JP2002363207A - Photopolymerizable composition and recording material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a photopolymerizable composition having high sensitivity to visible to infrared radiations and a recording material comprising the photopolymerizable composition and capable of forming a high-sensitivity, clear and high-contrast image. SOLUTION: The photopolymerizable composition comprises a polymerizable compound and at least one kind of compound represented by formula (1) [wherein, R<1> denotes hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group; R<2> and R<3> denote each hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an alkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, an aralkylthio group or an arylthio group; R<2> and R<3> may be linked to form a ring; and X denotes hydrogen atom, an alkyl group, an alkyloxy group, an alkenyl group, an alkynyl group, an alkenyloxy group, an alkynyloxy group, an alkylamino group or a halogen atom].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ink, a hologram, a proof, a sealant, an adhesive, a lithographic printing plate, a resin letterpress,
Regarding photopolymerizable compositions and recording materials that can be suitably used in a wide range of fields including photoresists, etc.
A novel photopolymerizable composition that can be sensitive to not only ultraviolet light but also visible light to infrared light, and a completely dry processing system that does not require the use of a developer or the like and generates no waste The present invention relates to a recording material capable of forming a black-and-white or color image.

[0002]

2. Description of the Related Art A photopolymerizable composition is basically a photopolymerization initiator and an addition-polymerizable compound containing two or more ethylenically unsaturated bonds in a molecule (hereinafter referred to as "polyfunctional monomer"). ), And is cured by irradiation with light, changes in tackiness, and becomes insoluble in a solvent. Utilizing these properties, it is widely used in photography, printing, metal surface processing, ink and the like. The functions and application examples of the photopolymerizable composition are described in many books. For example, J. "Lig" by Kosar
ht Sensitive Systems "(J.W.
iley & Sons, New York, 1965
Year, p. 158-193); I. Jacobso
n, R. E. FIG. "Imaging S" by Jacobson
systems (J. Wiley & Sons, Ne)
w York, 1976, pp. 181-222).

In recent years, as an image forming method using a photopolymerizable composition, an image forming system using photosensitive microcapsules in which the photopolymerizable composition is encapsulated in microcapsules has been proposed. For example, Japanese Unexamined Patent Publication No. 57-12434
No. 3, JP-A-57-179636, JP-A-57-19
No. 7538 discloses a dye formed by applying a pressure to the color-forming sheet coated with a photopolymerizable composition comprising a vinyl compound and a photopolymerization initiator and a microcapsule containing the dye and an image-receiving sheet after exposure. An image forming method is disclosed.

Further, JP-A-3-87827 and JP-A-4-21252 describe a light- and heat-sensitive color recording material containing two components, wherein one of the two components is encapsulated in a microcapsule and the other is encapsulated. Is disclosed as a curable compound of the photocurable composition, or the other is contained outside the microcapsules together with the photocurable composition. Further, in the latter recording material, a microcapsule containing an electron-donating colorless dye, and a photocurable composition containing an electron-accepting compound, a polymerizable vinyl monomer and a photopolymerization initiator outside the microcapsule. A light- and heat-sensitive recording material provided with a layer containing

As described above, a recording material using a photopolymerizable composition can record an image in a completely dry system without using a developer or the like, and is environmentally friendly in that no waste is generated. Very preferred. When an image is recorded on a photosensitive recording material, it is advantageous if an inexpensive infrared laser or green to red light can be used in addition to UV light and short-wave visible light. However, in a recording material using a photopolymerizable composition, although it is sensitive to ultraviolet light, it is not sensitive to visible light to infrared light, or its sensitivity is not sufficient even when exposed, and as a result, The formed image may be unclear or the contrast between the image portion and the non-image portion may be low. Therefore, further improvement in sensitivity is desired.

[0006]

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 ~
An object of the present invention is to provide a photopolymerizable composition that can be sensitive to infrared light with high sensitivity. Further, the present invention does not require the use of a developer or the like, and in a completely dry processing system that does not generate waste, high-sensitivity image recording using not only ultraviolet light but also visible light to infrared light is possible. It is an object of the present invention to provide a recording material capable of forming a clear, high-contrast black-and-white or color image.

[0007]

Means for solving the above problems are as follows. <1> A photopolymerizable composition comprising a polymerizable compound and at least one compound represented by the following general formula (1).

[0008]

Embedded image

[In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, or a heteroaromatic group; Ar is an aromatic group or a heterocyclic group which may have a substituent; R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group which may have a substituent; Represents an aryl group, an alkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, an aralkylthio group, or an arylthio group;
² and R ³ may combine to form a ring. X represents a hydrogen atom, an alkyl group, an alkyloxy group, an alkenyl group, an alkynyl group, an alkenyloxy group, an alkynyloxy group, an alkylamino group, or a halogen atom. ]

<2> Polymerizable compound, general formula (1)
And the compound capable of generating a radical or a cation by interacting with the compound represented by the general formula (1). The compound capable of generating a radical or a cation,
It is a compound that can generate at least one of a radical and a cation.

<3> Compounds capable of generating radicals or cations include organic boron compounds, iodonium salts, sulfonium salts, iron allene complexes, S-triazine derivatives, organic peroxides, titanocene, triarylimidazole dimers, and azinium The photopolymerizable composition according to <2>, which is at least one selected from salts.

<4> The photopolymerizable composition according to <2>, wherein the compound capable of generating a radical or a cation is a triarylimidazole dimer and an organic boron compound.

<5> The polymerizable compound having an ethylenically unsaturated bond, and the compound capable of generating a radical or a cation is a triarylimidazole dimer and / or an organic boron compound. <
2>.

<6> The photopolymerizable composition according to any one of <3> to <5>, wherein the organoboron compound is a compound represented by the following general formula (A).

[0015]

Embedded image

[0016] [In the general formula ^{_{(A), R a 1,}} R a 2, R a 3, and R _a ⁴ each independently an aliphatic group, an aromatic group, a heterocyclic group, or Si (R _a ⁵ ) (R _a ⁶⁾ represents a _{^{-R a 7, R a 5,}} R a 6,
And R _a ⁷ are each independently an aliphatic group, an aromatic group. G ⁺ represents a group capable of forming a cation. ]

<7> having a recording layer on a support,
The recording layer comprises: a coloring component A; a coloring component B having a portion that reacts with the coloring component A to form a color;
And a photopolymerizable composition according to any one of (1) to (3).

<8> The recording material according to <7>, wherein at least one of the polymerizable compounds is a coloring component B. <9> The recording material according to <7>, wherein the polymerizable compound is a color-suppressing compound having a site for suppressing the reaction between the color-forming components A and B in the same molecule. <10> The recording material according to any one of <7> to <9>, wherein the color-forming component A is included in a microcapsule.

<11> a first recording layer sensitive to light having a center wavelength λ ₁ , a second recording layer sensitive to light having a center wavelength λ ₂ and developing a color different from the first recording layer,... , Center wavelength λ
_The above <7> to << 7, which have a multilayer structure in which the first, second,..., and i-th recording layers that are sensitized to the _i-th light and develop colors different from the i-th recording layer in this order. 10>.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable composition of the present invention is characterized by containing a polymerizable compound and a compound represented by the following general formula (1) as a spectral sensitizing dye. And The recording material of the present invention is characterized in that the recording layer on the support contains the photopolymerizable composition of the present invention together with a coloring component and the like. Hereinafter, the photopolymerizable composition and the recording material of the present invention will be described in detail.

<Photopolymerizable composition> The photopolymerizable composition of the present invention contains at least a polymerizable compound and a compound represented by the following general formula (1). Contains components.

(Polymerizable Compound) The polymerizable compound is not particularly limited, and may be any of low molecular weight (monomer) to high molecular weight (oligomer) having a polymerizable site in the structure. It can be appropriately selected according to the purpose. Specifically, for example, a compound having at least one ethylenically unsaturated double bond in a molecule, an epoxy compound, a cyclic ether compound, an oxetane compound, a cyclic thioether compound, a spiroorthoester compound, a spiroorthocarbonate compound, and the like can be given. Can be

Among them, compounds having at least one ethylenically unsaturated double bond in the molecule are preferable, for example, acrylic acid such as acrylic acid esters and acrylamides and salts thereof, methacrylic acid esters, methacrylamides and the like. Methacrylic acid and salts thereof, maleic anhydride, maleic esters, itaconic acid, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, aryl ethers, allyl esters, maleimide And the like.

Examples of the monomer having a double bond include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
Examples thereof include an alkyl or hydroxyalkyl acrylate or methacrylate such as hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate or ethyl methacrylate. Also advantageous are silicone acrylates. Besides, acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl ester such as vinyl acetate, vinyl ether such as isobutyl vinyl ether, styrene, alkyl- and halostyrene, N
-Vinylpyrrolidone, vinyl chloride or vinylidene chloride and the like.

Examples of the monomer containing two or more double bonds include diacrylates such as ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and bisphenol A, and 4,4'-bis ( 2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2- (Acryloylethyl) isocyanurate and the like.

Examples of polyunsaturated compounds having a relatively high molecular weight (oligomer) 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.

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

As said polyols, aromatic and, in particular, aliphatic and cycloaliphatic polyols are preferred. Other suitable polyols include polymers and copolymers containing hydroxyl groups in the polymer chains or side chains (eg, polyvinyl alcohol and copolymers thereof or polyhydroxyalkyl methacrylates or copolymers thereof), oligoesters having hydroxyl end groups, and the like. No. As the polyepoxide, for example, the above polyols, especially aromatic polyols,
And those based on epichlorohydrin.

As the aromatic polyol, for example,
Hydroquinone, 4,4'-dihydroxydiphenyl,
2,2-di (4-hydroxyphenyl) propane, novolak and resorcin.

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

The polyols can be partially or completely esterified with one carboxylic acid or with a different unsaturated carboxylic acid, and the free hydroxyl groups in the partial esters can be modified, for example 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 trisitaconate, 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 having, 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 having further amino groups, preferably in the side chain, and oligoamides having amino terminal groups 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.

[0037] Polybutadienes and polyisoprenes and their copolymers are known. Examples of suitable comonomers are olefins such as ethylene, propene, butene and hexene, (meth) acrylate, 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 photopolymerizable composition. In the case of using the color image forming apparatus, a portion that promotes a coloring reaction of a coloring component constituting the image portion or a portion that suppresses coloring may be provided. These will be described later.

The content of the compound having an ethylenically unsaturated bond is usually in the total mass of the photopolymerizable composition.
It is 10 to 99% by mass, preferably 30 to 95% by mass.

(Compound Represented by General Formula (1)) The photopolymerizable composition of the present invention contains a compound represented by the following general formula (1) as a spectral sensitizing dye. The dye has a function of spectrally sensitizing a compound (radical or cation generator) capable of generating a radical or a cation. Therefore, when visible to infrared light corresponding to the absorption of the dye is irradiated, even when a radical or cation generator having no absorption is contained in this region, generation of radicals or cations from the generator is suppressed. Can be promoted.

[0041]

Embedded image

In the general formula (1), R ¹ is a hydrogen atom,
It represents an alkyl group or an aralkyl group which may have a substituent. The alkyl group preferably has 1 to 30 carbon atoms,
1-12 are more preferred. Examples of such alkyl groups include methyl, ethyl, methyl, ethyl, n-
Examples thereof include a propyl group, an i-propyl group, an n-butyl group, an n-octyl group, a 2-ethylhexyl group, a decyl group, and an octadecyl group.

When the alkyl group has a substituent, examples of the substituent 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 a compound having 30 or less carbon atoms. An alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group), an alkylsulfonylaminocarbonyl group having 30 or less carbon atoms,
Arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy Group),
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,
2-naphthoxy group, etc.), 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,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc., aryl group having 30 or less carbon atoms (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group) And the like, 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, 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 G ⁺ described below.

Examples of the alkenyl group represented by R ¹ include linear, branched and cyclic alkenyl groups. The alkenyl group preferably has 2 to 30 carbon atoms, and preferably has 2 to 30 carbon atoms.
~ 20 is more preferable. The alkenyl group may be a substituted alkenyl group having a substituent or an unsubstituted alkenyl group, and the preferred range of the number of carbon atoms in the alkenyl portion of the substituted alkenyl group is the same as that in the case of the 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 represented by R ¹ include linear, branched and cyclic alkynyl groups. The alkynyl group preferably has 2 to 30 carbon atoms, and preferably has 2 to 30 carbon atoms.
~ 20 is more preferable. The alkynyl group may be a substituted alkynyl group having a substituent or an unsubstituted alkynyl group, and the preferred range of the number of carbon atoms in the alkynyl portion of the substituted alkynyl group is the same as that in the case of the 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 represented by R ¹ include linear, branched and cyclic aralkyl groups.
To 30 are preferable, and 7 to 20 are more preferable. Specific examples include a benzyl group and a phenethyl group. The aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group.

In the general formula (1), Ar represents an aromatic group or a heterocyclic group which may have a substituent, and the aromatic group may be condensed. When Ar represents an aromatic group, examples thereof include an aryl group and a substituted aryl group. As carbon number of an aryl group, 6-30 are preferable, and 6-20 are more preferable. The preferred range of the carbon number of 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-
And a naphthyl group.

When Ar represents a heterocyclic group, examples of the heterocyclic group include a pyridyl group, a pyrimidinyl group, a furyl group and a triazinyl group.

In the general formula (1), R ² and R ³ each independently represent a hydrogen atom, an alkyl group which may have a substituent,
Represents an aralkyl group, an aryl group, an alkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, an aralkylthio group, or an arylthio group, and R ² and R ³ may be linked to form a ring.

The alkyl group represented by R ² and R ³ includes a linear, branched or cyclic alkyl group, and preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.
Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a 2-ethylhexyl group, a cyclohexyl group, an octadecyl group, and the like.

The aralkyl groups represented by R ² and R ³ include:
A linear, branched, or cyclic aralkyl group is mentioned, and as a carbon number, 7-30 are preferable and 7-20 are more preferable. Specific examples include a benzyl group and a phenethyl group. The aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group.

The aryl group represented by R ² and R ³ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. Examples of such aryl groups include phenyl, α-naphthyl, β-naphthyl and the like.

The alkyloxy group represented by R ² and R ³ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Examples of such an alkyloxy group include a methoxy group, an ethoxy group, a 2-ethylhexyloxy group, and a phenoxyethoxy group.

The aralkyloxy group represented by R ² and R ³ preferably has 7 to 12 carbon atoms, more preferably 7 to 10 carbon atoms. Examples of such an aralkyloxy group include a benzyloxy group and a phenethyloxy group.

The aryloxy group represented by R ² and R ³ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. Examples of such an aryloxy group include a phenoxy group, a 4-methylphenoxy group, and an α-naphthyloxy group.

The alkylthio group represented by R ² and R ³ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Examples of such an alkylthio group include a methylthio group, an ethylthio group, an n-butylthio group, a 2-ethylhexylthio group, and the like.

The aralkylthio group represented by R ² and R ³ preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms. Examples of such an aralkylthio group include a benzylthio group and a phenethylthio group.

The arylthio group represented by R ² and R ³ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. Examples of such arylthio groups include phenylthio, 4-methylphenylthio, α-naphthylthio, and the like.

In the general formula (1), X represents a hydrogen atom, an alkyl group, an alkyloxy group, an alkenyl group, an alkynyl group, an alkenyloxy group, an alkynyloxy group, an alkylamino group, or a halogen atom.

The alkyl group represented by X is the same as the alkyl group represented by R ¹ .

The alkyloxy group, alkenyl group, alkynyl group, alkenyloxy group and alkynyloxy group represented by X are the same as those described above for R ² and R ³ .

The alkylamino group represented by X preferably has 1 to 30 carbon atoms. Examples of such an alkyloxy group include a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a dioctylamino group, a didecylamino group, and the like.

Hereinafter, specific examples of the compound represented by Formula (1) (Exemplary Compound Nos. 1 to 40) are shown, but the present invention is not limited thereto.

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

The content of the compound represented by the general formula (1) in the photopolymerizable composition is 0.001 to 0.5 parts by mass with respect to 1 part by mass of a radical generator described later. Preferably, 0.01 to 0.3 parts by mass is more preferable. By setting the content to 0.001 to 0.5 parts by mass, the photopolymerization sensitivity can be improved, and the decolorization of the dye component can be performed in a short time. The compound represented by the general formula (1) may be used alone or in combination of two or more.

As long as the effects of the present invention are not impaired,
For the purpose of adjusting the photosensitive wavelength, a spectral sensitizing dye other than the compound represented by the general formula (1) may be contained. Examples of the other spectral sensitizing dye include, for example, methine dye, polymethine dye, triarylmethine dye, indoline dye, azine dye, xanthene dye, cyanine dye, hemicyanine dye, rhodamine dye, azomethine dye, azo dye, oxonol dye, Merocyanine dyes,
Known dyes such as an oxazine dye, an acridine dye, and a coumarin dye are exemplified.

As described above, by containing the compound represented by the general formula (1), the photopolymerization sensitivity of the photopolymerizable composition can be improved, and not only ultraviolet light but also visible light to red High sensitivity to external light can be achieved. Therefore, as described later, even when used for a recording material of a completely dry processing system that does not use a developer or the like, coloring of a non-image portion (background portion) of a formed image is reduced, and a clear and high-contrast image is obtained. Can be formed.

(Compound capable of generating a radical or a cation) In the photopolymerizable composition of the present invention, a radical is generated by interacting with the compound (spectral sensitizing dye) represented by the general formula (1). The resulting compound (hereinafter sometimes referred to as "radical generator") and the compound capable of generating a cation by interacting with the compound represented by formula (1) (hereinafter sometimes referred to as "cation generator"). .) (Hereinafter sometimes referred to as "radical or cation generator" including both of them). The radical or cation generator includes one that generates at least one of a radical and a cation and generates both. The radical or cation generator interacts with the generator when a spectral sensitizing dye (such as a compound represented by the general formula (1)) present in the vicinity thereof absorbs light, and efficiently reacts with the radical or cation generator. It has a function of generating a cation and initiating a polymerization reaction of a nearby polymerizable compound.
Therefore, by coexisting the generator with a spectral sensitizing dye, it is possible to achieve high sensitivity by sensitively irradiating light in the spectral absorption wavelength region, and to use any light source in the visible light to infrared light region. To control the generation of radicals or cations.

Among the above, a radical generator is preferred from the viewpoint of polymerization sensitivity. As the radical generator, one or more kinds can be selected and used from radical generators capable of initiating polymerization of a polymerizable compound contained in the photopolymerizable composition. For example, the following compounds are included.

Benzophenone, camphorquinone, 4,
4-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4 '
-Dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzylanthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone Bisacylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, acylphosphine oxides such as Lucirin TPO, α-hydroxy or α-aminoacetophenones, α-hydroxycycloalkylphenylketone , Aromatic ketones such as 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;
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, tertiary-butylperoxybenzoate, a, a'-bis (tertiary-butylperoxyisopropyl) benzene, dicumyl peroxide, 3,3 ', 4,4'-tetra- (tertiary-butylperoxycarbonyl) ) Japanese Patent Application Laid-Open No.
Organic peroxides described in No. 9-189340;

Azinium salts described in US Pat. No. 4,743,530; organic boron compounds; phenylglyoxalic esters such as methyl phenylglyoxalate; bis (η ^{5, 2} -cyclopentadien-1-yl) ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like; η ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluoro Iron allene complexes such as phosphate (1-); iodonium salts such as diaryliodonium salts such as diphenyliodonium salts; and sulfonium salts such as triarylsulfonium salts such as triphenylsulfonium salts.

For more detailed examples of the above-mentioned radical generators and examples of other types of radical generators, see JP-A-10-45816, paragraph [0067].
To [0132]. Further, among the above radical generators, sulfonium salts, iodonium salts, iron allene complexes, and the like are known to be compounds that generate radicals and also generate cations.

As the radical generator, a material composed of 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 kinds, a combination of 4,4′-bis (diethylamino) benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, Alternatively, a combination of 4,4′-bis (diethylamino) benzophenone and 2,4,5-triarylimidazole dimer, or a combination of a coumarin compound and 2,4,5-triarylimidazole dimer is used. Is preferred. Further, it is particularly preferable to use a combination of a coumarin compound, a 2,4,5-triarylimidazole dimer, and an organic boron compound.

Of the above radical generators,
In terms of being able to generate radicals effectively by interacting with the dye and increasing the sensitivity, an organic boron compound, an iodonium salt, a sulfonium salt, an iron allene complex, an S-triazine derivative having a trihalogen-substituted methyl group, Organic peroxides, titanocene, 2,4,5-triarylimidazole dimer, or azinium salts are preferred, and organic boron 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 organic boron compound include a compound represented by the following general formula (A) and “chemical chemistry of a functional dye”.
(1981, CMC Publishing Co., pp. 393 to 416), and a spectral sensitizer having a cationic dye described in “Coloring Material” (60 [4] 212-224 (1987)) as a cation moiety in the structure. Dye-sensitive organic boron compounds are also included. As the above-mentioned spectral sensitizing dye-based organic boron compound,
Compounds described in JP-A-2-143044, JP-A-1-138204, JP-A-6-505287, JP-A-4-261406 and the like can be mentioned.

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 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.

Among the organoboron compounds, compounds represented by the following general formula (A) are particularly preferred.

Embedded image

[0088] In the general formula ^{_{(A), R a 1,}} R a 2, R a 3 , and R
_a ⁴ is each independently an aliphatic group, an aromatic group, a heterocyclic group,
Or an ^{_{Si (R a 5) (R}} a 6) -R a 7. If R _a ¹ ~R _a ⁴ represents an aliphatic group, as the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, substituted alkynyl group, an aralkyl group,
Or a substituted aralkyl group, among which an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable,
Alkyl groups and substituted alkyl groups are particularly preferred. 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 a linear, branched and cyclic alkyl group. 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 dodecylthio group, etc.), an aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), a nitro group, having 30 or less carbon atoms. Alkyl group, 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,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc., aryl group having 30 or less carbon atoms (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group) And the like, 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, 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 G ⁺ described below.

Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups. The alkenyl group preferably has 2 to 30 carbon atoms, and 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. 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.

[0095] The case where R _a ¹ ~R _a ⁴ 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.

[0096] If R _a ¹ ~R _a ⁴ 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 ⁴ represents an aryl group having a substituent. Among them, as the heterocyclic group represented by R _a ¹ ~R _a ^4, 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.

[0097] If R _a ¹ ~R _a ⁴ represents ^{_{-Si (R a 5) (R}} a 6) -R a 7, R a 5, R a 6 and R _a ^7, is an aliphatic independently Represents an aromatic group. The aliphatic group and the aromatic group are represented by R
_a ^{1 to} R _a ⁴ have the same meanings as the aliphatic group and the aromatic group,
Preferred examples are also the same.

[0098] 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.

[0099]

Embedded image

In the ring of the above (C1), R
_b represents a divalent group shown below.

Embedded image

[0102] Among the above general formula (A) an organic boron compound represented by the terms of the R _a ¹ to R preferably has at least one of alkyl groups of _a ^4, improvement in sensitivity and preservability And a triarylalkyl-type organoboron compound in which one is an alkyl group and the other three are aryl groups are more preferred. 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. 36
~ +2.58 is 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 3-fluorophenyl group, 4-fluorophenyl group, 2-fluorophenyl group, 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.

The anion part of the general formula (A) includes
For example, tetramethyl borate, tetraethyl borate, tetrabutyl borate, triisobutyl methyl borate, di-n-butyl-di-t-butyl borate, tri-m-chlorophenyl-n-hexyl borate, triphenyl methyl borate, triphenyl ethyl Borate,
Triphenylpropyl borate, triphenyl-n-butyl borate, trimesityl butyl borate, tolyl isopropyl borate, triphenylbenzyl borate, tetra-m-fluorobenzyl borate, triphenylphenethyl borate, triphenyl-p-chlorobenzyl borate, Triphenylethenylbutyl borate, di (α-naphthyl) -dipropyl borate, triphenylsilyltriphenylborate, tritolylsilyltriphenylborate, tri-n-butyl (dimethylphenylsilyl) borate, diphenyldihexylborate, tri- m-fluorophenylhexyl borate,
Tri (5-chloro-4-methylphenyl) hexyl borate, tri-m-fluorophenylcyclohexyl borate, tri- (5-fluoro-2-methylphenyl) hexyl borate and the like can be mentioned.

In the general formula (A), G ⁺ 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.

As the quaternary ammonium cation,
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 the above G ⁺ , paragraphs [0020] to [00] of JP-A-9-188686.
38].

In each cationic compound (exemplary compound) 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 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.

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

The content of the radical or cation generator in the photopolymerizable composition is preferably 0.01 to 20% by mass based on the content of the polymerizable compound.
0.1-10 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.

(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 preferably added in an amount of 0.01 to 20% by mass, more preferably 0.2 to 15% by mass, based on the total weight of the photopolymerizable composition,
It is particularly preferable to add 0.5 to 10% by mass.

Specific examples of the above-mentioned 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 from 5 to 95% by mass, more preferably from 10 to 90% by mass, and more preferably from 15 to 90% by mass, based on the total solid content.
~ 85% by weight is most preferred. The choice of the binder is
This is done depending on the field of application and the properties required for that field, such as developing ability in aqueous or organic solvent systems, adhesion to substrates 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) Acetobutyrate, 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, polyvinyl pyrrolidone, styrene-maleic acid copolymer hydrolysate, sodium polystyrene sulfonate, sodium alginate and the like can also be mentioned.
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, such as 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 the additives are disclosed 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, it is more preferable to appropriately select a light source having a wavelength suitable for the absorption wavelength of the photopolymerizable composition, as the light source that can be used for decoloring the photopolymerizable composition and the recording material described below. . Specifically, mercury lamps, ultra-high pressure mercury lamps, electrodeless 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 compound represented by the general formula (1) as the spectral sensitizing dye, an image can be formed with high sensitivity not only when using ultraviolet light but also when using visible light to infrared light. Can be formed.

<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 that reacts with the color-forming component A to form a color, 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 this 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 coloring component A contained in the microcapsules and the coloring component B having a site in the molecule that reacts with the coloring 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 are transferred 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 erased.

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 comprises a color-forming component A
And at least the photopolymerizable composition of the present invention containing the coloring component B for coloring the coloring component A. Here, when the positive-type light- 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 the coloring component A, and the light irradiation part does not develop color.

The recording material according to the second embodiment 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 (reaction-suppressing site) that suppresses the reaction with a compound.

The image formation in the case where the recording material of the second embodiment is applied to a negative-type light- and heat-sensitive recording material in which the color-forming component A is encapsulated in heat-responsive microcapsules is shown below as an example. In the negative-type light- and heat-sensitive recording material of this embodiment, as in the first embodiment, the microcapsules are impermeable to substances at normal temperature, do not come into contact with the coloring components A and B, and are in a non-coloring state. . When the light and heat sensitive recording material is irradiated with light in an imagewise 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 color-forming component B penetrates into the microcapsules (and / or the color-forming component A is released outside the microcapsules). However, at the same time, in the non-light-irradiated portion, the polymerizable compound also penetrates 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, the polymerizable compound (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 color is formed only in the light-irradiated portion. 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 with 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 contains at least 1) a polymerizable compound and 2) a compound represented by the general formula (1) (a decolorizable spectral sensitizing dye). If necessary, 3) a compound capable of generating a radical or a cation by interacting with the dye of the above 2) (radical or cation generator), and 4) other components. Specifically, the recording material of the present invention preferably includes the photopolymerizable composition of the present invention described above, and preferably includes the above-described item 3). When the photopolymerizable composition is irradiated with light, the spectral sensitizing dye absorbs light and interacts with the radical generator, so that 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 may be contained in the photopolymerizable composition. As in the recording material of the first embodiment,
At least one of them may be a coloring component B having a site for coloring the coloring component A. In this case, 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. Coloring component B to be colored
A polymerizable compound having a site that suppresses the reaction with 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 a long-chain fatty acid iron salt such as ferric stearate and ferric myristate and a phenol 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, 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 and 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.

(B) A combination of a higher aliphatic heavy metal salt 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. (S) 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) A combination of a pigment precursor and an acid or a base (a combination formed by a 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 in thermal paper or pressure sensitive paper, phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, Various compounds such as spiropyran-based compounds, pyridine-based compounds, pyrazine-based compounds, and fluorene-based compounds can be exemplified.

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, p-nitrobenzyl leucomethylene blue and the like. 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 the spiropyran compound 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 developing cyan, magenta and yellow, the 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, which are known from heat-sensitive paper and pressure-sensitive paper.
Examples thereof include salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolak resins, metal-treated novolak resins, and electron accepting compounds such as metal complexes.
Specifically, Japanese Patent Publication No. 40-9309, Japanese Patent Publication No. 45-1
No. 4039, JP-A-52-140483, JP-A-48
JP-A-51510, JP-A-57-210886, JP-A-58-87089, JP-A-59-11286, JP-A-60-176799, JP-A-61-95988, and the like.

Of 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 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 the 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,
Examples thereof include compounds that can be synthesized with reference to the zinc halide N-vinylimidazole complex described in JP-A-62-1708 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.

[0151]

Embedded image

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-hydroxybenzoic acid ester
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.

When 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, a sufficient color density may not be obtained.

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 heterocyclic 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.

Details of the coupler compound are described in JP-A No. 4-20 / 1990.
No. 1483, Japanese Unexamined Patent Application Publication No. 7-223267, Japanese Unexamined Patent Application 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 is used for various purposes such as hue adjustment.
A plurality of types can be used in combination.

Specific examples of the coupler having a polymerizable group are shown below, but the present invention is not limited thereto.

[0174]

Embedded image

[0175]

Embedded image

[0176]

Embedded image

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

[0180]

Embedded image

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 dispersing the solid in a solid 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 disclosed 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 a microcapsule 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 microcapsule as the color forming component A, the diazo compound and the coupler are used in a combination in which a color reaction does not occur 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.

[0194] 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.

When the photopolymerizable monomer D1 is used as the polymerizable color formation suppressing compound, the amount of the photopolymerizable monomer D1 used may be ₁ % by mass of the electron donating compound used in combination with the coupler compound having no 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, sometimes referred to as “photopolymerizable monomer D ₂ ”).

[0197] As the photopolymerizable monomer D _2, for example, styrene sulfonylamino acid, vinyl benzyloxy phthalate, beta-methacryloxy ethoxy salicylic acid zinc, beta-acryloxy ethoxy salicylic acid zinc, vinyloxy ethyl oxybenzoate, beta -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, 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.

[0200] 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, the recording layer preferably contains the color-forming component A in a state of being encapsulated in microcapsules. As a method for microencapsulation, a conventionally known method can be used. For example, U.S. 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, an interfacial polymerization method, a method by polymer precipitation described in U.S. Pat. Nos. 3,418,250 and 3,660,304, and an 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 used as 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 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.

As the water-soluble polymer, for example, gelatin, polyvinylpyrrolidone, polyvinyl alcohol and the like can be mentioned. 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 include those 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 the 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.

Further, 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 performed 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.

[0211] The photopolymerizable composition of the present invention may contain, in addition to the above-mentioned 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 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, and the like, 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.

The recording material of the present invention is suitably used for applications such as lithographic printing, a resin convex plate, a resist or photomask for producing a printed substrate, a black and white or color transfer coloring sheet or a coloring sheet. For example, when the recording material of the present invention is applied to a light- and heat-sensitive coloring sheet, each component is individually or in combination of several types, and dissolved or dispersed in an appropriate solvent to prepare a solution or dispersion. The mixture can be prepared by mixing and applying the mixture as a coating liquid on a support such as paper or a plastic film and drying. For example, when microencapsulating a predetermined component, a microcapsule dispersion in which any component is encapsulated is prepared, and a liquid in which other components are dispersed or dissolved in a solvent is separately prepared. They can be mixed to form a coating liquid. In preparing the coating solution, each component can be brought into a preferable dispersed state using a homogenizer or the like. The coating and drying can be performed by a conventionally known method.

With the recording material of the present invention, an image can be formed by performing a heat development treatment simultaneously with or after the exposure for forming a latent image. As a heating method at the time of the heat development processing, a conventionally known method can be used. Generally, the heating temperature is 80 to 20.
0 ° C is preferable, and 85 to 130 ° C is more preferable. The heating time is preferably from 1 second to 5 minutes, more preferably from 3 seconds to 1 minute.

After the heating and developing treatment, the entire surface of the recording layer is irradiated with light to polymerize the unpolymerized region and fix the formed image, and to remove the white color of the background portion such as the spectral sensitizing dye remaining in the recording layer. It is preferable to decolor, decompose or deactivate the component that reduces the property. The recording material of the present invention can prevent the residual color of the background portion and the like, and can further improve the whiteness of the background portion by a shorter image fixing process than the conventional recording material.

When an image is formed by the above method, the sensitivity can be further improved by providing a process of uniformly preheating the entire surface of the material at a predetermined temperature lower than the color development temperature during the image formation. Also, not only the recording method,
It can be used for other known recording methods.

As described above, in a completely dry processing system that does not require the use of a developer or the like and does not generate waste, highly sensitive image recording using not only ultraviolet light but also visible light to infrared light can be performed. It is possible to form a clear and high-contrast black and white or color image.

[0221]

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”.

(Examples 1 to 13) As shown in Table 1 below, a photopolymerizable composition having the following composition was prepared using the above exemplified spectral sensitizing dye (compound represented by the general formula (1)) and an organic boron compound. Was prepared. [Composition of 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-Spectral sensitizing dye (the above-mentioned compound; the following table) 1 × 10 ^-4 mol ・ The following organoboron compound (see Table 1 below) ・ ・ ・ ・ ・ ・ ・ 6 × 10 ^-4 mol ・ 2- (o-chlorophenyl) -4,5 -Diphenylimidazole dimer 2 × 10 ^-3 mol methanol 6 g Borates (1) to (3) in Tables 1 and 2 below (organic The structure of (boron compound) is shown below.

[0223]

Embedded image

Each of the prepared photopolymerizable compositions was added to 100
2 μm on polyethylene terephthalate film
And dried at 100 ° C. for 5 minutes. Further, the following coating solution (1) for a protective layer was applied in a thickness of 1 μm and dried at 100 ° C. for 2 minutes to form a photosensitive material (1) to
(13) was produced.

[Composition of Coating Solution (1) for Protective Layer] Water 98 g Polyvinyl alcohol 98 g 1.7g Hydroxypropyl methylcellulose 1.7g Polyvinylpyrrolidone・ ・ ・ ・ 8.7g

(Comparative Examples 1 to 3) The spectral sensitizing dye (Exemplary Compound No. 1) used in Example 1 was replaced with one of the following spectral sensitizing dyes d-1 to d-3 as shown in Table 1 below. Except that the photosensitive materials (14) to (1) were changed in the same manner as in Example 1.
6) was produced.

[0227]

Embedded image

<Image formation and evaluation>
The 13 photosensitive materials (1) to (13) and the photosensitive materials (14) to (16) of Comparative Examples 1 to 3 were respectively exposed using a vacuum frame apparatus. Exposure to the photosensitive material is performed using a step wedge (density step 0.15, density step number 1 to 15 steps, "Fuji Step Guide P" (manufactured by Fuji Photo Film Co., Ltd.) and "SC38 filter" Through a sharp cut filter (manufactured by Fuji Photo Film Co., Ltd.) for 10 seconds with a 500 W xenon lamp (manufactured by Ushio). After the exposure, each of the photosensitive materials was developed using a developer having the following composition.

[Composition of Developer]-Anhydrous sodium carbonate ... 10 g-Butyl cellosolve ...・ ・ ・ ・ ・ 5g ・ Water ・ ・ ・ ・ ・ ・ ・ 1l

[0230] By the above development, the amount of exposure to the region corresponding to the high step number of the step wedge was small, so that the photopolymerizable composition in the region was eluted into the developer and the polyethylene terephthalate (PET) surface was exposed. For the photosensitive material of each example, the photopolymerizable composition was completely eluted and PET
The area where the surface was exposed was examined, and the step number (clear step number) of the step wedge corresponding to the area having the highest exposure was obtained. The higher the determined number of steps, the higher the sensitivity of the photosensitive material. The results are shown in Table 1 below. In addition, when the photopolymerizable composition was eluted into the developer over all the exposed areas due to low sensitivity, the result was indicated as "flow" in the table. still,
The number (No.) in the column of the spectral sensitizing dye in Table 1 below is the number (N) of the exemplified compound represented by the aforementioned general formula (1).
o.). Hereinafter, the same applies to Table 2.

[0231]

[Table 1]

From the results shown in Table 1, the photosensitive materials (1) to (13) of this example using the compound represented by the general formula (1) as the spectral sensitizing dye can form images with high sensitivity. Was completed. On the other hand, the photosensitive materials (14) to (1) of Comparative Examples, in which the spectral sensitizing dye specified in the present invention was not used.
In 6), sufficient sensitivity could not be obtained.

<Preparation of photosensitive and heat-sensitive recording material> (Example 14)-Preparation of microcapsule solution containing electron-donating colorless dye (1)-The following electron-donating colorless dye (1) having a yellow color was added to 18.4 g of ethyl acetate. ) 4.4 g was dissolved in a capsule wall agent (trade name: Takenate D-110N, Takeda Pharmaceutical Co., Ltd.)
21 parts and capsule wall material (trade name: Millionate MR)
200, manufactured by Nippon Polyurethane Industry Co., Ltd.). The resulting solution was treated with 8% phthalated gelatin 5
It was added to a mixture of 2 g and 0.3 g of a 10% sodium dodecylbenzenesulfonate solution, and then emulsified and dispersed at a temperature of 20 ° C. to obtain an emulsion. 54 g of a 1.1% tetraethylenepentamine aqueous solution was added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring. After 2 hours, the average particle size of the electron-donating colorless dye (1) as a core was measured. A microcapsule solution having a diameter of 0.5 μm was obtained. Further, it was adjusted by adding water so that the solid content became 25%.

[0234]

Embedded image

-Preparation of Photopolymerizable Composition Emulsion (1)-100.0 g of a mixture of the following electron-accepting compounds (1) and (2) having a polymerizable group (mixing ratio: 50:50)
And 0.1 g of the following thermal polymerization inhibitor (ALI) in 125.0 g of isopropyl acetate (4.3% solubility in water).
The mixture was dissolved at a temperature of ° C to obtain a mixed solution I. In this mixed solution I,
Hexaarylbiimidazole (1) [2,2'-
18.0 g of bis (2-chlorophenyl) -4,4 ', 5,5'tetraphenyl-biimidazole]
The mixture was dissolved at 2 ° C. to obtain a mixed solution II. The above mixed solution I
I was added to 300.0 g of an 8% gelatin aqueous solution and the following 10%
The surfactant (1) was added to a mixed solution of 17.4 g of an aqueous solution, and the mixture was emulsified at 10,000 rpm for 5 minutes using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion of the photopolymerizable composition (1). ) Got. Then, after performing a desolvation treatment at 40 ° C. for 3 hours, the solid content was adjusted to 30%.

[0236]

Embedded image

[0237]

Embedded image

<Preparation of Coating Solution for Recording Layer> -Preparation of Coating Solution (I) for Recording Layer- 6.3 parts of the microcapsule solution containing the electron-donating colorless dye (1), and an emulsion of the photopolymerizable composition (1) 9.5 parts,
1.8 parts of a 15% aqueous gelatin solution were mixed, and 6.3 parts of water were further added to prepare a recording layer coating solution (I).

<Preparation of Coating Solution for Protective Layer> 8.8 parts of an 18% gelatin aqueous solution, 7.0 parts of distilled water, 0.4 part of the following 2% surfactant (2) aqueous solution, and 2% of the following 2% surfactant 1.2 parts of an aqueous solution of an activator (3), 8.8 parts of a 2% aqueous solution of a vinyl sulfone-based compound (hardening agent), and 20% of Julimer AC1
This was mixed with 1.8 parts of 0LA (polyacrylic acid; manufactured by Nippon Pure Chemical Co., Ltd.) to prepare a coating solution for a protective layer.

[0240]

Embedded image

On a 198 μm-thick WP support, using a coating bar, the dry weight of the entire coating layer was 4.8 g.
/ M ² , the recording layer coating solution (I) was applied and dried to form a recording layer. On the recording layer, the coating liquid (1) for the protective layer was applied by lamination using a coating bar such that the dry mass of the coating layer was 2 g / m ² ,
After drying, a light and heat sensitive recording material (a) of the present invention was obtained.

Examples 15 to 19 The spectral sensitizing dyes (Exemplary Compound No. 1) used in Example 14 were respectively replaced with the spectral sensitizing dyes (exemplary compounds represented by the general formula (1)) shown in Table 2 below. In the same manner as in Example 14, except that the organic boron compound (borate (3)) was added except for Example 18.
(F) was obtained.

(Comparative Examples 4 and 5) As in Example 14 except that the spectral sensitizing dye (exemplified compound No. 1) used in Example 14 was not added, as shown in Table 2 below. Photosensitive and heat-sensitive recording materials (g) to (h) were obtained.

The light and heat sensitive recording materials (a) to
Regarding (h), an image was formed as follows. Here, the photosensitive and heat-sensitive recording material (a) is shown as an example. The light- and heat-sensitive recording material (a) has a wavelength of 40 from the protective layer side.
Using a 5 nm semiconductor laser beam, the maximum irradiation energy was set to 12 mJ / cm ^2, and exposure was performed in a step wedge-like image shape such that the irradiation energy was changed gradually (exposure step). Subsequently, the photosensitive and heat-sensitive recording material (a) on which the latent image has been formed by the above exposure is heated on a hot plate at 110 ° C. for 10 seconds (color developing step), and the recording layer is further irradiated using a 38000 lux fluorescent lamp irradiator. Was irradiated with light for 30 seconds (fixing step). Then, the light and heat sensitive recording material (a) ~
In the recording layer of (f), yellow was clearly formed, and a step wedge-shaped yellow image having high whiteness in the background was obtained.

<Evaluation of Sensitivity> The sensitivity was calculated by calculating the energy required to form the background portion of each material (the energy required to form the background portion) and used as an index indicating the sensitivity. The smaller the value, the higher the sensitivity. The measurement results are shown in Table 2 below.

[0246]

[Table 2]

From the results shown in Table 2 above, Examples 14 to 1 using the compound represented by the general formula (1) as the spectral sensitizing dye were obtained.
In the light and heat sensitive recording materials (a) to (f) of No. 9, high sensitivity was obtained. On the other hand, the light and heat sensitive recording materials (g) to
In (h), high sensitivity was not obtained.

[0248]

According to the present invention, it is possible to provide a photopolymerizable composition which is sensitive to not only ultraviolet light but also visible light to infrared light. In addition, it is a completely dry processing system that does not require the use of a developer or the like and generates no waste, and enables high-sensitivity image recording using not only ultraviolet light but also visible light to infrared light, and is clear and high-performance. A recording material capable of forming a contrast black-and-white or color image can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/029 G03F 7/029 7/031 7/031 7/26 511 7/26 511 (72) Inventor Masanobu Takashima 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd. GA52 4J011 QA02 QA03 QA06 QA08 QA09 QA12 QA13 QA15 QA19 QA20 QA23 QA24 QA26 QA27 QA32 QA33 QA34 QA35 QA38 QA39 QA42 QA45 QA46 QB04 QB12 QB13 QB14 QB18 SA24 SA28 SABSA SAB SA28 SA75 SA76 SA78 SA80 SA83 SA85 SA86 SA87 SA88 UA02 UA06 VA01 WA01 4J031 CA02 CA06 CA69 CA83 CA85 CB04 CB05 CB06 CE03

Claims (11)

[Claims] 1. A polymerizable compound having the following general formula (1)
A photopolymerizable composition comprising at least one compound represented by the formula: Embedded image [In the general formula (1), R ¹ represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, or a heteroaromatic group;
Is an aromatic group or a heterocyclic group which may have a substituent, R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group which may have a substituent, Represents an aryl group, an alkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, an aralkylthio group, or an arylthio group, and R ² and R ³ may be linked to form a ring; X represents a hydrogen atom, an alkyl group, an alkyloxy group, an alkenyl group, an alkynyl group,
Represents an alkenyloxy group, an alkynyloxy group, an alkylamino group, or a halogen atom. ] 2. A compound comprising a polymerizable compound, a compound represented by the general formula (1), and a compound capable of generating a radical or a cation by interacting with the compound represented by the general formula (1). 2. The photopolymerizable composition according to 1. 3. The compound capable of generating a radical or a cation is an organic boron compound, an iodonium salt, a sulfonium salt, an iron allene complex, an S-triazine derivative, an organic peroxide, titanocene, a triarylimidazole dimer, and an azinium salt. The photopolymerizable composition according to claim 2, which is at least one selected from the group consisting of: 4. The photopolymerizable composition according to claim 2, wherein the compound capable of generating a radical or a cation is a triarylimidazole dimer and an organic boron compound. 5. A polymerizable compound having an ethylenically unsaturated bond, wherein the compound capable of generating a radical or a cation is a triarylimidazole dimer and / or an organic boron compound. 3. The photopolymerizable composition according to 2. 6. An organic boron compound represented by the following general formula (A):
The photopolymerizable composition according to any one of claims 3 to 5, which is a compound represented by the following formula: Embedded image [In the general formula (A), Ra ¹ , Ra ² , Ra ³ , and Ra ⁴ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, or Si.
(Ra ⁵ ) (Ra ⁶ ) -Ra ⁷ , wherein Ra ⁵ , Ra ⁶ and Ra ⁷ are
Each independently represents an aliphatic group or an aromatic group. G ⁺ represents a group capable of forming a cation. ] 7. A recording layer having a recording layer on a support, wherein the recording layer has a color-forming component A, a color-forming component B having a site that reacts with the color-forming component A to form a color, and And a photopolymerizable composition according to any one of the above. 8. The recording material according to claim 7, wherein at least one of the polymerizable compounds is a coloring component B. 9. The recording material according to claim 7, wherein the polymerizable compound is a color-suppressing compound having a site for suppressing the reaction between the color-forming components A and B in the same molecule. 10. The recording material according to claim 7, wherein the coloring component A is encapsulated in a microcapsule. 11. A first recording layer sensitized to light having a center wavelength λ ₁ , a second recording layer sensitized to light having a center wavelength λ ₂ and developing a color different from that of the first recording layer,... 8. A multi-layer structure in which the first, second,..., And i-th recording layers that are sensitive to light having the center wavelength λ _i and develop colors different from the i-th recording layer are stacked in this order. 11. The recording material according to any one of items 1 to 10.