,3-diallylimidazo [4,5-b] quinoxalin),

Oxadiazole nucleus, thiadiazole nucleus,
Pyrimidine nucleus, imidazo [4,5-b] pyrazine nucleus (for example, 1,3-diethyl [4,5-b] pyrazine, 1,3
-Diallyl [4,5-b] pyrazine), imidazo [4,
5-b] 1,4-quinone nucleus, pyrrolopyridine nucleus, pyrazolopyridine nucleus, 1,3,3a, 7-tetraazaindene nucleus, indolizine nucleus, 1,8-naphthyridine nucleus, pyran nucleus (for example, α -Pyran, γ-pyran, benzo-α-pyran, benzo-γ-pyran), a thiapiran nucleus (for example,
α-thiapiran, γ-thiapiran, benzo-α-thiapiran, benzo-γ-thiapiran), indolenine nucleus,

[0075]

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And the like.

In the general formula (4), m represents an integer of 0 to 3.

-2 Compound represented by formula (2)

[0079]

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In the general formula (2), X ¹ represents NR ¹² , a sulfur atom, a selenium atom or an oxygen atom. Among them, a sulfur atom and an oxygen atom are preferred.

In the general formula (2), R ⁴ , R ⁵ and R
Each ¹² independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. As the aliphatic group, aromatic group and heterocyclic group represented by R ⁴ , R ⁵ and R ¹² , the aliphatic group, aromatic group and heterocyclic group represented by R ¹ and R ^{2 in} the above general formula (1) Each has the same meaning as the ring group, and preferred examples are also the same.

In the general formula (2), R ⁶ , R ⁷ , R ⁸ ,
R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom or 1
Represents a valent substituent. As the monovalent substituent, a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group, trifluoromethyl group, benzyl group, sulfopropyl group, diethylaminoethyl group, Cyanopropyl group, adamantyl group, p
-Chlorophenethyl group, ethoxyethyl group, ethylthioethyl group, phenoxyethyl group, carbamoylethyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminoethyl group, etc., substituted or unsubstituted alkenyl group (for example, allyl group) , Styryl group, etc.), substituted or unsubstituted aryl groups (for example, phenyl group, naphthyl group, p-carboxyphenyl group, 3,5-dicarboxyphenyl group, m-sulfophenyl group, p-acetamidophenyl group, 3 -Caprylamidophenyl group, p-sulfamoylfetyl group, m-hydroxyphenyl group,
p-nitrophenyl group, 3,5-dichlorophenyl group,
p-anisyl group, o-anisyl group, p-cyanophenyl group, p-N-methylureidophenyl group, m-fluorophenyl group, p-tolyl group, m-tolyl group, etc.),

A substituted or unsubstituted heterocyclic group (eg, pyridyl group, 5-methyl-2-pyridyl group, thienyl group, etc.), a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), a mercapto group, Cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, nitro group, substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-phenylethoxy group, etc.) A substituted or unsubstituted aryloxy group (eg, phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, α-naphthoxy group, etc.), a substituted or unsubstituted acyl group (eg, acetyl group, benzoyl group, etc.) ), Substituted or unsubstituted acylamino group (eg, acetylamino group, caproylamino group, etc.), substituted or unsubstituted (For example, methanesulfonyl group, benzenesulfonyl group, etc.), sulfonylamino group (for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), substituted or unsubstituted amino group (for example, diethylamino group, hydroxyamino group) ), An alkylthio group or an arylthio group (eg, a methylthio group, a carboxyethyl group, a sulfobutylthio group, a phenylthio group, etc.), an alkoxycarbonyl group (eg, a methoxycarbonyl group), an aryloxycarbonyl group (eg, a phenoxycarbonyl group, etc.) ) And the like.

Further, on these substituents, an alkyl group, alkenyl group, aryl group, hydroxy group, carboxyl group, sulfo group, nitro group, cyano group, halogen atom, alkoxy group, aryloxy group, alkoxycarbonyl group, An acyl group, an amino group, a sulfonamino group, a carbamoyl group, a sulfamoyl group and the like may be substituted.

R ⁶ and R ⁷ are preferably a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, etc.), or an electron-withdrawing group. Here, the “electron-withdrawing group” refers to a group having a positive Hammett σ value. Where σ
The value is based on the structure-activity relationship social gathering edition, “Chemical Field”, sensitization 122
No. "Drug activity correlation-Guidelines for drug design and mechanism of action research", pp. 96-103, published by Nankodo Co., Ltd., by Corwin Hansch, Albert Leo, "Subtitou" Ant Constants for Correlation Analysis in Chemistry and Biology "(Substitute Constan
ts for Correlation Analysis
is in Chemistry and Biolog
y) pages 69-161, John Wiley &
Published by Jhon Wiley and Sons, Corwin Hansc
h), A. Leo, R.W. Taft, Chemical.
Review (Chemical Reviews) 9
1, pages 165 to 195, and the like. For substituents whose σ _p is unknown, see Chemical Reviews, Vol. 17, No. 1,
25 to 136 (1935).

R ⁹ and R ¹⁰ are preferably a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, etc.), or an aryl group (eg, a phenyl group, etc.).
R ⁸ and R ¹¹ are preferably a hydrogen atom, an alkyl group (eg, a methyl group or an ethyl group), an aryl group (eg, a phenyl group), or an electron-withdrawing group. Two or more of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may combine to form a ring. For example, R ⁸ and R ⁹ , and R ¹⁰ and R ¹¹ may combine with each other to form a ring such as a benzene ring.

-3 Compound represented by Formula (3)

[0088]

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In the general formula (3), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent. As the monovalent substituent, a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group, trifluoromethyl group, benzyl group,
Sulfopropyl group, diethylaminoethyl group, cyanopropyl group, adamantyl group, p-chlorophenethyl group,
Ethoxyethyl, ethylthioethyl, phenoxyethyl, carbamoylethyl, carboxyethyl,
Ethoxycarbonylmethyl group, acetylaminoethyl group, etc., substituted or unsubstituted aryl group (for example, phenyl group, naphthyl group, p-carboxyphenyl group, 3,5-
Dicarboxyphenyl group, m-sulfophenyl group, p-
Acetamidophenyl group, 3-caprylamidophenyl group, p-sulfamoylfetyl group, m-hydroxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-anisyl group, o-anisyl group, p -Cyanophenyl group, p-N-methylureidophenyl group, m
-Fluorophenyl group, p-tolyl group, m-tolyl group, etc.),

A substituted or unsubstituted alkylthio group or a substituted or unsubstituted arylthio group (eg, a methylthio group, an ethylthio group, a sulfobutylthio group, a phenylthio group, etc.), a halogen atom (eg, a chlorine atom, a bromine atom,
Fluorine atom), carbamoyl group, sulfamoyl group,
A substituted or unsubstituted acyl group (eg, acetyl group, benzoyl group, etc.), a substituted or unsubstituted alkoxycarbonyl group (eg, methoxycarbonyl group), a substituted or unsubstituted aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.) ), Carboxyl group, formyl group, substituted amino group, nitrile group and the like. In the general formula (3), R ¹³ and R ¹⁴ may be bonded to each other to form an aromatic ring or a heterocyclic ring.

In the formula (3), Z ³ and Z ⁴ each independently represent a substituent necessary for the compound represented by the formula (3) to be a dye. Examples of the substituent represented by Z ³ and Z ⁴ include a group capable of forming a conjugated chain.

Among the compounds represented by the general formula (3), a compound represented by the following general formula (5) is preferable.

[0093]

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In the general formula (5), L ¹ and L ² each independently represent a methine group which may be substituted. The methine group represented by L ¹ and L ^2, the general formula (4) has the same meaning as methine group represented by L ¹ and L ² of the preferred examples are also the same. In the general formula (5), G ¹ and G ² each independently represent an electron-withdrawing group, or G ¹ and G ²
To form an aromatic or heterocyclic ring. Examples of the electron withdrawing group represented by G ¹ and G ^2, have the same meanings as electron-withdrawing group represented by G ¹ and G ² in the general formula (4), and preferred examples are also the same. When G ¹ and G ² are bonded to form an aromatic ring or a heterocyclic ring, the aromatic ring and the heterocyclic ring include:
The same aromatic rings and heterocyclic rings (heterocyclic nuclei) as those exemplified when the aromatic ring or heterocyclic ring is formed by bonding G ¹ and G ² in the general formula (4) can be mentioned. The general formula (5)
In the formula, m represents an integer of 0 to 3.

The following formulas (1) to (3)
Illustrative compounds 1 to 115 of the compounds represented by
The compounds used in the present invention are not limited to the following exemplified compounds.

[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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In the photopolymerizable compositions of the first to third embodiments, the compounds represented by the general formulas (1) to (3) each correspond to 1 part by mass of a radical generator described later. Is preferably 0.01 to 5% by mass.
More preferably, the content is 5 to 2% by mass.

Organic Boron Compound or Radical Generator Represented by General Formula (A) In the photopolymerizable composition of the first embodiment, the organic boron compound represented by the general formula (A) is present in the vicinity thereof. When the compound represented by the general formula (1) absorbs light, it has a function of interacting with the compound, generating radicals and the like with high efficiency, and initiating the polymerization of the polymerizable compound present in the vicinity. Have.

General formula (A)

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In the general formula (A), R_a ¹, R_a ^Two, R_a ^ThreeIs
Each independently represents an aliphatic group, an aromatic group, a heterocyclic group, or -S
iR_a ^FiveR_a ⁶R_a ⁷Represents Also, R_a ^FourRepresents an aliphatic group
You. R _a ¹~ R_a ^ThreeAnd R_a ^FourWhen represents an aliphatic group,
Examples of the aliphatic group include an alkyl group and a substituted alkyl
Group, alkenyl group, substituted alkenyl group, alkynyl group,
Substituted alkynyl group, aralkyl group, or substituted aralkyl
Groups, among which alkyl groups, substituted alkyl
Group, alkenyl group, substituted alkenyl group, aralkyl group,
Or a substituted aralkyl group,
Alkyl groups are particularly preferred. Further, the aliphatic group is cyclic.
It may be an aliphatic group or a chain aliphatic group. Chain aliphatic groups are
It may have a fork.

Examples of the alkyl group include linear, branched and cyclic alkyl groups. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkyl portion of the substituted alkyl group is the same as in the case of the alkyl group. The alkyl group may be a substituted alkyl group or an unsubstituted alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, neopentyl, isopropyl, isobutyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, A dodecyl group, an octadecyl group and the like.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, , A methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group), an alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylaminosulfonyl group having 30 or less carbon atoms, An alkoxy group having 30 or less carbon atoms (eg, a methoxy group, an ethoxy group, a benzyloxy group, a phenethyloxy group, etc.) and an alkylthio group having 30 or less carbon atoms (eg,
A methylthio group, an ethylthio group, a methylthioethylthioethyl group, etc., an aryloxy group having 30 or less carbon atoms (eg, a phenoxy group, a p-tolyloxy group, a 1-naphthoxy group, a 2-naphthoxy group, etc.), a nitro group, a carbon number An alkyl group having 30 or less, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acyloxy group having 30 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (eg, acetyl group, Propionyl group, benzoyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfur) Famoyl group, morpholinosulfonyl , Or a piperidinosulfonyl group), aryl group having 30 or less carbon atoms (e.g., phenyl group, 4-
A chlorophenyl group, a 4-methylphenyl group, an α-naphthyl group, etc.), a substituted amino group (eg, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acylamino group, etc.), a substituted ureido group, Examples include a substituted phosphono group and a heterocyclic group. Here, the carboxyl group, sulfo group, hydroxy group, and phosphono group may be in a salt state. At that time, examples of the cation forming a salt include Y ⁺ described below.

Examples of the alkenyl group include linear, branched and cyclic alkenyl groups. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkenyl portion of the substituted alkenyl group is the same as in the case of the alkenyl group. The alkenyl group may be a substituted alkenyl group or an unsubstituted alkenyl group. Examples of the substituent of the substituted alkenyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the alkynyl group include linear, branched and cyclic alkynyl groups. The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkynyl portion of the substituted alkynyl group is the same as in the case of the alkynyl group. Further, the alkynyl group may be either an alkynyl group having a substituent or an unsubstituted alkynyl group. Examples of the substituent of the substituted alkynyl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

Examples of the aralkyl group include linear, branched and cyclic aralkyl groups, and the aralkyl group preferably has 7 to 35 carbon atoms, more preferably 7 to 25 carbon atoms. The preferred range of the number of carbon atoms in the aralkyl portion of the substituted aralkyl group is the same as in the case of the aralkyl group. Further, the aralkyl group may be either an aralkyl group having a substituent or an unsubstituted aralkyl group. Examples of the substituent of the substituted aralkyl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

[0121] If the R _a ¹ ~R _a ³ represents an aromatic group an alkyl group, as the aromatic group, for example, an aryl group, and a substituted aryl group. The number of carbon atoms in the aryl group is preferably from 6 to 30, and more preferably from 6 to 20. The preferred range of the number of carbon atoms in the aryl portion of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, and a β-naphthyl group. Examples of the substituent of the substituted aryl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

[0122] If R _a ¹ ~R _a ³ represents a heterocyclic group, the heterocyclic group, a heterocyclic group having a substituent, an unsubstituted heterocyclic group. Examples of the substituent of the heterocyclic group having a substituent group, include the same substituents as substituents exemplified in the case where R _a ¹ ~R _a ³ represents an aryl group having a substituent. Among them, as the heterocyclic group represented by R _a ¹ ~R _a ^3, a furan ring,
A heterocyclic group containing a nitrogen atom, a sulfur atom, or an oxygen atom such as a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyridine ring is preferable.

[0123] If R _a ¹ ~R _a ³ represents ^{_{-SiR a 5 R a 6 R a}} 7, R a 5, R a 6 and R _a ⁷ are each independently an aliphatic group,
Represents an aromatic group. The aliphatic group, aromatic group, R _a ¹ ~R _a ³
And aliphatic groups R _a ⁴ is represented, are each synonymous with the aromatic group represented by R _a ¹ ~R _a ^3, and preferred examples are also the same.

[0124] In the general formula ^{_{(A), R a 1,}} R a 2, R a 3,
And 2 or more of R _a ⁴ is connected directly or via a substituent, may form a ring. When forming a ring,
As the ring, any ring selected from the following rings (C1) to (C3) is preferable, and among them, the ring (C2) is preferable.

[0125]

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In the ring (1), R _b represents the following divalent group.

[0127]

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In the general formula (A), _Ra ^{1 to} _Ra ³ are preferably an aryl group, and _Ra ⁴ is an alkyl group, from the viewpoints of high sensitivity and improved storage stability. In particular, a triarylalkyl-type organoboron compound in which an aryl group is substituted with an electron-withdrawing group is preferable. In particular, the sum of Hammet (σ) values of the substituents (electron-withdrawing groups) on three aryl groups is +0. Those having 36 to +2.58 are more preferable. As the electron-withdrawing group, a halogen atom and a trifluoromethyl group are preferable, and a fluorine atom and a chlorine atom are more preferable.

The aryl group substituted by the electron-withdrawing group includes a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-fluorophenyl group, a 3-chlorophenyl group,
4-chlorophenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-difluorophenyl group, 4-bromophenyl group, 3,4-
Examples include a difluorophenyl group, a 5-fluoro-2-methylphenyl group, a 5-fluoro-4-methylphenyl group, a 5-chloro-2-methylphenyl group, and a 5-chloro-4-methylphenyl group.

Specific examples of the anion moiety of the general formula (A) include, for example, tetramethyl borate, tetraethyl borate, tetrabutyl borate, triisobutyl methyl borate, di-n-butyl-di-t-butyl borate, -N-butyl borate, tri-m-chlorophenyl-n-hexyl borate, triphenylmethyl borate, triphenylethyl borate, triphenylpropyl borate, triphenyl-n-butyl borate,
Trimesityl butyl borate, tolyl isopropyl borate, triphenylbenzyl borate, m-fluoro-tetrabenzyl borate, triphenylphenethyl borate, triphenyl-p-chlorobenzyl borate, triphenylethenyl butyl borate, di (α-naphthyl) -Dipropyl borate, tri-n-butyl (dimethylphenylsilyl) borate, diphenyl dihexyl borate, tri-m-fluorophenylhexyl borate, tri- (5-chloro-4-methylphenyl) hexyl borate, tri-m-fluoro Phenylcyclohexyl borate, tri-m-fluorophenylbenzyl borate, tri- (5-fluoro-2-methylphenyl)
Hexyl borate and the like can be mentioned.

In the general formula (A), Y ⁺ represents a group capable of forming a cation. Among them, an organic cationic compound, a transition metal coordination complex cation (such as the compound described in Japanese Patent No. 2991143), or a metal cation (for example, Na ⁺ ,
K ⁺ , Li ⁺ , Ag ⁺ , Fe ²⁺ , Fe ³⁺ , Cu ⁺ , Cu ²⁺ ,
Zn ²⁺ , Al ³⁺ , 1 / 2Ca ²⁺ ) are preferable. Examples of the organic cationic compound include a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, an iodonium cation, a sulfonium cation, and a dye cation.

The quaternary ammonium cations include
Examples include tetraalkylammonium cations (eg, tetramethylammonium cation, tetrabutylammonium cation), tetraarylammonium cations (eg, tetraphenylammonium cation), and the like. As the quaternary pyridinium cation,
N-alkylpyridinium cations (eg, N-methylpyridinium cations), N-arylpyridinium cations (eg, N-phenylpyridinium cations), N-alkoxypyridinium cations (eg,
4-phenyl-N-methoxy-pyridinium cation), N-benzoylpyridinium cation and the like. Examples of the quaternary quinolinium cation include an N-alkyl quinolinium cation (for example, N-methyl quinolinium cation) and an N-aryl quinolinium cation (for example, N-phenyl quinolinium cation). Can be Examples of the phosphonium cation include a tetraarylphosphonium cation (eg, a tetraphenylphosphonium cation). Examples of the iodonium cation include a diaryliodonium cation (for example, a diphenyliodonium cation). Examples of the sulfonium cation include a triarylsulfonium cation (for example, a triphenylsulfonium cation).

Further, as a specific example of Y ⁺ , paragraphs [0020] to [00] of JP-A-9-188686.
38].

In each of the cationic compounds (exemplary compounds) exemplified above, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group,
An ethyl group, a propyl group, an isopropyl group, a butyl group, or an unsubstituted alkyl group such as hexyl group, the substituted alkyl group represented by R _a ¹ ~R _a ⁴ are preferred. Among them, particularly, having 1 to 1 carbon atoms
Twelve alkyl groups are preferred. In each of the cationic compounds exemplified above, the aryl group is
For example, a phenyl group, a phenyl group substituted with a halogen atom (eg, a chlorine atom), a phenyl group substituted with an alkyl (eg, a methyl group), and a phenyl group substituted with an alkoxy (eg, a methoxy group) are preferable.

Specific examples of the organoboron compound represented by the general formula (A) include US Pat. No. 3,567,453.
No. 4,343,891, JP-A-62
JP-A-143044, JP-A-62-150242, JP-A-9-188684, JP-A-9-188
No. 685, JP-A-9-188686, JP-A-9-188710, JP-B8-9643,
The compounds described in JP-A-11-269210 and the compounds (b-1 to 33) exemplified below are exemplified. The organic boron compound may be used in combination with a radical generator described below. However, the organic boron compound used in the present invention is not limited to this.

[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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In the photopolymerizable composition according to the first embodiment, the amount of the organic boron compound represented by the general formula (A) is 0.1 to 10% based on the content of the polymerizable compound having an ethylenically unsaturated bond. 0.1-20 mass% is preferable, and 0.1-1
0 mass% is more preferable. However, the preferred range varies depending on the type of the “polymerizable compound having an ethylenically unsaturated bond” used in combination, and is not limited thereto.

The photopolymerizable compositions of the second and third embodiments are compounds (radicals) capable of generating radicals by interacting with the compounds represented by the general formulas (2) and (3), respectively. Generator). When the compound represented by the general formula (2) or the general formula (3) present in the vicinity absorbs light, the radical generator interacts with the compound, generates a radical, and generates a radical in the vicinity. It has a function of initiating a polymerization reaction of the existing polymerizable compound. In the photopolymerizable composition of the second and third aspects,
It is preferable that the radical generator is an organic boron compound represented by the general formula (A), since radicals can be generated with high efficiency and sensitivity is further improved. In the photopolymerizable compositions of the second and third embodiments, as the radical generator,
When the organic boron compound represented by the general formula (A) is used, the preferable range of the content is the same as that of the first embodiment.

Examples of the radical generator include benzophenone, camphorquinone, 4,4-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, and 4-dimethylaminobenzophenone. , 4-dimethylaminoacetophenone, benzylanthraquinone, 2
Bisacyl such as -tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Phosphine oxides, Lucirin TP
Aromatic ketones such as acylphosphine oxides such as O, α-hydroxy or α-aminoacetophenones, α-hydroxycycloalkylphenyl ketones, and dialkoxyacetophenones;

Benzoin and benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin phenyl ether; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) ) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenylimidazole dimer, 2-
2,4,6-triarylimidazole dimers such as (p-methoxyphenyl) -4,5-diphenylimidazole dimer, and other U.S. Patent Nos. 3,784,557 and 42.
Nos. 52887, 4311783, 4459349
Nos. 4,410,621 and 4,622,286;

Polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone and phenyltrichloromethylketone; JP-A-59-133428, JP-B-57
No.-1819, JP-B-57-6096, U.S. Pat.
A compound described in 615455;

2,4,6-tris (trichloromethyl)
-S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6
-Bis (trichloromethyl) -S-triazine, 2-
JP-A-58-29803 such as (P-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine
S-triazine derivatives having a trihalogen-substituted methyl group described in (1);

Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, di-tert-butyldiperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) ) Hexane, tert-butylperoxybenzoate, a, a'-bis (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 3,3 ', 4,4'-tetra- (tert-butylperoxycarbonyl) ) Japanese Patent Application Laid-Open No.
Organic peroxides described in No. 9-189340;

Azinium salts described in US Pat. No. 4,743,530; organoboron compounds as described above; phenylglyoxalic esters such as phenylglyoxalic acid methyl ester; bis (η ⁵ -2,4-cyclopentadiene- 1
- yl) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanocene such as titanium; eta ⁵ - cyclopentadienyl eta ⁶ - cumenyl -
Iron (1 +)-hexafluorophosphate (1
-) And the like; diaryliodonium salts such as a diphenyliodonium salt; and triarylsulfonium salts such as a triphenylsulfonium salt.

For more detailed examples of the radical generator and examples of other types of radical generators, see paragraph [0067] of JP-A-10-45816.
To [0132].

Further, as the radical generator, a material comprising a combination of two or more compounds can be used. For example, a combination of 2,4,5-triarylimidazole dimer with mercaptobenzoxazole and the like, 4,4 described in U.S. Pat. No. 3,427,161.
Combination of 4'-bis (dimethylamino) benzophenone, benzophenone and benzoin methyl ether, benzoyl-N described in U.S. Pat. No. 4,239,850.
Combination of -methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6- (4'-methoxyphenyl) -triazole, dialkylaminobenzoate and dimethylthioxanthone described in JP-A-57-23602. And three combinations of 4,4'-bis (dimethylamino) benzophenone, benzophenone and a polymethyl halide compound described in JP-A-59-78339.

In the case of a radical generator comprising a combination of two or more, a combination of 4,4'-bis (diethylamino) benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, Alternatively, it is preferable to use a combination of 4,4′-bis (diethylamino) benzophenone and 2,4,5-triarylimidazole dimer.

Of the above radical generators,
An organic boron compound, a diaryliodonium salt, an iron allene complex, an S-triazine derivative having a trihalogen-substituted methyl group, an organic peroxide, Oxides, titanocene, 2,4,5-triarylimidazole dimer, or azinium salt compounds are preferred, and organoboron compounds are particularly preferred. The organoboron compound is
Even when a spectral sensitizing dye is used as the spectral sensitizing compound, it is preferable in that the coexisting spectral sensitizing dye can be satisfactorily decolored when the image is fixed by light irradiation. The organic boron compound may be used in combination with the above-mentioned radical generator.

Examples of the organoboron compound include the compound represented by the above general formula (A) and “Functional dye chemistry”.
(1981, CMC Publishing Co., pp. 393-416) and spectroscopy having a cationic dye described in “Coloring Material” (60 [4] 212-224 (1987)) or the like as a cation moiety in the structure. Sensitizing dye-based organic boron compounds are also included.
Examples of the spectral sensitizing dye-based organic boron compounds include compounds described in JP-A-62-143044, JP-A-1-138204, JP-A-6-505287, JP-A-4-261406 and the like.

As the dye constituting the cation portion of the spectral sensitizing dye-based organic boron compound, a cationic dye having a maximum absorption wavelength in a wavelength region of 300 nm or more, preferably in a wavelength region of 400 to 1100 nm is used. Can be. Among them, cationic methine dye, polymethine dye, triarylmethane dye, indoline dye, azine dye, xanthene dye, cyanine dye, hemicyanine dye, rhodamine dye, azomethine dye, oxazine dye or acridine dye are preferable, and cationic cyanine Dyes, hemicyanine dyes, rhodamine dyes or azomethine dyes are more preferred.

In the photopolymerizable composition of the second embodiment, the content of the radical generator is the same as that of the photopolymerizable composition of the first embodiment, and the preferred range is The value varies depending on the type of the “polymerizable compound having an ethylenically unsaturated bond” used in combination, and is not limited thereto.

Other Components The photopolymerizable composition of the present invention may contain known additives appropriately selected as other components according to the purpose within a range that does not impair the effects. Examples of the other components include, for example, a photopolymerization initiator, an oxygen scavenger, a thermal polymerization inhibitor, an ultraviolet absorber, a fluorescent brightener, a chain transfer agent, an antioxidant, and the like, and precursors thereof. These are 0.01 to 20 based on the total weight of the photopolymerizable composition.
It is preferably added in an amount of 0.2% by mass, more preferably 0.2% to 15% by mass, and particularly preferably 0.5% to 10% by mass.

Specific examples of the additives such as the chain transfer agent and the antioxidant include paragraphs [0135] to [0141] of JP-A-10-45816 and JP-A-9-188686.
Paragraphs [0087] to [0096] of Japanese Patent Application Laid-Open No.
182621, paragraphs [0079] to [011]
8], paragraph [0080] of JP-A-9-95487
To [0089], and JP-A-1-1314.
No. 0, No. 1-1141, No. 1-1143, No. 1
No. -13144, No. 1-107048, No. 1-2290
No. 03, No. 1-298348, No. 10-138338
And compounds described in JP-A-11-269210, JP-A-2-187762, and the like.

The photopolymerizable composition of the present invention may contain a binder. In particular, it is convenient when the photopolymerizable composition is a liquid or a viscous substance. The content of the binder is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and more preferably 1 to 90% by mass, based on the total solid content.
Most preferred is 5 to 85% by weight. The choice of the binder depends on the field of application and the properties required for that field,
For example, this depends on the developing ability in an aqueous or organic solvent system, adhesion to a substrate, and sensitivity to oxygen.

As the binder, about 5000 to 20
Polymers having a molecular weight of 00000, preferably 10,000 to 1,000,000 are desirable. For example, acrylate and methacrylate homo or copolymers (eg, methyl methacrylate / ethyl acrylate / methacrylic acid copolymers, poly (alkyl methacrylate), poly (alkyl acrylate), etc.), cellulose esters or cellulose ethers (eg, cellulose acetate, cellulose acetate) Butyrate, methylcellulose, ethylcellulose, etc.), polyvinyl butyral,
Polyvinyl formal, cyclized rubber, polyether (for example, polyethylene oxide, polypropylene oxide,
Polytetrahydrofuran), polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, polyvinyl chloride, vinyl chloride / vinylidene copolymer, copolymer of vinylidene chloride and acrylonitrile, methyl methacrylate, vinyl acetate, polyvinyl acetate, copoly (ethylene / vinyl acetate), poly Examples include caprolactam, poly (hexamethylene adipamide), polyester (for example, poly (ethylene glycol terephthalate), poly (hexamethylene glycol succinate), etc.), polyamide, and polyurea.

Further, water-soluble polymers such as gelatins, (modified) polyvinyl alcohol, polyvinylpyrrolidone, styrene-maleic acid copolymer hydrolyzate, sodium polystyrene sulfonate and sodium alginate are also included.
Further, latexes such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, and methyl acrylate-butadiene rubber latex may be used.

Unsaturated compounds can also be used as a mixture with non-photopolymerizable film-forming components, for example, physically dried polymers or polymer solutions in organic solvents, such as nitrocellulose or cellulose acetate. Butyrate. But they are chemically
And / or a thermosetting (thermosetting) resin, for example,
Polyisocyanate, polyepoxide, melamine resin,
In addition, it may be a polyimide precursor. The simultaneous use of thermosetting resins is important for use in systems known as hybrid systems which are photopolymerized in a first step and crosslinked by a thermal post-treatment in a second step. Also, a binder having a polymerizable group can be used.

Other examples of additives include those described in
-269210.

The light source that can be used for imagewise exposure can be appropriately selected from known light sources having a light source wavelength in the visible to infrared region, and among them, a light source having a maximum absorption wavelength of 300 to 1000 nm. A light source is preferable, and a (semiconductor) laser light source of blue, green, red, or the like or an LED is more preferable from the viewpoint of simple and compact device and low cost. In order to obtain higher sensitivity, it is preferable to appropriately select a light source having a wavelength suitable for the absorption wavelength of a light absorbing material such as a spectral sensitizing dye. On the other hand, as the light source that can be used for decoloring the photopolymerizable composition and the recording material described below, it is more preferable to appropriately select a light source having a wavelength suitable for the absorption wavelength of the photopolymerizable composition. . Specifically, mercury lamps, ultra-high pressure mercury lamps, electrodeless discharge mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, (semiconductors)
A wide range of light sources, such as a laser light source, an LED, and a fluorescent lamp, are preferably mentioned.

As described above, by using the compounds represented by the general formulas (1) to (3) (including the general formulas (1a) and (1b)) as the spectral sensitizing dye, if only ultraviolet light is used, In addition, even when visible light to infrared light is used, an image can be formed with high sensitivity, and since the compound itself has excellent decoloring properties, an image without residual color due to a dye component can be obtained.

<Recording Material> The recording material of the present invention comprises a recording layer on a support, and the recording layer comprises a color-forming component A
And at least a color-forming component B having a site to be colored by reacting with the color-forming component A, and the above-described photopolymerizable composition of the present invention. It may have another layer such as a layer, a light absorbing layer, a protective layer, and a back coat layer.

The basic constitution of the recording material of the present invention is not particularly limited, and the recording material can be appropriately constituted according to the purpose. As a basic embodiment, for example, image formation in the case where the recording material of the present invention is applied to a positive-type photosensitive and heat-sensitive recording material in which a color-forming component A is encapsulated in a thermoresponsive microcapsule is shown as an example. That is, in the positive-type photosensitive and heat-sensitive recording material of the present embodiment, when light is irradiated imagewise, radicals are generated from a radical generator contained in the photopolymerizable composition in the light-irradiated portion, and polymerization of the polymerizable compound is performed. The reaction is initiated and cured, fixing the photopolymerizable composition in place and forming a latent image. The microcapsules are impermeable to substances at normal temperature, and do not come into contact with the color-forming component A contained in the microcapsules and the color-forming component B having a site in the molecule that reacts with the color-forming component A to form a color. It is in a colored state.

Thereafter, when heat is applied to the entire surface of the light- and heat-sensitive recording material, the microcapsules shift to a material-permeable state, and the color-forming component B in the non-light-irradiated portion penetrates into the microcapsules (and / or the color-forming component). A is released outside the microcapsule), and the color forming components A and B react with each other to form a color only in the non-light-irradiated portion. On the other hand, in the light irradiating section, the photopolymerizable composition is in a cured and fixed state by a polymerization reaction, so that the coloring components A and B are both immobilized and cannot contact,
No color develops in the light-irradiated part. Thereafter, by exposing the photosensitive and heat-sensitive recording material over the entire surface, the unpolymerized region is also polymerized (fixed), and the dye component contained in the photopolymerizable composition can be decolorized.

The recording material of the present invention may be a recording material of the following embodiments (first and second embodiments).
The image forming method can be appropriately selected according to each mode. That is, the recording material of the first embodiment is an embodiment in which at least one of the polymerizable compounds contained in the photopolymerizable composition is the color forming component B itself, and the recording layer is formed of the color forming component A.
And at least a photopolymerizable composition of the present invention containing a coloring component B for coloring the coloring component A. Here, when the positive-type photosensitive and heat-sensitive recording material of the above-described basic mode is applied to the example, as described above, the color forming component B has a site for forming the color forming component A and also has an ethylenically unsaturated bond. When light is irradiated imagewise, the color-forming component B starts a polymerization reaction and cures, and the color-forming component B is fixed in place to form a latent image. Therefore, in the light irradiation part, the coloring component B is immobilized and cannot contact with the coloring component A, and the light irradiation part does not develop color.

The recording material according to the second aspect of the present invention is characterized in that the recording layer comprises a coloring component A, a coloring component B which reacts with the coloring component A to form a color, and the photopolymerizable composition of the present invention. And the polymerizable compound having an ethylenically unsaturated bond (polymerizable compound) contained in the photopolymerizable composition contains the color-forming component A and the color-forming component B in the same molecule.
This is an embodiment in which the compound is a color-suppressing compound having a site that inhibits a reaction with a compound (reaction inhibiting site).

The image formation in the case where the recording material of the second embodiment is applied to a negative-type photosensitive and heat-sensitive recording material in which the color-forming component A is encapsulated in heat-responsive microcapsules will be described below as an example. In the negative-type photosensitive and heat-sensitive recording material of this embodiment, as in the first embodiment, the microcapsules are impermeable to substances at room temperature, do not come into contact with the color forming components A and B, and are in a non-colored state. . When the light and heat sensitive recording material is irradiated with light in an image-like manner, a polymerization reaction of the polymerizable compound in the light irradiated portion starts and cures, and the polymerizable compound is fixed in place and a latent image is formed. . Thereafter, when heat is applied to the entire surface of the light- and heat-sensitive recording material, the microcapsules are transferred to a material-permeable state, and the coloring component B penetrates into the microcapsules (and / or the coloring component A is released outside the microcapsules). However, at the same time, in the non-light-irradiated portion, the polymerizable compound also permeates into the microcapsules as a color-suppressing compound, and the color-forming reaction between the color-forming components A and B is suppressed. Therefore, the non-light irradiation part is maintained in a non-colored state. On the other hand, a polymerizable compound (a color-suppressing compound) in the light irradiation part
Is fixed in place by the polymerization reaction, so that the color development reaction proceeds irrespective of the reaction between the color forming components A and B, and the color is formed only in the light irradiation part. Thereafter, the dye contained in the photopolymerizable composition can be decolorized by exposing the entire photosensitive and heat-sensitive recording material to light.

As the light source used for image formation using the recording material of the present invention, the same light sources as those usable for exposure of the photopolymerizable composition of the present invention can be used. Hereinafter, constituent components used in the recording material of the present invention will be described.

(Photopolymerizable composition) The photopolymerizable composition includes 1) a polymerizable compound having an ethylenically unsaturated bond (polymerizable compound), and 2) a decolorizable organic dye (spectral sensitization). Dye), 3) a radical generator capable of generating a radical by interacting with the dye, and, if necessary, 4) other components may be contained. Uses the above-described photopolymerizable composition of the present invention. That is, each of the recording materials of the present invention of the first and second aspects is constituted by using the photopolymerizable composition of the first aspect or the second aspect described above. When the photopolymerizable composition is irradiated with light, the spectral sensitizing dye absorbs light and interacts with the radical generator, and the radical generator generates a radical. The radicals cause the polymerizable compound to undergo radical polymerization and cure to form an image.

For details of the polymerizable compound,
As described above, a plurality of types can be contained in the photopolymerizable composition. Like the recording material of the first aspect,
At least one of them may be a coloring component B having a site for coloring the coloring component A, and a coloring component having an ethylenically unsaturated bond (polymerizable group) in the same molecule is used as described later. On the other hand, as in the recording material of the second embodiment, the polymerizable compound may also serve as a color-suppressing compound, and the color-forming component A and the color-forming component A are contained in the same molecule. A polymerizable compound having a site that suppresses the reaction with the coloring component B to be colored is used. These polymerizable compounds will be described later together with the coloring components (A and B) contained in the recording layer.

The content of the photopolymerizable composition in the recording layer is preferably from 0.1 to 50 g / m ² ,
-30 g / m < ² > is more preferable.

(Coloring Component) In the recording material of the present invention, the recording layer contains the coloring component A and the coloring component B as a coloring source together with the photopolymerizable composition. In the case of the recording material of the first embodiment, the coloring component A is contained together with the photopolymerizable composition, and the coloring component B contained as a polymerizable compound on the photopolymerizable composition side is the same as the coloring component A. Reacts and develops color. Coloring component A as a color source constituting image part
And the color-forming component B are as follows:
(T) combinations. In addition, the following combination
The coloring component A and the coloring component B are shown in this order.

(A) Combination of an electron donating dye precursor and an electron accepting compound. (A) A combination of a diazo compound and a coupling component (hereinafter, appropriately referred to as a “coupler compound”). (C) A combination of a metal salt of an organic acid such as silver behenate and silver stearate with a reducing agent such as protocatechinic acid, spiroindane and hydroquinone. (D) A combination of iron salts of long-chain fatty acids such as ferric stearate and ferric myristate and phenols such as tannic acid, gallic acid and ammonium salicylate. (E) Organic acid heavy metal salts such as nickel, cobalt, lead, copper, iron, mercury, and silver salts such as acetic acid, stearic acid, and palmitic acid; and alkali metals or alkaline earths such as calcium sulfide, strontium sulfide, and potassium sulfide. A combination with a metal-like sulfide or a combination of the organic acid heavy metal salt with an organic chelating agent such as s-diphenylcarbazide and diphenylcarbazone.

(F) heavy metal sulfates such as sulfates such as silver, lead, mercury, and sodium, and sodium tetrathionate;
Combination with sulfur compounds such as sodium thiosulfate and thiourea. (G) an aliphatic ferric salt such as ferric stearate;
Combination with an aromatic polyhydroxy compound such as 4-hydroxytetraphenylmethane. (H) organic acid metal salts such as silver oxalate and mercury oxalate;
Combination with organic polyhydroxy compounds such as polyhydroxy alcohol, glycerin and glycol. (K) A combination of a ferric fatty acid salt such as ferric pelargonate or ferric laurate with a thiocetyl carbamide or isothiocesyl carbamide derivative. (Co) A combination of a lead salt of an organic acid such as lead caproate, lead pelargonate or lead behenate with a thiourea derivative such as ethylenethiourea or N-dodecylthiourea.

(Sa) Combination of higher aliphatic heavy metal salts such as ferric stearate and copper stearate with zinc dialkyldithiocarbamate. (B) Those which form an oxazine dye such as a combination of resorcinol and a nitroso compound. (S) A combination of a formazan compound and a reducing agent and / or a metal salt. (C) A combination of a protected dye (or leuco dye) precursor and a deprotecting agent. (So) A combination of an oxidizing color former and an oxidizing agent. (T) Combination of phthalonitriles and diiminoisoindolines. (A combination in which a phthalocyanine is formed.) (H) A combination of an isocyanate and a diiminoisoindoline (a combination in which a colored pigment is formed). (T) Combination of pigment precursor and acid or base (combination formed by pigment). (T) Combination of an oxidized precursor of a paraphenylenediamine derivative or a paraaminophenol derivative with a coupling component (coupler compound).

Examples of the combination of the two components as the color-forming source include (a) a combination of an electron-donating dye precursor and an electron-accepting compound, and (a) a diazo compound and a coupling component (hereinafter, appropriately referred to as a “coupler compound”). ).
(C) Combination of a protected dye (or leuco dye) precursor and a deprotecting agent, and (T) Combination of an oxidized precursor of a paraphenylenediamine derivative or a paraaminophenol derivative with a coupling component (coupler compound) Is preferred. That is, the color-forming component A is preferably an electron-donating dye precursor, a diazo compound, a dye precursor or an oxidant precursor, and the color-forming component B is preferably an electron-accepting compound, a coupler compound or a deprotecting agent.

When an electron-donating colorless dye precursor is used as the color-forming component A, the electron-donating colorless dye precursor includes:
Known phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, known in heat-sensitive papers and pressure-sensitive papers, Various compounds such as spiropyran compounds, pyridine compounds, pyrazine compounds, and fluorene compounds can be given.

Examples of the phthalide compound include, for example, US Pat. No. Re. 23,024 and US Pat. No. 3,491,
No. 111, No. 3,491,112, No. 3,49
1,116 and 3,509,174, specifically, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3,3-bis (p-diethylaminophenyl) phthalide, 3,3-bis (2-methyl-1-octylindol-3-yl) phthalide, 3- (4-dipropylamino-2-acetylaminophenyl)- 3- (2-methyl-
1-octylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindole-3
-Yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-
Diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,3-bis (4-diethylamino-2-butyloxyphenyl) -4-azaphthalide, 3- (4-diethylamino-2-butyloxyphenyl) -3- (2
-Methyl-1-pentylindol-3-yl) -4-
Azaphthalide and the like.

Examples of the fluoran compounds include, for example, US Pat. Nos. 3,624,107 and 3,627,78.
No. 7, No. 3,641,011, No. 3,462,8
No. 28, No. 3,681, 390, No. 3,920,
No. 510 and 3959, 571, specifically, 2-anilino-3-methyl-6
Diethylaminofluoran, 2-anilino-3-methyl-6-dibutylaminofluoran, 2-anilino-3-
Methyl-6-N-ethyl-N-isoamylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N
-Cyclohexylaminofluoran, 2-anilino-3
-Methyl-6-N-ethyl-N-isobutylaminofluoran, 2-anilino-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-
Tetrahydrofurfurylaminofluoran and the like.

Examples of the thiazine-based compound include benzoyl leucon methylene blue and p-nitrobenzyl leucomethylene blue. Examples of leuco auramine compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like. . Examples of rhodamine lactam compounds include rhodamine-B-anilinolactam and rhodamine- (p-nitrino) lactam.

Examples of spiropyran compounds include, for example,
The compounds described in U.S. Pat. No. 3,971,808 are specifically mentioned, and specifically, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3- Benzylspiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like can be mentioned.

Examples of the pyridine and pyrazine compounds include the compounds described in US Pat. Nos. 3,775,424, 3,853,869 and 4,246,318. Examples of the fluorene-based compound include compounds described in Japanese Patent Application No. 61-240989.

As the dye precursors for producing cyan, magenta and yellow, the respective dye precursors described in US Pat. No. 4,800,149 can be used. Further, as an electron donating dye precursor for a yellow coloring dye, US Pat. Nos. 4,800,148 and 51,623.
No. 3, JP-B-7-88105 and the like. Dye precursors described in JP-A-63-53542 can be used as electron-donating dye precursors for cyan coloring dyes. Can also be used.

When the above-mentioned electron-donating dye precursor is used,
An electron-accepting compound is used as a coloring component B for coloring the electron-donating dye precursor. Examples of the electron-accepting compound include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolak resins, metal-treated novolak resins, and metal phenol derivatives, salicylic acid derivatives, and the like, which are known from thermal paper and pressure-sensitive paper (registered trademark). Electron accepting compounds such as complexes; More specifically, Japanese Patent Publication No. 40-9309, Japanese Patent Publication No. 45-14039, and Japanese Patent Laid-Open No. 52-140483
JP-A-48-51510, JP-A-57-2108
No. 86, JP-A-58-87089, JP-A-59-11
No. 286, Japanese Unexamined Patent Publication No.
95988 and the like.

Among the above, for example, phenol derivatives include 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, and 4-hydroxyphenyl-4 '
-Isopropyloxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, α, α'-
Bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, benzyl p-hydroxybenzoate and the like can be mentioned.

Examples of the salicylic acid derivatives include 4-pentadecylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (tert-octyl) salicylic acid, 5-octadecylsalicylic acid, and 5-α- (p -Α-
Methylbenzylphenyl) ethylsalicylic acid, 3-α-
Methylbenzyl-5-tert-octylsalicylic acid,
5-tetradecylsalicylic acid, 4-hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid, 4-pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid and the like, and zinc and aluminum thereof , Calcium, copper salts and the like.

In the recording material of the first embodiment, the color-forming component B also functions as a polymerizable compound having an ethylenically unsaturated bond. Therefore, at least one of the polymerizable compounds of the recording material of the first embodiment is an electron-accepting compound, and in the molecule, an electron-accepting group and an ethylenically unsaturated bond (hereinafter, referred to as “polymerizable group”) .). As the coloring component B in this case, for example,
3-halo-4-hydroxybenzoic acid described in JP-A-226455, methacryloxyethyl ester, acryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682, and 59-83693.
Nos. 60-141587 and 62-99190, esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene, hydroxystyrenes described in EP 29323, JP-A-62-167077,
Compounds which can be synthesized with reference to the N-vinylimidazole complex of zinc halide described in JP-A-62-16708 and the electron-accepting compound described in JP-A-63-317558.

Of these compounds having an electron-accepting group and a polymerizable group in the same molecule, the compounds represented by the following general formula:
-Halo-4-hydroxybenzoic acid is preferred.

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In the above formula, X represents a halogen atom, and among them, a chlorine atom is preferable. Y represents a monovalent group having a polymerizable ethylene group, and among them, an aralkyl group having a vinyl group, an acryloyloxyalkyl group or a methacryloyloxyalkyl group is preferable, and an acryloyloxyalkyl group having 5 to 11 carbon atoms or 6 to 6 carbon atoms is preferable. Twelve methacryloyloxyalkyl groups are more preferred. Z represents a hydrogen atom, an alkyl group or an alkoxy group.

Examples of the 3-halo-4-hydroxybenzoic acid include 3-chloro-4-hydroxybenzoic acid ester vinylphenethyl ester and 3-chloro-4-acid
Hydroxybenzoic acid vinylphenylpropyl ester,
3-chloro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2 −
Acryloyloxypropyl) ester, 3-chloro-
4-hydroxybenzoic acid- (2-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (3-acryloyloxypropyl) ester,
3-chloro-4-hydroxybenzoic acid- (3-methacryloyloxypropyl) ester,

3-chloro-4-hydroxybenzoic acid
(4-acryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (4-methacryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester,
3-chloro-4-hydroxybenzoic acid- (5-acryloyloxypentyl) ester, 3-chloro-4-hydroxybenzoic acid- (5-methacryloyloxypentyl) ester, 3-chloro-4-hydroxybenzoic acid-
(6-acryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (6-methacryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (8-acryloyloxyoctyl) ester, 3-chloro 4-hydroxybenzoic acid- (8-methacryloyloxyoctyl) ester and the like.

Further, for example, styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, β-
Zinc methacryloxyethoxysalicylate, zinc β-acryloxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β-methacryloxyethylorselinate,
β-acryloxyethylorselinate, β-methacryloxyethoxyphenol, β-acryloxyethoxyphenol,

Β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate, hydroxystyrenesulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p -Hydroxybenzoate, methacryloxymethylphenol, acryloxymethylphenol, methacrylamidopropanesulfonic acid, acrylamidopropanesulfonic acid, β-
Methacryloxyethoxy-dihydroxybenzene, β-
Acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β-methacryloxypropanecarboxylic acid,

Γ-acryloxypropyl-α-hydroxyethyloxysalicylic acid, β-hydroxyethynylphenol, β-methacryloxyethyl-p-hydroxycinnamate, β-acryloxyethyl-p-hydroxycinnamate, 3,5 Distyrenesulfonic acid amide phenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid, acrylic acid,
Methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid,

3-β-hydroxyethoxyphenol,
β-methacryloxyethyl-p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate, β′-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid, β-acryloxyethyloxy Carbonylhydroxybenzoic acid, N, N′-di-β-methacryloxyethylaminosalicylic acid, N, N′-di-β-acryloxyethylaminosalicylic acid, N, N′-di-β-
Methacryloxyethylaminosulfonylsalicylic acid,
N, N′-di-β-acryloxyethylaminosulfonylsalicylic acid and metal salts thereof (eg, zinc salt) can also be suitably mentioned.

In the case where an electron-donating dye precursor is used as the color-forming component A and an electron-accepting compound is used as the color-forming component B, the content of the electron-donating dye precursor in the recording layer is preferably from 0.05 to 0.05%. 5 g / m ² is preferred,
1-3 g / m < ² > is more preferable. The amount of the electron accepting compound used is preferably 0.5 to 20 parts by mass, and more preferably 3 to 20 parts by mass, based on 1 part by mass of the electron donating colorless dye used.
-10 parts by mass is more preferred. If the amount is less than 0.5 part by mass, it may not be possible to obtain a sufficient color density, and if it exceeds 20 parts by mass, the sensitivity may be lowered or the suitability for coating may be deteriorated.

On the other hand, when a diazo compound is used as the coloring component A, it is preferable to use a compound represented by the following formula. Ar—N ₂ ⁺ · Y ⁻ [wherein, Ar represents an aromatic ring group, and Y ⁻ represents an acid anion. ]

In the above formula, Ar represents a substituted or unsubstituted aryl group. As the substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxamide group, a sulfonyl group, a sulfamoyl group, a sulfonamide group, a ureido group, Examples thereof include a halogen group, an amino group, and a heterocyclic group, and these substituents may be further substituted.

The aryl group has 6 carbon atoms.
~ 30 aryl groups are preferable, for example, a phenyl group,
2-methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2
-Ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group,
2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2 -Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group,
3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group,

3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, -Benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2
-Ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5 −
Butoxyphenyl group, 4- (N-benzyl-N-methylamino) -2-dodecyloxycarbonylphenyl group,
And the like.

These groups further include an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group,
It may be substituted by a substituted amino group, a halogen atom, a heterocyclic group or the like.

As the diazo compound which can be suitably used as the color forming component A, for example, the diazo compounds exemplified in paragraphs 44 to 49 of JP-A-7-276808 can be mentioned. However, the present invention is not limited to these compounds.

The maximum absorption wavelength λ _max of the diazo compound is preferably 450 nm or less from the viewpoint of the effect, and more preferably 290 to 440 nm. Further, the diazo compound has 12 or more carbon atoms,
It is desirable that the solubility in water is 1% or less and the solubility in ethyl acetate is 5% or more. The diazo compound as the coloring component A may be used alone or in combination of two or more depending on various purposes such as hue adjustment.

When the diazo compound is used, a coupler compound (having no polymerizable group) may be used as the coloring component B.
Alternatively, a coupler compound having a polymerizable group is used. The two coupler compounds couple with a diazo compound in a basic atmosphere and / or a neutral atmosphere to form a dye, and a plurality of types can be used in combination according to various purposes such as hue adjustment. . Specific examples of the coupler compound having a polymerizable group include a so-called active methylene compound having a methylene group next to a carbonyl group, a phenol derivative, a naphthol derivative, an azole derivative, and a heterocyclic fused azole derivative. These are appropriately selected and used within a range that meets the purpose of the present invention.

Examples of the coupler skeleton compound (coupler) in the coupler compound having a polymerizable group include a so-called active methylene compound having a methylene group next to a carbonyl group, a phenol derivative, a naphthol derivative, an azole derivative, a hetero-fused azole derivative and the like. It is preferable to use a coupler of Specifically, resorcin, phloroglucin, 2,3-dihydroxynaphthalene, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1
-Hydroxy-2-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthalenesulfonic acid sodium salt, 2-hydroxy-3-naphthalenesulfonic acid anilide, 2-hydroxy-3-naphthalenesulfonic acid morpholinopropylamide, 2-hydroxy- 3-naphthalenesulfonic acid-2-ethylhexyloxypropylamide, 2-hydroxy-3-naphthalenesulfonic acid-2-
Ethylhexylamide, 5-acetamido-1-naphthol,

Sodium 1-hydroxy-8-acetamidonaphthalene-3,6-disulfonate, 1-hydroxy-8-acetamidonaphthalene-3,6-disulfonic acid dianilide, 1,5-dihydroxynaphthalene, 2-
Hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid octylamide,
2-hydroxy-3-naphthoic acid anilide, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclopentanedione, 5- (2-n-tetradecyloxyphenyl) -1,3-cyclohexanedione , 5-phenyl-4-methoxycarbonyl-1,3-cyclohexanedione, 5- (2,5-di-n-octyloxyphenyl) -1,3-cyclohexanedione, N, N'-dicyclohexylbarbituric acid, N, N′-di-n-dodecyl barbituric acid,

Nn-octyl-N'-n-octadecyl barbituric acid, N-phenyl-N '-(2,5-di-n-octyloxyphenyl) barbituric acid, N,
N'-bis (octadecyloxycarbonylmethyl) barbituric acid, 1-phenyl-3-methyl-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-
Anilino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-benzamido-5-pyrazolone,
6-hydroxy-4-methyl-3-cyano-1- (2-
Ethylhexyl) -2-pyridone, 2,4-bis- (benzoylacetamide) toluene, 1,3-bis- (pivaloylacetoamidomethyl) benzene, benzoylacetonitrile, thenoylacetonitrile, acetoacetanilide, benzoylacetanilide, pivaloyl Acetanilide, 2-chloro-5- (Nn-butylsulfamoyl) -1-pivaloylacetamidebenzene, 1
-(2-ethylhexyloxypropyl) -3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (dodecyloxypropyl) -3
-Acetyl-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (4-n-octyloxyphenyl) -3-tert-butyl-5-aminopyrazole and the like.

The details of the coupler compound are described in JP-A No. 4-20 / 1990.
No. 1483, Japanese Unexamined Patent Publication No. 7-223267, Japanese Unexamined Patent Publication No. 7-2
23368, JP-A-7-323660, JP-A5-
278608, JP-A-5-297024, JP-A-6-297
-18669, JP-A-6-18670, JP-A-7-
No. 316280, JP-A-9-216468, JP-A-9-216468
JP-216469, JP-A-9-319025, JP-A-10-03513, JP-A-10-193801,
Reference can also be made to those described in JP-A-10-264532.

The coupler compound forms a dye by coupling with a diazo compound in a basic atmosphere and / or a neutral atmosphere, and may be used for various purposes such as hue adjustment.
A plurality of types can be used in combination.

Hereinafter, specific examples of the coupler having a polymerizable group will be shown, but the present invention is not limited thereto.

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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Examples of the coupler compound having no polymerizable group include the compounds listed as the coupler skeleton compound in the coupler compound having a polymerizable group.

When a diazo compound is used as the coloring component A and a coupler is used as the coloring component B, the content of the diazo compound in the recording layer is preferably 0.02 to 5.0.
preferably ^{g / m 2, 0.05~3.0g / m} 2 is more preferable. If the content is less than 0.02 g / m ² , a sufficient color density may not be obtained,
If it exceeds 5.0 g / m ² , the applicability of the coating solution may be deteriorated.

The amount of the coupler compound used is 0.5 to 20 parts by mass per 1 part by mass of the diazo compound.
A mass part is preferable and 1-10 mass parts is more preferable. If the amount is less than 0.5 part by mass, sufficient coloring properties may not be obtained, and if the amount is more than 20 parts by mass, coating suitability may be deteriorated.

The coupler compound used as the color-forming component B can be used by adding a water-soluble polymer together with other components and solid-dispersing it with a sand mill or the like. It can also be used. Here, the method of solid dispersion or emulsification is not particularly limited, and a conventionally known method can be used. For more information on these methods,
JP-A-59-190886, JP-A-2-141279
And JP-A-7-17145.

For the purpose of accelerating the coupling reaction between the diazo compound and the coupler, tertiary amines, piperidines, piperazines, amidines, formamidines,
It is preferable to use an organic base such as pyridines, guanidines, and morpholines. Examples of the organic base include N, N'-bis (3-phenoxy-2-hydroxypropyl) piperazine, N, N'-bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine, N , N'-bis [3- (p-methoxyphenoxy)
-2-hydroxypropyl] piperazine, N, N'-bis (3-phenylthio-2-hydroxypropyl) piperazine, N, N'-bis [3- (β-naphthoxy) -2
-Hydroxypropyl] piperazine, N-3- (β-naphthoxy) -2-hydroxypropyl-N′-methylpiperazine,

Piperazines such as 1,4-bis {[3- (N-methylpiperazino) -2-hydroxy] propyloxy} benzene; N- [3- (β-naphthoxy) -2;
-Hydroxy] propylmorpholine, 1,4-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, 1,3-bis [(3-morpholino-2-
Morpholines such as (hydroxy) propyloxy] benzene, piperidines such as N- (3-phenoxy-2-hydroxypropyl) piperidine and N-dodecylpiperidine, triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine, 4
-Hydroxybenzoic acid 2-N-methyl-N-benzylaminoethyl ester, 4-hydroxybenzoic acid 2-N,
N-di-n-butylaminoethyl ester, 4- (3-
(N, N-dibutylaminopropoxy) benzenesulfonamide, 4- (2-N, N-dibutylaminoethoxycarbonyl) phenoxyacetic acid amide and the like. These organic bases may be used alone or in combination of two or more.

These are described in JP-A-57-123086,
JP-A-60-49991, JP-A-60-94381
No., Japanese Patent Application No. 7-228731, Japanese Patent Application No. 7-23515
No. 7, Japanese Patent Application No. 7-235158, and the like.

When the above-mentioned organic base is used, an organic base having a polymerizable group may be used as the organic base. When an organic base having a polymerizable group is used for the recording material of the first embodiment, both a diazo compound and a coupler are contained in the microcapsules as the color-forming component A, and the organic base having a polymerizable group is used as the organic base. It can also function as the coloring component B. When the diazo compound and the coupler are encapsulated in the microcapsules as the color forming component A, the diazo compound and the coupler are used in a combination that does not cause a color reaction unless a base is present. Further, in the recording material of the first aspect, a diazo compound may be used as the color-forming component A, and a coupler having a polymerizable group and an organic base having a polymerizable group may be used in combination as the color-forming component B. It is.

The amount of the organic base to be used is not particularly limited, but is preferably 1 mol of the diazo compound.
It is preferable to use it in the range of 1 to 30 mol.

Further, a coloring aid may be added for the purpose of accelerating the coloring reaction. Examples of the coloring aid include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, and sulfonamide compounds.

Next, the polymerizable compound used in the recording material of the second embodiment will be described. In the recording material of the second aspect, the recording layer has, as a polymerizable compound, a site for suppressing the reaction between the color-forming component A and the color-forming component B which reacts with the color-forming component A to form a color. A color-suppressing compound having a saturated bond in the same molecule (hereinafter sometimes referred to as a “polymerizable color-suppressing compound”). When an electron-donating dye precursor is used as the color-forming component A, and an electron-accepting compound having no polymerizable group is used as the color-forming component B, the polymerizable color-suppressing compound includes an electron-donating dye precursor and an electron-donating dye. It is preferable to use a photopolymerizable monomer having a site that suppresses the reaction with the acceptor compound and at least one vinyl group in the molecule (hereinafter, may be referred to as “photopolymerizable monomer D ₁ ”).

Specific examples of the photopolymerizable monomer D ₁ include acrylic acid and salts thereof, acrylic esters and acrylamides; methacrylic acid and salts thereof, methacrylic esters and methacrylamides; and maleic anhydride. Maleic esters; itaconic acid, itaconic esters; styrenes; vinyl ethers; vinyl esters; N-vinyl heterocycles;
Allyl esters and the like can be mentioned.

Of these, compounds having a plurality of vinyl groups in the molecule are preferable, and specifically, acrylates and methacrylates of polyhydric alcohols such as trimethylolpropane and pentaerythritol; resorcinol, pyrogallol, phlorogol Acrylic esters and methacrylic esters of polyhydric phenols such as lucinol and bisphenols; acrylate or methacrylate terminated epoxy resins; acrylate or methacrylate terminated polyesters are preferred. Among them, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate are particularly preferable.

[0235] As the photopolymerizable monomer D ₁ is preferably one a molecular weight of from about 100 to about 5000, about 3
More preferably, the number is from about 2000 to about 2000.

[0236] As the polymerizable coloring inhibiting compound, the case of using the photopolymerizable monomer D _1, as the amount thereof, the electron-donating compound 1 mass to be employed in combination with a coupler compound free of polymerizable group Parts
It is preferably from 10 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass. If the amount is less than 0.1 parts by mass, a latent image may not be formed in the exposure step,
If the amount exceeds the parts by mass, the color density may decrease.

When a diazo compound is used as the color-forming component A and a coupler compound having no polymerizable group is used as the color-forming component B, the polymerizable color-suppressing compound may be a coupling reaction between the diazo compound and the coupler compound. It is preferable to use a photopolymerizable monomer having an acidic group to be suppressed and at least one vinyl group in the molecule (hereinafter, may be referred to as “photopolymerizable monomer D ₂ ”).

Examples of the photopolymerizable monomer D ₂ include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, zinc β-methacryloxyethoxysalicylate, zinc β-acryloxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β -Methacryloxyethyl orselinate, β-acryloxyethylorselinate, β-methacryloxyethoxyphenol, β-acryloxyethoxyphenol, β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate , Hydroxystyrenesulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p-hydroxybenzoate, methacryloxymethylphenol, acryloyl Shi-methyl phenol,
Methacrylamidopropanesulfonic acid, acrylamidopropanesulfonic acid, β-methacryloxyethoxy-dihydroxybenzene, β-acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β
-Methacryloxypropanecarboxylic acid,

Γ-acryloxypropyl-α-hydroxyethyloxysalicylic acid, β-hydroxyethynylphenol, β-methacryloxyethyl-p-hydroxycinnamate, β-acryloxyethyl-p-hydroxycinnamate, 3,5 Distyrenesulfonic acid amide phenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid, acrylic acid,
Methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid, 3-β-hydroxyethoxyphenol, β-methacryloxyethyl-
p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate,

Β′-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid, β-acryloxyethyloxycarbonylhydroxybenzoic acid, N, N-di-β-methacryloxyethylaminosalicylic acid, N, N-di-β-acryloxyethylaminosalicylic acid, N, N-di-β-
Methacryloxyethylaminosulfonylsalicylic acid,
N, N-di-β-acryloxyethylaminosulfonylsalicylic acid and the like are preferred.

[0241] As the polymerizable coloring inhibiting compounds, when using the photopolymerizable monomer D _2, as the amount thereof, the coupler compound 1 part by weight for use in combination with the coupler compound free of polymerizable group On the other hand, 0.1
It is preferably from 10 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass. If the amount is less than 0.1 part by mass, a latent image may not be formed in the exposure step, and if it exceeds 10 parts by mass, the color density may decrease.

(Microcapsules) In the recording material of the present invention, it is preferable that the recording layer contains the coloring component A in a state of being encapsulated in microcapsules. As a method for microencapsulation, a conventionally known method can be used. For example, US Pat. No. 2,800,457.
U.S. Pat. No. 3,328,458, a method utilizing coacervation of a hydrophilic wall forming material described in U.S. Pat.
No. 7154, British Patent No. 990443, Japanese Patent Publication No. 38-
Nos. 19574, 42-446 and 42-771, the interfacial polymerization method described in U.S. Pat. Nos. 3,418,250 and 3,660,304, and the isocyanate polyol wall described in U.S. Pat. No. 3,796,669. US Patent No. 3,914,511 using a material
No. 4,001,140, U.S. Pat. No. 4,087,376, U.S. Pat.
No. 9802, a method using a urea-formaldehyde-based, urea-formaldehyde-resorcinol-based wall-forming material, and a melamine-described in US Pat. No. 4,025,455.
A method using a wall-forming material such as formaldehyde resin and hydroxybromocellulose, JP-B-36-9168.
JP-A-51-9079, the in-situ method by polymerization of monomers, the electrolytic dispersion cooling method described in British Patent Nos. 952807 and 965074, and U.S. Pat.
No. 111407 and British Patent No. 930422.

The method for microencapsulation is not limited to these. In particular, the oil phase prepared by dissolving or dispersing the color-forming component A in a hydrophobic organic solvent serving as the core of the capsule is mixed with a water-soluble polymer. Is mixed with a dissolved aqueous phase, emulsified and dispersed by means such as a homogenizer, and then heated to cause a polymer formation reaction at the oil droplet interface, thereby forming a microcapsule wall of the polymer substance. It is preferable to employ it. According to this method, a capsule having a uniform particle size can be formed in a short time, and a recording material having excellent raw preservability can be obtained.

The reactant for forming the polymer is added inside the oil droplet and / or outside the oil droplet. Specific examples of the polymer substance include polyurethane, polyurea, polyamide,
Examples include polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer and the like. Among them, polyurethane, polyurea,
Polyamide, polyester, and polycarbonate are preferred, and polyurethane and polyurea are particularly preferred. The above polymer substances can be used in combination of two or more kinds.

Examples of the water-soluble polymer include gelatin, polyvinylpyrrolidone, and polyvinyl alcohol. For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance (eg, polyol, polyamine) which reacts with the polyisocyanate to form a capsule wall should be encapsulated in a water-soluble polymer aqueous solution (aqueous phase) or encapsulated. After mixing in an oily medium (oil phase), emulsifying and dispersing these, and then heating, a polymer formation reaction occurs at the oil droplet interface, and microcapsule walls can be formed.

Examples of the polyvalent isocyanate and the polyol and polyamine to be reacted therewith are described in US Pat. Nos. 3,281,383, 3,737,695 and 3,792.
No. 68, JP-B-48-40347, JP-B-49-2415
9, JP-A-48-80191 and JP-A-48-84086.
The one described in the item can be used.

When preparing microcapsules containing the coloring component A, the coloring component A contained in the microcapsules is prepared.
May be present in a solution state or a solid state in the capsule. When the coloring component A is encapsulated in a microcapsule in a solution state, the coloring component A may be encapsulated in a state dissolved in a hydrophobic organic solvent. The amount of the organic solvent used is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the coloring component A.

As the hydrophobic organic solvent, generally,
Phosphate, phthalate, acrylate, methacrylate, other carboxylate, fatty acid amide, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diallylethane, solid compound at room temperature , Oligomer oil, polymer oil and the like. In particular,
JP-A-59-178451 to JP-A-59-178455,
JP-A-59-178457, JP-A-60-242094, JP-A-63-85633, JP-A-6-194825 and JP-A-6-194825
No. -13310 to No. 7-13311, No. 9-1060
Organic solvents described in JP-A No. 39 and Japanese Patent Application No. 62-75409 are exemplified.

Also, the coloring component A to be encapsulated
When the solvent has poor solubility in the organic solvent, a low-boiling solvent having high solubility can be used in combination. Examples of the low boiling point solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

On the other hand, an aqueous solution in which a water-soluble polymer is dissolved is used for the aqueous phase to be used. After the oil phase is charged into the aqueous phase, emulsification and dispersion are carried out by means of a homogenizer or the like. It acts uniformly and easily and acts as a dispersion medium for stabilizing the emulsified aqueous solution. Here, in order to more uniformly emulsify and disperse and stabilize, a surfactant may be added to at least one of the oil phase and the aqueous phase. As the surfactant, a known emulsifying surfactant can be used. When a surfactant is added, the amount of the surfactant is 0.1% to 5% based on the mass of the oil phase.
%, Particularly preferably 0.5% to 2%.

When the color forming component A is microencapsulated, the average particle size of the microcapsules is preferably 20 μm or less, and more preferably 5 μm or less from the viewpoint of obtaining high resolution. If the formed microcapsules are too small, the surface area with respect to a certain solid content becomes large and a large amount of a wall material is required. Therefore, the average particle diameter is preferably 0.1 μm or more.

The photopolymerizable composition of the present invention may further comprise, in addition to the above-described recording material of the present invention, inks, color filters, holograms, proofs, sealants, adhesives, lithographic printing, resin relief printing plates,
It can be used in a wide range of fields such as photoresist,
Other components may be added according to each application.
Further, when it is used for other than the recording material of the present invention, 3)
The polymerizable compound does not need to function as the color forming component B and the color formation suppressing compound as described above, and a polymerizable compound having an ethylenically unsaturated bond can be widely used.

In the case of a multicolor recording material, a plurality of monochromatic recording layers are laminated on a support, and each recording layer has a coloring component A having a different coloring hue (may be encapsulated in microcapsules). And a color-forming component B (which may have a polymerizable group) having in its molecule a site that reacts with each of the color-forming components A to form a color, and photopolymerization that forms a latent image by being exposed to light of different wavelengths. , A multicolor recording material can be obtained. That is, by using spectral sensitizing dyes having different absorption wavelengths for the photopolymerizable composition, a photopolymerizable composition sensitive to light of different wavelengths can be obtained. In this case, an intermediate layer may be provided between the recording layers of each single color.

The recording layer of the multicolor multi-layer recording material of the present invention comprises:
For example, it can be formed as follows. And microcapsules encapsulating the color forming component A ^Y of yellow color, the containing and color forming component B ^Y to develop the color forming component A ^Y, a photopolymerizable composition which is sensitive to a latent image formed on the light source center wavelength lambda ₁ 1 Is provided on a support, and on the layer, a microcapsule containing a coloring component A ^M for magenta coloring, a coloring component B ^M for coloring the coloring component ^AM, and a light source center wavelength λ ₂ are exposed. a second recording layer containing a photopolymerizable composition a latent image formed is provided, more that layer on the microcapsules encapsulating the color forming component a ^C of cyan color, the color developing component to develop the color forming component a ^C B ^C and light source center wavelength λ
_{And a third} recording layer containing a photopolymerizable composition for forming a latent image upon exposure to a third recording layer. The multi-layer recording layer α has a laminated structure, and if necessary, has an intermediate layer between the respective layers of the multi-layer recording layer α. It is composed of a recording layer β provided with a layer.

In the case of forming an image using the recording material having the multi-colored multi-layer recording layer, the image is formed by using a plurality of light sources having different wavelengths suitable for the absorption wavelength of each recording layer during the imagewise exposure process. By exposing, the recording layer having the absorption wavelength of the light source selectively forms a latent image, so that a multicolor image can be formed with high sensitivity and sharpness, and the entire surface of the recording layer is irradiated with light. By doing so, it is possible to eliminate the coloring of the background portion by the photopolymerizable composition including the spectral sensitizing dye remaining in the layer, and to form a high-contrast high-quality multicolor image. .

(Support) As the support, any paper support used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copy paper, etc., as well as acid paper, neutral paper, and the like can be used. Paper, coated paper, plastic film laminated paper, synthetic paper, plastic film and the like can be used.

In the recording materials of the first and second embodiments, other layers such as an undercoat layer, an intermediate layer, a light absorbing layer, a protective layer, and a back coat layer may be provided in addition to the recording layer. Each layer such as the undercoat layer, the intermediate layer, the light absorbing layer, the protective layer, and the back coat layer preferably contains a curing agent, and particularly preferably, the protective layer contains a curing agent. . This case is preferable in that the tackiness of the protective layer is reduced. As the curing agent, for example, a "gelatin curing agent" used in the production of a photographic light-sensitive material is useful. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, and the reaction described in US Pat. No. 3,635,718 and others. Compound having a neutral halogen, US Patent No. 3
No. 6,357,718 and others, compounds having a reactive ethylenically unsaturated bond, U.S. Pat. No. 3,017,280 and others, aziridine compounds, U.S. Pat.
No. 091537 and other epoxy compounds, halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, vinyl compounds described in US Pat. No. 3,642,486 and US Pat. No. 3,687,707. Sulfones, vinyl sulfone precursors described in U.S. Pat. No. 3,841,872, U.S. Pat. No. 3,640,720.
And the like, or chromium alum, zirconium sulfate, boric acid or the like can be used as an inorganic curing agent.

Among these curing agents, 1,3,5-triacroyl-hexahydro-s-triazine, 1,2
-Bisvinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamido) ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt,
2,4,6-triethylenimino-s-triazine, boric acid and the like are preferred. The amount of the curing agent to be added is 0.1 to the binder contained in the layer to which the curing agent is added.
5 to 5% by mass is preferred.

Further, layers such as the undercoat layer, the intermediate layer, the light absorbing layer, the protective layer, and the back coat layer may be coated with a coating aid, an antistatic agent, an improvement in slipperiness, an emulsifying dispersion, an adhesion preventing agent, and the like. It can be formed using various surfactants for various purposes.

Examples of the surfactant include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, and the like.
Alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkylsulfate, N-acyl-N-
Alkyl taurines, sulfosuccinates, anionic surfactants such as sulfoalkyl polyoxyethylenalkylphenyl ethers, alkyl betaines,
Amphoteric surfactants such as alkylsulfobetaines; and cationic surfactants such as aliphatic or aromatic quaternary ammonium salts.

Further, the layers such as the undercoat layer, the intermediate layer, the light absorbing layer, the protective layer, and the back coat layer may further contain other additives as necessary.
Examples of the other additives include, for example, dyes for preventing irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents, slip improvers And the like, and typical examples of these are
Research Disclosure, Vol. 1
76, December 1978, Item 17643, and Vol. 187, November 1979, Item 18
716 etc.

The protective layer may contain colloidal silica in order to reduce the adhesiveness of the protective layer in addition to the curing agent. Suitable examples of the colloidal silica include Snowtex 20, Snowtex 30, Snowtex C, Snowtex O, and Snowtex N manufactured by Nissan Chemical. The amount of the colloidal silica to be added is preferably 5 to 80% by mass based on the binder contained in the protective layer.

Preferably, the protective layer contains a matting agent. As the matting agent, for example, silica, magnesium oxide, barium sulfate, strontium sulfate, inorganic compounds such as silver halide and polymer particles such as polymethyl methacrylate, polyacrylonitrile, polystyrene, carboxy starch, corn starch, carboxynitrophenyl And starch particles such as starch. These may be used alone or in combination of two or more. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred.

As the silica particles, for example, FUJ
I-DEVICE CHEMICAL LTD. SYLOID AL-1, 65, 72, 79, 74, 40
4, 620, 308, 978, 161, 162, 24
4, 255, 266, 150 and the like.

The average particle size of the matting agent is from 1 to 2
0 μm is preferred. The content of the matting agent in the protective layer is preferably ² to 500 mg / m ² ,
-100 mg / m ² is more preferred.

The protective layer may contain a fluorescent whitening agent for increasing the whiteness of the recording material or a blue dye as a bluing agent.

The intermediate layer is a layer having a barrier function against oxygen permeation, and usually contains mainly a binder, and may further contain the above-mentioned curing agent and additives such as polymer latex, if necessary. . In the present invention, a light absorbing agent such as an ultraviolet absorbing agent described below may be added to the intermediate layer, so that the intermediate layer has a function as a light absorbing layer.

The light absorbing layer is a layer having a function of absorbing light such as ultraviolet rays, and usually contains mainly a binder and a light absorbing agent such as an ultraviolet absorbing agent. And an additive such as a polymer latex. As the light absorber, an ultraviolet absorber is generally used. Examples of the ultraviolet absorber include known benzotriazole compounds, cinnamic acid ester compounds, aminoarylidenemalon nitrile compounds, and benzophenone compounds. Can be used. The ultraviolet absorber can be preferably added to the intermediate layer by an oil-in-water dispersion method or a latex dispersion method, but can be emulsified and dispersed and added to a desired layer.

In the oil-in-water dispersion method, the boiling point is, for example, 1
High boiling organic solvent of 75 ° C. or higher and boiling point of, for example, 30 to 1
After dissolving in a single solution of a so-called auxiliary solvent at 60 ° C. or a mixture thereof, it is finely dispersed in water or an aqueous medium such as an aqueous gelatin solution or an aqueous polyvinyl alcohol solution in the presence of a surfactant.

Specific examples of the high boiling point organic solvent are described in US Pat. No. 2,322,027. As the high boiling point organic solvent and the auxiliary solvent, the same solvents as those used in the above-described microencapsulation can be preferably used. In addition, the fine dispersion includes
Phase inversion may be involved. Further, after the fine dispersion, if necessary, the auxiliary solvent may be removed or reduced by distillation, Nudel washing, ultrafiltration or the like, and then used for coating.

The details of the latex dispersion method and specific examples of the latex are described in, for example, US Pat. No. 4,199,363 and West German Patent Application (OLS) No. 2,541,274.
No. 2,541,230, JP-A-49-74538, JP-A-51-59943,
No. 54-32552 and Research Di
sclosure, Vol. 148, August 1976,
Item 14850 and the like. Suitable examples of the latex include acrylates or methacrylates (eg, ethyl acrylate, n
-Butyl acrylate, n-butyl methacrylate, 2
Acetoacetoxyethyl methacrylate) and acid monomers (eg, acrylic acid, 2-acrylamide-2-
Latex with methylpropanesulfonic acid).

In the present invention, as the ultraviolet absorber, an ultraviolet absorber having a structure hardly diffused into an adjacent layer,
For example, an ultraviolet absorber copolymerized with a polymer or latex is mentioned as a particularly preferred example. As such an ultraviolet absorber, for example, European Patent No. 127,81
No. 9, JP-A-59-68731, and JP-A-59-68731.
26733, 59-23344, British Patent 2,118,315, JP-A-58-11194.
No. 2, U.S. Pat. Nos. 4,307,184, 4,202,836, 4,202,834, 4,207,253, and 4,17.
No. 8,303, JP-A-47-560 and the like can be referred to. These are usually added to the light absorbing layer, but if necessary, the intermediate layer, the protective layer,
It is added to layers such as the recording layer and the antihalation layer.

In the recording materials of the first and second embodiments, the binder in the recording layer, the undercoat layer, the intermediate layer, the light absorbing layer, the back coat layer, the protective layer, etc. is as described above. In addition, the water-soluble polymer that can be used for emulsification and dispersion of the photocurable composition and microencapsulation of the electron-donating colorless dye, and others, such as polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, and poly Butyl methacrylate, acrylic resins such as copolymers thereof, polystyrene, polyvinyl formal, polyvinyl butyral, phenolic resin, styrene-butadiene resin, ethyl cellulose, epoxy resin, urethane resin, etc. It can also be used. Among these, gelatin and polyvinyl alcohol are preferred.

Each layer can be formed by preparing a coating solution for forming each layer, coating the solution on a support (layer), and drying. The application method is the same as for the recording layer. As the solvent for the coating liquid, for example, methanol,
Ethanol, n-propanol, isopropanol, n
Alcohols such as -butanol, sec-butanol, methyl cellosolve, 1-methoxy-2-propanol,
Methylene chloride, halogen solvents such as ethylene chloride, acetone, cyclohexanone, ketones such as methyl ethyl ketone, methyl cellosolve acetate, ethyl acetate,
Examples include esters such as methyl acetate, toluene, xylene, water and the like. These may be used alone or in combination of two or more. Among these, water is particularly preferred.

As described above, the thickness of each layer formed on the support is preferably 0.1 to 50 μm.

When the recording materials of the first and second embodiments are used for full-color image formation, two or more recording layers containing color-forming components that develop colors different from each other are laminated. Each recording layer contains a color-forming component that develops a different hue, and a light having a wavelength different from each other so that a polymerization reaction is started by light having a different wavelength to form a latent image. It preferably contains a polymerizable composition. The sensitive wavelength of the photopolymerizable composition can be adjusted by changing the combination of the contained organic boron compound and organic dye.

When image recording is performed using the recording materials of the first and second aspects, contact exposure of an original such as a lithographic film, enlargement exposure of a slide or liquid crystal image, reflection exposure using reflected light of the original, etc. Various exposure methods can be used. Further, when performing multi-color image recording using the recording material of the first and second aspects, exposure is performed once or multiple times using light having different wavelengths.
It can be obtained by changing the light source, changing the optical filter, and the like.

The recording materials of the first and second embodiments are subjected to a heat development treatment simultaneously with or after the imagewise exposure. As the heating method in the thermal development treatment, various conventionally known methods can be used, and the heating temperature is usually 80 to 200 ° C, preferably 100 to 160 ° C, and the heating time is Usually 1 second to 5 minutes,
3 seconds to 1 minute is preferred.

It is preferable that the recording material of the first and second embodiments is subjected to the entire surface exposure after the heat development treatment, and the non-cured portion is also light-cured. When the entire surface exposure is performed, the color development reaction of the background and the color erasure reaction of the color development part are suppressed, which is advantageous in that the storability of the image is improved.

The recording materials of the first and second embodiments can be suitably used for various uses such as Copier (registered trademark), facsimile, printer, label, color proof, and second original drawing.

[0281]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples, “%” is used unless otherwise specified.
Means "% by mass", and "parts" means "parts by mass".

(Examples 1 to 23) A photopolymerizable composition having the following composition using an exemplary compound represented by any of the general formulas (1) to (3) shown in Table 1 and an organic boron compound Was prepared. [Photopolymerizable composition] Pentaerythritol tetraacrylate 1.41 g Benzyl methacrylate / methacrylic acid 1.29 g (molar ratio 73/27 copolymer) ) Methyl ethyl ketone 12 g Propylene glycol monomethyl ether acetate 8.62 g Exemplary compounds (see Table 1) ··· 1 × 10 ^-4 mole organic boron compound (see Table 1) ··· 6 × 10 ^-4 mole methanol ··· ... 6 g Each of the prepared photopolymerizable compositions was applied on a 100 µm polyethylene terephthalate film to a thickness of 2 µm, and dried at 100 ° C for 5 minutes. Further, the following protective layer coating solution (1) was applied to a thickness of 1 μm, and dried at 100 ° C. for 2 minutes to produce photosensitive recording materials of Examples 1 to 20.

[Coating Solution for Protective Layer (1)] Water 98 g Polyvinyl Alcohol 7.1.7 g hydroxypropyl methylcellulose 1.7 g polyvinylpyrrolidone 7g

Comparative Examples 1 and 2 The same procedures as in Example 1 were carried out except that the organic dye and the organic boron compound used in Example 1 were changed to the organic dye and the organic boron compound shown in Table 1, respectively. Thus, the photosensitive recording materials of Comparative Examples 1 and 2 were produced. The structures of the organic dyes d-1 and d-2 shown in Table 1 are shown below.

[0285]

Embedded image

The photosensitive recording materials prepared in Examples 1 to 23 and Comparative Examples 1 and 2 were exposed using a vacuum flame apparatus. Exposure to the photosensitive recording material is performed using a step wedge (a density step of 0.15, a density step of 1 to 15 steps, "Fuji Step Guide P" (manufactured by Fuji Photo Film Co., Ltd.) and "S
C38 filter ”(Fuji Photo Film Co., 380n
Sharp cut filter that cuts light below m))
Through, 500W xenon lamp (made by Ushio Corporation)
For 10 seconds. After the exposure, each of the photosensitive recording materials was developed using a developer having the following composition.

[Developer] Sodium carbonate anhydrous 10 g Butyl cellosolve 10 g・ 5g water ・ ・ ・ ・ ・ 1l After development, the amount of exposure to the area corresponding to the high step number of the step wedge is small. The photopolymerizable composition in this region eluted into the developer, and a polyethylene terephthalate surface appeared. For the photosensitive recording material of each example, the region where the photopolymerizable composition was completely eluted was examined, and the step number (clear step number) of the step wedge corresponding to the region having the highest exposure amount was determined. The higher the determined number of steps, the higher the sensitivity of the photosensitive recording material. Table 1 shows the results. In addition, when the photopolymerizable composition was eluted into the developer over all the exposed areas due to low sensitivity, "flow" was indicated in the table.

The photosensitive recording materials of Examples 1 to 23 and Comparative Examples 1 and 2 were manufactured by using a fluorescent lamp (3
(0000 lux) for 10 minutes, and the densities of yellow, magenta and cyan were measured with a transmission Macbeth densitometer. The better the decoloring property of the contained organic dye compound by exposure is, the lower the fogging density of the background portion is. Table 1 shows the results. In addition, in the following Table 1, the example compound No. The symbol in the column of the above indicates the exemplified compound N of the aforementioned general formulas (1) to (3).
o. And the symbol in the column of the organic boron compound is exemplified compound No. of the aforementioned organic boron compound. Is equivalent to Hereinafter, the same applies to Table 2.

[0289]

[Table 1]

From the results shown in Table 1, the photosensitive recording materials of Examples 1 to 23 were higher in sensitivity than Comparative Examples 1 and 2, and
It was demonstrated that the decoloration of the organic dye by exposure was good and the fogging density was low.

(Example 24) [Preparation of Electron-donating Colorless Dye Capsule Solution] -1-a. Preparation of Electron-donating Colorless Dye (1) Capsule Solution- 8.9 g of the following electron-donating colorless dye (1) is dissolved in 16.9 g of ethyl acetate, and "Encapsulating agent Takenate D-110N" (Takeda Pharmaceutical Co., Ltd.) 20 g of “Millionate MR200” (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added. This solution was added to a mixture of 42 g of 8% phthalated gelatin and 1.4 g of a 10% sodium dodecylbenzenesulfonate solution, and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 72 g of a 2.9% aqueous solution of tetraethylenepentamine were added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, the electron-donating colorless dye (1) was encapsulated in the core. Average particle size 0.5μm
Was obtained.

[0292]

Embedded image

[0293] 2. [Preparation of emulsion of photopolymerizable composition] -2-a. Preparation of an emulsion of the photopolymerizable composition (24)-0.05 g of the organic dye shown in Table 2, 0.3 g of the organic boron compound shown in Table 2, and 0.05 g of the following polymerization aid (1)
Then, 5.3 g of isopropyl acetate was added to 4.2 g of the following polymerizable electron-accepting compound (1) and dissolved by stirring.

[0294]

Embedded image

This solution was added to an 8% aqueous gelatin solution (13 g).
And 0.8 g of a 2% surfactant (1) aqueous solution and 0.8 g of a 2% surfactant (2) aqueous solution,
10,000 with a homogenizer (Nippon Seiki Co., Ltd.)
The mixture was emulsified for 5 minutes by rotation to obtain an emulsion of the photopolymerizable composition (24).

[0296]

Embedded image

[0297] 3. [Preparation of coating solution for recording layer] -3-a. Preparation of Coating Solution for Recording Layer (24)-4 g of the above-mentioned electron-donating colorless dye (1) capsule solution, 12 g of an emulsion of the photopolymerizable composition (24), and 12 g of a 15% aqueous gelatin solution were mixed and recorded. A coating solution for layer (24) was prepared.

[0298] 4. [Preparation of Coating Solution (2) for Protective Layer] -4-a. Preparation of Coating Solution (2) for Protective Layer- 4.5 g of 10% gelatin aqueous solution, 4.5 g of distilled water,
0.5 g of a 2% surfactant (3) aqueous solution, 0.3 g of a 2% surfactant (4) aqueous solution, 0.5 g of a 2% hardener (1) aqueous solution, and “Syloid 72” (FUJI- DEVI
SON CHEMICAL LTD. 50) applied amount
mg / m ² and “Snowtex N” 1
g) to prepare a coating solution (2) for a protective layer.

[0299]

Embedded image

[0300] 5. [Support] A white polyester film filled with a white pigment and having a thickness of 100 μm (“Lumirror E68L”, manufactured by Toray Industries, Inc.) was used as a support. The recording coating solution (24) was applied on the support using a coating bar so that the dry weight of the coating layer was 6 g / m ² , and dried at 30 ° C. for 10 minutes. The protective layer coating solution (2) was applied thereon using a coating bar so that the dry weight of the applied layer became 2 g / m ² , and dried at 30 ° C. for 10 minutes.
Was obtained.

(Examples 25 to 35) The organic dyes and organic boron compounds used in Example 24 are exemplified by the compounds represented by any of formulas (1) to (3) shown in Table 2. Except having changed to and the organic boron compound, it carried out similarly to Example 24, and obtained the photosensitive heat-sensitive sheet of Examples 25-35.

(Comparative Examples 3 and 4) The same procedures as in Example 24 were carried out except that the organic dye and the organic boron compound used in Example 24 were changed to the organic dye and the organic boron compound shown in Table 2, respectively. Thus, photosensitive and heat-sensitive sheets of Comparative Examples 3 and 4 were obtained.

The photosensitive and heat-sensitive sheets of Examples 24 to 35 and the photosensitive and heat-sensitive sheets of Comparative Examples 3 and 4 were prepared using a stepping wedge and SC
30 with a 500 W xenon lamp through a 38 filter
Irradiated for 2 seconds, each formed a latent image. Thereafter, each photosensitive and heat-sensitive sheet was heated with a hot plate at 125 ° C. for 15 seconds. The unexposed portion was formed when the electron donating colorless dye (1) and the polymerizable electron accepting compound (1) reacted. A magenta color was formed, and the color density was not reduced or no color was formed in the exposed portion. The area where color development did not occur was examined, and the step number (clear step number) of the step wedge corresponding to the area with the least exposure amount was obtained. The higher the determined number of steps, the higher the sensitivity of the photosensitive heat-sensitive sheet.
Table 2 shows the results. When the sensitivity was low and coloring occurred at all stages, "solid" was indicated in the table.

Further, after exposure under a fluorescent lamp (30000 lux) for 10 minutes, the density of the yellow, magenta and cyan background portions was measured by a transmission Macbeth densitometer. The better the decoloring property of the exemplified compound represented by any of the general formulas (1) to (3) contained by exposure is, the lower the fogging density of the background portion is. Table 2 shows the results.

[0305]

[Table 2]

From the results shown in Table 2, the heat-sensitive and heat-sensitive sheets of Examples 24 to 35 have high sensitivity and good decolorization of the organic dye by post-exposure, as compared with Comparative Examples 3 and 4.
The fog density was demonstrated to be low.

[0307]

According to the present invention, a photopolymerizable composition sensitive to not only ultraviolet light but also visible light to infrared light can be provided. Further, it is possible to provide a recording material capable of recording an image in a completely dry system and capable of easily forming a clear and high-contrast black and white or color image. In particular, it is possible to provide a recording material in which the covering of the background portion is reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 514 G03F 7/004 514 7/028 7/028 7/095 7/095 (72) Inventor Shintaro Washisu 200 Fuji, Omiyazato, Fujinomiya City, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. 4,000 Kawajiri, Yoshida-cho, Haibara-gun Fujisha Shin Film Co., Ltd. F-term (reference) 2H025 AA01 AB09 AB20 AC01 AC08 AD01 BC13 BC42 BC83 BH05 CA39 CA41 CA48 CC13 CC14 CC20 DA10 DA11 FA22 4J011 AA06 DA02 FA01 FB01 FB19 PA43 PC45 PA48 P48B PC08 QA01 QA02 QA03 QA05 QA06 QA09 QA11 QA12 QA21 QA27 QB12 QB14 QB15 QB17 QB23 SA71 UA06 VA01 WA01 WA05 WA06

Claims (10)

[Claims] 1. A polymerizable polymer having an ethylenically unsaturated bond.
And a compound represented by the following general formula (1):
And an organic boron compound represented by the general formula (A).
Photopolymerizable composition. Embedded image(In general formula (1), Q¹~ Q^ThreeAre each independently an oxygen atom
Or a sulfur atom; ¹And R^TwoAre each independently water
Represents an atom, an aliphatic group, an aromatic group, or a heterocyclic group,
Z¹And Z^TwoAre each independently represented by the general formula (1)
It represents a substituent necessary for the compound to become a dye. )(In the general formula (A), R_a ¹, R_a ^Two, And R_a ^ThreeAre independent
To form an aliphatic group, an aromatic group, a heterocyclic group, or -SiR
_a ^FiveR_a ⁶R_a ⁷And R_a ^Five, R_a ⁶, And R_a ⁷Are independent
Represents an aliphatic group or an aromatic group;_a ^FourIs aliphatic
Y represents a group⁺Represents a group capable of forming a cation. ) 2. A polymerizable compound having an ethylenically unsaturated bond, a compound represented by the following general formula (2), and a compound represented by the following general formula (2) interact with each other to generate a radical. A photopolymerizable composition containing a compound which can be used. Embedded image (In the general formula (2), X ¹ represents NR ¹² , a sulfur atom, a selenium atom, or an oxygen atom, and R ⁴ , R ⁵ , and R ¹² each independently represent a hydrogen atom, an aliphatic group, or an aromatic group. Or a heterocyclic group, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹
Each independently represents a hydrogen atom or a monovalent substituent, and two or more selected from R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are bonded, It may form a ring. ) 3. A compound capable of generating a radical by interacting with the compound represented by the general formula (2) is represented by the following general formula (A):
The photopolymerizable composition according to claim 2, which is an organic boron compound represented by the following formula: Embedded image (In the general formula ^{_{(A), R a 1,}} R a 2, and R _a ³ are each independently an aliphatic group, an aromatic group, a heterocyclic group or -SiR,
_a ⁵ represents _{^{R a 6 R a 7, R}} a 5, R a 6 , and R _a ^7, each independently represents an aliphatic group or an aromatic group,, R _a ⁴ each represents an aliphatic group, Y ⁺ represents a group capable of forming a cation. ) 4. A polymerizable compound having an ethylenically unsaturated bond, a compound represented by the following general formula (3) and a compound represented by the following general formula (3) interacting with each other to generate a radical. A photopolymerizable composition containing a compound which can be used. Embedded image (In the general formula (3), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent, and Z ³ and Z ⁴ each independently represent a general formula (3) It represents a substituent necessary for the compound to become a dye.) 5. A compound capable of generating a radical by interacting with the compound represented by the general formula (3) is represented by the following general formula (A):
The photopolymerizable composition according to claim 4, which is an organic boron compound represented by the following formula: Embedded image (In the general formula ^{_{(A), R a 1,}} R a 2, and R _a ³ are each independently an aliphatic group, an aromatic group, a heterocyclic group or -SiR,
_a ⁵ represents _{^{R a 6 R a 7, R}} a 5, R a 6 , and R _a ^7, each independently represents an aliphatic group or an aromatic group,, R _a ⁴ each represents an aliphatic group, Y ⁺ represents a group capable of forming a cation. ) 6. The photopolymerizable composition according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (4). Embedded image (In the general formula (4), L ¹ and L ² each independently represent a methine group which may be substituted, m represents an integer of 0 to 3, and G ¹ and G ² each independently represent an electron. Represents an attractive group or is bonded at G ¹ and G ² to form an aromatic ring or a heterocyclic ring.) 7. The photopolymerizable composition according to claim 4, wherein the compound represented by the general formula (3) is represented by the following general formula (5). Embedded image (In the general formula (5), L ¹ and L ² each independently represent a methine group which may be substituted, m represents an integer of 0 to 3, and G ¹ and G ² each independently represent an electron. Represents an attractive group or is bonded at G ¹ and G ² to form an aromatic ring or a heterocyclic ring.) 8. A photopolymerizable composition comprising a recording layer on a support, wherein the recording layer includes a microcapsule containing a color-forming component, and the photopolymerizable composition according to any one of claims 1 to 7. A recording material containing at least a composition and a polymerizable compound having an ethylenically unsaturated bond and having a site that reacts with the color-forming component to form a color of the color-forming component. 9. A recording medium having a recording layer on a support, wherein the recording layer includes a microcapsule containing a color-forming component, and a color-forming compound that reacts with the color-forming component to form a color. 7. A polymerizable compound having at least the photopolymerizable composition according to any one of (1) to (7), and a polymerizable compound having an ethylenically unsaturated bond, having a site that suppresses a reaction between the coloring component and the coloring compound. A recording material that is a color formation suppressing compound. 10. A first recording layer sensitized to light having a center wavelength λ1, a second recording layer sensitized to light having a center wavelength λ2 and developing a color different from that of the first recording layer,... 9. A multi-layer structure in which the first, second,..., and i-th recording layers that are sensitive to light of λi and develop a color different from the i-th recording layer are stacked in this order. 10. The recording material according to item 9.