JP2003005378A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive and heat sensitive recording material having excellent stability and preservability and further having enhanced photopolymerization sensitivity. SOLUTION: The recording material is obtained by disposing a recording layer containing a photopolymerizable composition containing a compound having a structure of formula (I) and a photopolymerization initiator, a color developing component A and a color developing component B which reacts with the component A to allow the component A to develop a color on a support. In the formula (I), X<1> and X<2> are each a heteroatom or halogen; R<a> and R<b> are each H, halogen, cyano or an organic residue; and X<1> and X<2> , R<a> and R<b> , or X<1> and R<a> or R<b> may combine with each other to form a cyclic structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light and heat sensitive recording material, and more particularly to a light and heat sensitive recording material having improved photopolymerization sensitivity.

[0002]

2. Description of the Related Art In recent years, as an image forming method using a photopolymerizable composition, an image forming system using a photosensitive microcapsule containing a photopolymerizable composition in a microcapsule has been proposed. For example, JP-A-57-124343
JP-A-57-179836 and JP-A-57-197.
No. 538, a dye by applying pressure to the whole of a color-developing sheet coated with a microcapsule containing a photopolymerizable composition comprising a vinyl compound and a photopolymerization initiator and a dye after exposure and overlaying with an image-receiving sheet. 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, one of the two components being contained in a microcapsule and the other. Is disclosed as a curable compound of the photocurable composition, or the other is contained outside the microcapsules together with the photocurable composition. 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 is illustrated.

As described above, the recording material using the photopolymerizable composition is capable of image recording in a completely dry system without using a developing solution, etc. It is very preferable.

[0005]

The problem common to all of these image forming materials is how the ON-OFF of the image can be enlarged in the above-mentioned various energy irradiated parts and non-irradiated parts, that is, image formation. It is both high sensitivity and storage stability of the material. Usually, the photoradical polymerization system has high sensitivity, but the sensitivity is greatly lowered due to the inhibition of polymerization by oxygen in the air. Therefore, a means for providing an oxygen barrier layer on the image forming layer is adopted. However, when an oxygen-blocking layer is provided, conversely, fogging occurs due to dark polymerization and the storage stability deteriorates. Therefore, achieving both high sensitivity and storage stability is a difficult problem, and the conventional technology has not obtained sufficiently satisfactory results, and a new technology that has never been achieved has been required.

As the most general radically polymerizable compound from the past, monomers, oligomers and polymers having a highly polymerizable acrylic acid ester group, acrylic acid amide group, methacrylic acid ester group, methacrylic acid amide group, etc. have been used. However, these compounds are subject to polymerization inhibition by oxygen, and therefore, when used in a photopolymerizable composition, the problems of achieving both sensitivity and storage stability cannot be achieved.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to use a method of converting a polymer image obtained by photocuring into a visible image by heat development, A light and heat sensitive recording material having improved photopolymerization sensitivity while maintaining storage stability.

[0008]

[Means for Solving the Problems] As a constituent component of a polymer, a compound (monomer) having an α-hetero-substituted methylacryl group or an α-halogen-substituted methylacryl group as a group having a polymerizability comparable to that of an acrylic type is known. ing.
These compounds are different from low-polymerizable itaconic acid groups and α-alkylacryl groups having a substituent at the same α-position, and the electronic and steric effects of the heteroatom or halogen atom substituted at the α-position. Is said to improve the polymerizability as a constituent of the polymer.

The present inventor has used a compound having a structure having a polymerizable group substituted with a hetero atom or a halogen atom at the α-position in a photopolymerizable composition together with a photopolymerization initiator to obtain a conventional radical polymerizable compound. It was found that the problem of the compound, that is, the influence of the above-mentioned inhibition of polymerization of oxygen can be significantly reduced, and that both the high sensitivity and the excellent storage stability, which are the problems peculiar to the photopolymerizable composition, can be solved.

Although the mechanism for reducing the effect of inhibiting the polymerization of oxygen is not clear, the compound having a structure represented by the general formula (I) in the present invention has a conventional acryl compound due to its α-position substituent effect. Although the polymerization growth rate constant is not so high compared to the methacrylic and methacrylic systems, the termination rate constant is extremely small, so it is difficult to react with oxygen during chain growth, and as a result, it is less susceptible to oxygen polymerization inhibition. It is thought to be.

As a result of intensive studies by the present inventors, by using a photopolymerizable composition containing a compound having a specific polymerizable group, stability and storability are excellent and recording with high polymerization sensitivity is achieved. The material has been completed.

Means for solving the above problems are as follows. <1> On a support, a photopolymerizable composition containing a compound having a structure represented by the following general formula (I) and a photopolymerization initiator, a color-forming component A, and a color-forming component A A recording material comprising a recording layer containing a color-forming component B for forming a color-forming component A.

[Chemical 2] [In the general formula (I), X ¹ and X ² each independently represent a hetero atom or a halogen atom. R ^a and R ^b are each independently
It represents a hydrogen atom, a halogen atom, a cyano group or an organic residue. Here, X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure. <2> The color-forming component A is an electron-donating dye precursor,
The recording material according to <1>, wherein the color-forming component B is an electron-accepting compound. <3> The coloring component A is a diazonium salt compound,
The recording material according to <1>, wherein the color-forming component B is a coupler compound. <4> The recording material according to <1>, wherein the coloring component A is a protected dye (or leuco dye) precursor, and the coloring component B is a deprotecting agent.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The recording material of the present invention is a photopolymerizable composition containing a compound having a structure represented by the following general formula (I) and a photopolymerization initiator in a recording layer provided on a support. The composition is characterized by containing a composition, a color-forming component A, and a color-forming component B that reacts with the color-forming component A to develop the color-forming component A.

[0014]

[Chemical 3] In formula (I), X ¹ and X ² each independently represent a hetero atom or a halogen atom. R ^a and R ^b each independently represent a hydrogen atom, a halogen atom, a cyano group or an organic residue.
Further, X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure.

(Compound Having Structure of General Formula (I)) The photopolymerizable composition of the present invention contains the compound having the structure represented by General Formula (I) as one of the essential components. First, the compound having the structure represented by formula (I) will be described in detail below. The structure represented by the general formula (I) may be a monovalent or divalent or higher valent substituent, and R ^a , R ^b , X ¹ in the general formula (I),
X ² may all represent a terminal group, and may itself be one compound. When the structure represented by the general formula (I) is a monovalent or divalent or higher valent substituent, at least one of R ^a , R ^b , X ¹ and X ^{2 in} the general formula (I) is Have more than one bond. Further, X ¹ and X ² may be a linking group having n linkable moieties, and n groups of the general formula (I) may be linked to the ends (n is 2 or more). Integer) (multimer).

Further, in at least one of X ¹ and X ² ,
It may be attached to the polymer chain. That is, the structure represented by the general formula (I) may be added as a side chain of the polymer chain. Here, examples of the polymer chain include linear organic high molecular polymers described later. Specifically, polyurethane, novolac, vinyl polymers such as polyvinyl alcohol, polyhydrostyrene, polystyrene,
Examples thereof include poly (meth) acrylic acid ester, poly (meth) acrylic acid amide, and polyacetal. These polymers may be homopolymers or copolymers.

In the general formula (I), X ¹ and X ² are
Represents a hetero atom or a halogen atom, which may serve as a terminal group or a linking group, and other substituents (wherein the substituents are the structure of formula (I) or the heavy chain as described above). (Including a combined chain). The hetero atom is preferably a non-metal atom, and specific examples thereof include an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom.

X ¹ is preferably a halogen atom or a group in which X ¹ is a linking group to which other substituents are linked, and examples thereof include a hydroxyl group, a substituted oxy group, a mercapto group, a substituted thio group and an amino group. , Substituted amino group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonato group,
It represents a substituted phosphonato group, a nitro group, or a heterocyclic group (provided that they are linked by a hetero atom).

X ² is preferably a halogen atom or a group in which X ² is a linking group to which another substituent is linked, and examples thereof include a hydroxyl group, a substituted oxy group, a mercapto group, a substituted thio group and an amino group. , A substituted amino group and a heterocyclic group (provided that they are linked by a hetero atom).

In the case where X ¹ or X ² is a linking group and another substituent is linked to it, n hydrogens are removed from these groups, and n linkable moieties are It may be a linking group having n, and n groups of the general formula (I) may be linked to the terminal (n is an integer of 2 or more). Further, X ¹ and X ² may be bonded to each other to form a ring structure.

R ^a and R ^b are each independently more preferably a hydrogen atom, a halogen atom, a cyano group, or an organic residue which may have a substituent and contains an unsaturated bond. Represents a hydrocarbon group, a substituted oxy group, a substituted thio group, a substituted amino group, a substituted carbonyl group or a carboxylate group, and R ^a and R ^b may combine with each other to form a cyclic structure.

Next, X ¹ in the general formula (I),
Specific examples of the above-mentioned substituents for X ² , R ^a and R ^b are shown below. The above-mentioned hydrocarbon group which may have a substituent and may contain an unsaturated bond includes an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group and an alkynyl group. And substituted alkynyl groups.

The alkyl group has 1 carbon atom.
Up to 20 linear, branched, or cyclic alkyl groups, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group,
Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s
-Butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group can be mentioned. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metal atomic group excluding hydrogen is used, and preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, Alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N- Diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N -Arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group,
N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group Group, N-arylureido group, N'-alkyl-N-alkylureido group,
N'-alkyl-N-arylureido group, N ', N'
-Dialkyl-N-alkylureido group, N ', N'-
Dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'- Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-
An N-arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N- Aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugated base group (hereinafter referred to as carboxylate), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group,
N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO
₃ H) and its conjugate base group (hereinafter, referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-
Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N −
Arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group ( -SO
₂ NHSO ₂ (alkyl)) and its conjugate base group, N-
Aryl acylsulfamoyl group (-SO ₂ NHS
O ₂ (allyl)) and its conjugate base group,

N-alkylsulfonylcarbamoyl group
(-CONHSO₂(Alkyl)) and its conjugate base
Group, N-arylsulfonylcarbamoyl group (-CON
HSO ₂(Allyl)) and its conjugate base group, alco
Xysilyl group (-Si (Oalkyl)₃), Arilo
Xysilyl group (-Si (Oallyl))₃), Hydroxy
Cysilyl group (-Si (OH)₃) And its conjugated base group,
Phosphono group (-PO₃H₂) And its conjugate base group (hereinafter,
Phosphonato group), dialkylphosphono group (-PO
₃(Alkyl)₂), A diarylphosphono group (-PO₃
(Aryl)₂), An alkylarylphosphono group (-P
O₃(Alkyl) (aryl)), monoalkylphos
Hono group (-PO₃H (alkyl)) and its conjugate base
Group (hereinafter referred to as alkylphosphonato group), monoary
Ruphosphono group (-PO₃H (aryl)) and its conjugate
Basic group (hereinafter referred to as arylphosphonato group), phospho
Nooxy group (-OPO₃H₂) And its conjugate base group (hereinafter
Later called phosphonatooxy group), dialkylphosphono
Oxy group (-OPO₃(Alkyl)₂), Diarylho
Suphonoxy group (-OPO₃(Aryl)₂), Alkyl
Arylphosphonooxy group (-OPO₃(Alkyl)
(Aryl)), monoalkylphosphonooxy group (-O
PO₃H (alkyl)) and its conjugate base group (hereinafter,
Alkylphosphonatooxy group), monoarylphos
Suphonoxy group (-OPO₃H (aryl)) and its
Conjugated base group (hereinafter referred to as arylphosphonatooxy group
), Cyano group, nitro group, aryl group, alkenyl
Group, an alkynyl group.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group and mesityl group. , Cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylcaphyl group Ba carbamoylphenyl group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group,
Examples thereof include a phosphonatophenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro- group.
Examples thereof include a 1-ethenyl group, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, and a phenylethynyl group.

As the above-mentioned acyl group (R ⁴ CO--),
Examples of R ⁴ include a hydrogen atom and the above-mentioned alkyl group, aryl group, alkenyl group and alkynyl group. On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to form a divalent organic residue. Can be a straight-chain alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. Specific examples of preferred substituted alkyl groups include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, an allyloxymethyl group, a phenoxymethyl group, a methylthiomethyl group, and a trimethylmethyl group. Ruthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group,
Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group,
Butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group Group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group,

[0029]

[Chemical 4]

Phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxy Propyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring, and specific examples include: Phenyl group, naphthyl group, anthryl group,
Examples thereof include a phenanthryl group, an indenyl group, an acenabutenyl group and a fluorenyl group, and among these, a phenyl group and a naphthyl group are more preferable.

The substituted aryl group is a group in which a substituent is bonded to an aryl group, and a group having a monovalent non-metal atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aryl group is used. To be Examples of preferable substituents include the above-mentioned alkyl groups, substituted alkyl groups, and the substituents described above for the substituted alkyl groups. Preferred specific examples of these substituted aryl groups include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxy group. Phenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group,
Methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxy Phenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group,
Allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-
Methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfa Moylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, Phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1 -Propenylmethyl group, 2 Butenyl, 2-methyl-allyl phenyl group, 2-methyl propenyl phenyl group, 2-propynyl phenyl group, 2-butynyl phenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group include those mentioned above. As the substituent of the substituted alkenyl group, the substituent in the above-mentioned substituted alkyl group is used,
On the other hand, as the alkenyl group, the above-mentioned alkenyl group can be used. Examples of preferred substituted alkenyl groups include

[0034]

[Chemical 5]

And the like. Examples of the alkynyl group include those mentioned above. As the substituent of the substituted alkynyl group, the substituent in the above-mentioned substituted alkyl group is used, while the alkynyl group can be the above-mentioned alkynyl group.

The heterocyclic group is a monovalent group obtained by removing one hydrogen atom on the heterocycle, and one hydrogen atom is further removed from the monovalent group, and the substituent group in the above-mentioned substituted alkyl group is bonded to the heterocyclic group. It is a monovalent group (substituted heterocyclic group) formed by Examples of preferred heterocycles include:

[0037]

[Chemical 6]

[0038]

[Chemical 7] Etc. can be mentioned.

As the substituted oxy group (R ⁵ O—), those in which R ⁵ is a monovalent non-metal atomic group excluding hydrogen can be used. Preferred substituted oxy groups are alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group. Examples of the alkyl group and the aryl group in these groups include those described above as the alkyl group, the substituted alkyl group, the aryl group and the substituted aryl group. Further, an acyl group (R
Examples of ⁶ CO-) include those in which R ⁶ is the aforementioned alkyl group, substituted alkyl group, aryl group or substituted aryl group. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group,
Benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, Morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyl Examples thereof include an oxy group, a naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group and a phosphonatoxy group.

As the substituted thio group (R ⁷ S-), those in which R ⁷ is a monovalent non-metal atomic group excluding hydrogen can be used. Examples of preferred substituted thio groups include an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, and an acylthio group. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group, those can be mentioned as shown as the substituted aryl group, R ⁶ acyl group in the acylthio group (R ⁶ CO-) in As described above. Of these, an alkylthio group and an arylthio group are more preferable. Specific examples of the preferred substituted thio group include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group and a methoxycarbonylthio group.

Substituted amino group (R ⁸ NH--, (R ⁹ )
The ^{(R 10) N-), R} 8, R 9, R 10 can be used a monovalent nonmetallic radical other than hydrogen. Preferred examples of the substituted amino group include N-alkylamino group, N, N
-Dialkylamino group, N-arylamino group, N, N
-Diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-
Alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-
Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-
Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N ' -Aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl Examples thereof include -N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group and N-aryl-N-aryloxycarbonylamino group.

Examples of the alkyl group and the aryl group in these groups include the above-mentioned alkyl group, substituted alkyl group, and those shown as the aryl group and the substituted aryl group. Examples of the acylamino group, N-alkylacylamino group, N- Acyl group in arylacylamino group (R
R ^{6 of 6} CO-) is as described above. Of these, more preferred are N-alkylamino groups, N,
Examples thereof include an N-dialkylamino group, an N-arylamino group and an acylamino group. Specific examples of the preferred substituted amino group include a methylamino group, an ethylamino group, a diethylamino group, a morpholino group, a piperidino group, a pyrrolidino group, a phenylamino group, a benzoylamino group and an acetylamino group.

As the substituted carbonyl group (R ¹¹ —CO—), those in which R ¹¹ is a monovalent non-metal atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, Examples thereof include N, N-diarylcarbamoyl group and N-alkyl-N-arylcarbamoyl group. Examples of the alkyl group and aryl group in these groups include the alkyl group, the substituted alkyl group, the aryl group and the substituted aryl group described above. Among these, more preferable substituted carbonyl groups include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-aryl. Examples thereof include a rucarbamoyl group, and more preferable examples thereof include a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-phenylcarbamoyl group,
Examples thereof include N, N-diethylcarbamoyl group and morpholinocarbonyl group.

As the substituted sulfinyl group (R ¹² —SO—), those in which R ¹² is a monovalent nonmetallic atomic group can be used. Preferred examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group. Group, and an N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these groups include the alkyl group, the substituted alkyl group, the aryl group and the substituted aryl group described above. Among these, more preferable examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples thereof include a benzylsulfinyl group and a tolylsulfinyl group.

As the substituted sulfonyl group (R ¹³ —SO ₂ —), one in which R ¹³ is a monovalent nonmetallic atomic group can be used.
More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and aryl group in these, the aforementioned alkyl group,
Examples thereof include a substituted alkyl group, an aryl group, and a substituted aryl group. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

[0046] The sulfonato group (-SO ₃ ^-) are as described above, means a conjugate base anion group of a sulfo group (-SO ₃ H), is usually used preferably in combination with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , C).
a ²⁺ , Zn ^2+, etc.).

The carboxylate group (--CO₂ ^-) Is before
As mentioned above, the carboxyl group (CO ₂H) Conjugate base anion
Means an ionic group, usually used with a counter cation
Is preferred. Such counter cations are generally
Known ones, namely various oniums (ammoni
Um, sulfonium, phosphonium, iodonium
Mums, aziniums, etc.), and metal ions (Na
⁺, K⁺, Ca²⁺, Zn ²⁺Etc.) can be mentioned.

The substituted phosphono group means one in which one or two of the hydroxyl groups on the phosphono group are substituted by another organic oxo group, and preferable examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, Examples thereof include an alkylarylphosphono group, a monoalkylphosphono group and a monoarylphosphono group. Among these, a dialkylphosphono group and a diarylphosphono group are more preferable. Specific examples thereof include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group and the like.

The phosphonato group (--PO ₃ ^2- , --PO ₃ H
^-) as described above and, phosphono group (-PO ₃ H _2),
It means a conjugated base anion group derived from acid first dissociation or acid second dissociation. Usually, it is preferably used together with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums: aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphonate group is a conjugated base anion group obtained by substituting one hydroxyl group with an organic oxo group among the above-mentioned substituted phosphono groups, and specific examples thereof include the above-mentioned monoalkylphosphono group (--PO ₃ H (alkyl)) and a conjugated base of a monoarylphosphono group (—PO ₃ H (aryl)). Usually, it is preferably used together with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums,
Iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

Next, X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a
Alternatively, an example of a cyclic structure formed by R ^b and each other is shown. X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b
Examples of the aliphatic ring formed by combining with each other include a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered aliphatic ring, more preferably a 5-membered ring and a 6-membered ring. The aliphatic ring of can be mentioned. These may further have a substituent on the carbon atom constituting them (examples of the substituent include the substituents on the above-mentioned substituted alkyl group), and the ring-constituting carbon May be partially substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Furthermore, part of this aliphatic ring may form part of the aromatic ring. Next, specific examples of the compound having the structure represented by formula (I) are shown.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

[Table 6]

[0058]

[Table 7]

[0059]

[Table 8]

[0060]

[Table 9]

[0061]

[Table 10]

[0062]

[Table 11]

[0063]

[Table 12]

[0064]

[Table 13]

[0065]

[Table 14]

[0066]

[Table 15]

[0067]

[Table 16]

[0068]

[Chemical 8]

[0069]

[Chemical 9]

[0070]

[Chemical 10]

[0071]

[Chemical 11]

[0072]

[Chemical 12]

[0073]

[Chemical 13]

[0074]

[Chemical 14]

[0075]

[Chemical 15]

The compound of the present invention is most preferably a polyfunctional type (bifunctional or higher and polymeric type) having two or more structures represented by formula (I) in the molecule, or It has a structure represented by the general formula (I) and another radically polymerizable group, and substantially contributes polyfunctionality in photopolymerization.

In the photopolymerizable composition of the present invention, a compound having a structure represented by the above general formula (I) alone or a mixture of two or more thereof as a radically polymerizable compound,
Alternatively, a mixture with a conventionally known radically polymerizable compound described below is used.

The amount of all polymerizable group-containing compounds, including the compound having the structure represented by formula (I), is usually 1 to 99.99 with respect to the weight of all components of the photopolymerizable composition.
%, Preferably 5 to 90.0% by weight, more preferably 10 to 70% by weight are used. However, the general formula (I) of the present invention contained in all polymerizable group-containing compounds
The content of the compound is 0.005 to 100% by weight, preferably 1% to 100% by weight, and more preferably 30 to 1%.
It is 00% by weight, and if the content is less than 0.005, the effect of the present invention may not be exhibited.

(Photopolymerization Initiator) The photopolymerizable composition of the present invention contains a photopolymerization initiator as an essential component together with the compound having the structure represented by the general formula (I). Next, the photopolymerization initiator used in the present invention will be described in detail.

Examples of the photopolymerization initiator of the present invention include benzophenone, 4,4-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone and 4-dimethylaminobenzophenone. , 4-dimethylaminoacetophenone, benzylanthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone,
2,4-diethylthioxanthone, fluorenone, acridone, bis (2,4,6-trimethylbenzoyl)-
Bisacylphosphine oxides such as phenylphosphine oxide, aromatic ketones such as acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like;

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 double body, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole double body, 2- (o-fluorophenyl) -4,5-diphenylimidazole double body, 2- (o-methoxyphenyl) -4,5-diphenylimidazole double 2-mer
(P-Methoxyphenyl) -4,5-diphenylimidazole double body and other 2,4,6-triarylimidazole double bodies; carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone and other polyhalogen compounds; JP-A-59-133428, JP-B-57-
1819, Japanese Examined Patent Publication No. 57-6096, and U.S. Pat. No. 36.
The compound described in 15455;

2,4,6-Tris (trichloromethyl)
-S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6
-Bis (trichloromethyl) -S-triazine, 2-
(P-Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine and the like, JP-A-58-29803.
S-triazine derivative having a trihalogen-substituted methyl group described in No.

Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditertiary-butyl diveroxy isophthalate, 2,5-dimethyl-2,5-di (benzoyl peroxy) Hexane, tert-butyl peroxybenzoate, a, a'-bis (tert-butyl peroxyisopropyl) benzene, dicumyl peroxide, 3,3 ', 4,4'-tetra- (tertiary butyl peroxycarbonyl) Japanese Patent Application Laid-Open No. Sho 5 such as benzophenone
Organic peroxides described in 9-189340;

An azinium salt compound described in US Pat. No. 4,743,530; tetramethylammonium salt of triphenyl butyryl borate, tetrabutylammonium salt of triphenyl butyryl borate, tetramethylammonium salt of tri (P-methoxyphenyl) butyl borate. And other organic boron compounds described in European Patent No. 0223587; diaryliodonium salts, iron allene complexes, and the like.

Further, a combination of two or more kinds of compounds is also known, and these can also be used in the photopolymerizable composition of the present invention. Examples of the combination of two or more compounds include a combination of a 2,4,5-triarylimidazole dimer and a mercaptobenzoxazole or the like, 4,4′-described in US Pat. No. 3,427,161. A combination of bis (dimethylamino) benzophenone and benzophenone or benzoin methyl ether, benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromerch) -6- (4'- as described in U.S. Pat. No. 4,239,850. Methoxyphenyl)-
Combination of triazole, combination of dialkylaminobenzoic acid ester described in JP-A-57-23602 and dimethylthioxanthone, combination of 4,4'-bis (dimethylamino) benzophenone and benzophenone described in JP-A-59-78339. And a combination of three kinds of polyhalogenated methyl compounds.

As other photopolymerization initiators, organic borate compounds described in JP-A-62-143044, JP-A-9-188685, JP-A-9-188686 and JP-A-9-188710, or Examples thereof include a spectral sensitizing dye type borate compound obtained from a cationic dye.

(Dye) A dye is preferably contained in the photopolymerizable composition containing a borate compound as a photopolymerization initiator. The dye is preferably a spectral sensitizing dye having a maximum absorption wavelength in the range of 300 to 1000 nm.
By coexisting the spectral sensitizing dye with a borate compound, it is possible to efficiently respond to an exposure light source in the spectral absorption wavelength region, so that high sensitivity is achieved and any light source in the ultraviolet to infrared region is used. The generation of radicals can be controlled.

High sensitivity can be obtained by arbitrarily selecting the spectral sensitizing dye from the spectral sensitizing dyes in the above wavelength range and using it for the purpose of adjusting the photosensitive wavelength to suit the light source to be used. Further, as a light source used for image exposure, a blue, green, or red light source, an infrared laser, or the like can be selected. Therefore, for example, when a color image is formed by using a multicolor recording material in which monochromatic recording layers that emit different hues are laminated, a spectral enhancement having different absorption wavelengths in each monochromatic layer having different hues. Since a dye is present and a light source adapted to the absorption wavelength thereof is used, each layer (each color) forms a highly sensitive and sharp image even in a recording material in which a plurality of layers are laminated, Higher sensitivity and higher sharpness can be achieved for the multicolor recording material as a whole.

As the spectral sensitizing dye, known cationic dyes, neutral dyes or anionic dyes can be used. Specific examples of the spectral sensitizing dye include “Research Disclosure, Vol. 200, 1980 1
February, Item 20036 "and" sensitizer "(p.160
~ P.163, Kodansha; Katsumi Tokumaru, Shin Okawara / ed., 198
7 years) and the like.

Specifically, 3-ketocoumarin compounds described in JP-A-58-15603 and JP-A-58-4030.
No. 2 thiopyrylium salt, Japanese Examined Patent Publication No. 59-2832
No. 8 and No. 60-53300, naphthothiazole merocyanine compounds, Japanese Patent Publication Nos. 61-9621 and 62.
-3842, JP-A-59-89303, 60-6.
And the merocyanine compound described in No. 0104.

Also, "Chemistry of Functional Dyes" (1981)
Year, CMC Publishing Company, p.393-p.416) and "coloring materials"
(60 [4] 212-224 (1987)) and the like. Specific examples thereof include cationic methine dyes, cationic carbonium dyes, cationic quinoneimine dyes, cationic indoline dyes, and cationic styryls. Examples include dyes.

The spectral sensitizing dyes include coumarin (including ketocoumarin and sulfonocoumarin) dyes, metostyryl dyes, oxonol dyes, hemioxonol dyes and other keto dyes; non-ketopolymethine dyes, triarylmethane dyes, xanthenes. Non-keto dyes such as dyes, anthracene dyes, rhodamine dyes, acridine dyes, aniline dyes, azo dyes; non-keto dyes such as azomethine dyes, cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes, hemicyanine dyes, and styryl dyes Ketopolymethine dyes; quinoneimine dyes such as azine dyes, oxazine dyes, thiazine dyes, quinoline dyes, and thiazole dyes are included.

By properly using the above-mentioned spectral sensitizing dye, the spectral sensitivity of the photopolymerization initiator used in the photopolymerizable composition of the present invention can be obtained in the ultraviolet to infrared region. The above various spectral sensitizing dyes may be used alone or in combination of two or more.

The use ratio of the spectral sensitizing dye and the borate compound is very important in order to obtain high sensitivity and to obtain sufficient decoloring property by light irradiation in the fixing step when used as a recording material. . In addition to the spectral sensitizing dye / borate compound ratio (= 1/1: molar ratio) required for the photopolymerization reaction, the amount of borate necessary to sufficiently decolor the spectral sensitizing dye remaining in the layer. It is preferable to add a compound from the viewpoint of obtaining sufficiently high sensitivity and decoloring performance. That is, the ratio of the spectral sensitizing dye / borate compound is preferably in the range of 1/1 to 1/50, more preferably in the range of 1 / 1.2 to 1/30, Most preferably, it is used in the range of 1.2 to 1/20. If the spectral sensitizing dye exceeds 1/1 with respect to the borate compound, sufficient polymerization reactivity and decoloring property may not be obtained, and if it is less than 1/50, coating suitability may deteriorate. .

The total amount of the spectral sensitizing dye and the borate compound is based on the amount of the radically polymerizable compound used.
0.1-25 wt% is preferable, 0.1-20 wt% is more preferable, 0.1-15 wt% is the most preferable. If the amount used is less than 0.1% by weight, the effect of the present invention may not be obtained, and if it exceeds 25% by weight, storage stability may be reduced and coating suitability may be reduced.

When the photopolymerizable composition of the present invention is used in the recording layer of a recording material, the content of the spectral sensitizing dye is 0.1 to 5% by weight based on the total weight of the recording layer. Preferably
0.5 to 2% by weight is more preferable. The spectral sensitizing dye and the borate compound may be mixed in advance and then added to the coating liquid for the recording layer, and when the coating liquid for the recording layer is prepared, the spectral sensitizing dye and the borate compound are prepared. And may be added separately.

(Radical Polymerizable Compound) The photopolymerizable composition of the present invention may contain a radical polymerizable compound in addition to the compound having the structure represented by the general formula (I). I do not care. When the photopolymerizable composition of the present invention is used as a recording material, the radically polymerizable compound is contained for the purpose of imparting resistance to an image after recording and improving the sensitivity of the recording material. The radically polymerizable compound is a compound having at least one ethylenically unsaturated bond in its chemical structure, and is a monomer, a prepolymer (dimer, trimer, or oligomer thereof),
A compound having a chemical structure such as a mixture thereof or a copolymer thereof is preferable. Specific examples thereof include unsaturated carboxylic acids and salts thereof, esters of aliphatic polyhydric alcohol compounds with unsaturated carboxylic acids, and amides of aliphatic polyhydric amine compounds with unsaturated carboxylic acids.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid. Specific examples of the salt of the unsaturated carboxylic acid include the sodium salt and potassium salt of the aforementioned unsaturated carboxylic acid. Examples of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester and the like. These will be described more specifically.

Examples of the acrylic ester include ethylene glycol diacrylate, triethylene glycol triacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane. Triacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol. Tetraacrylate, sorbitol pe Data, sorbitol hexaacrylate, polyester acrylate oligomer.

As the methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,
3-butanediol dimethacrylate, pentaerythritol ditacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate,
Sorbitol tetramethacrylate, bis- [p- (3
-Methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (acryloxyethoxy) phenyl] dimethylmethane and the like.
Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate and 1,4-
Examples thereof include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate and sorbitol tetracrotonate.
Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. As maleic acid ester, ethylene glycol dimaleate, triethylene glycol dimaleate,
Examples thereof include pentaerythritol dimaleate and sorbitol tetramaleate. These esters may be used alone or in combination of two or more.

Specific examples of the amide of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide,
1,6-hexamethylenebis-acrylamide, 1,6
-Hexamethylene bis-methacrylamide, diethylene triamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide and the like.

In addition to the above, a vinyl monomer represented by the following general formula is added to a polyisocyanate compound having two or more kinds of isocyanate groups in one molecule described in JP-B-48-41708. Examples thereof include vinyl urethane compounds having two or more polymerizable vinyl groups in the molecule. CH ₂ = C (R) COOCH ₂ CH (R) OH [In the above formula, R represents a hydrogen atom or a methyl group. Represents ] Further, a polymer compound having a vinyl group or a vinylidene group,
For example, a condensation compound of a polymer compound having a hydroxyl group, an amino group, an epoxy group, a halogen atom, or a sulfonyloxy group in a side chain with acrylic acid, methacrylic acid, or a derivative thereof can be given.

The radical-polymerizable compounds may be used alone or in combination of two or more. The content of the radically polymerizable compound contained in the photopolymerizable composition of the present invention is preferably 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 1 part by weight of the photopolymerization initiator. preferable. When the content is less than 10 parts by weight,
The color density may decrease, and if it exceeds 50 parts by weight, the storage stability may decrease.

(Other Components) As the other components, for the purpose of accelerating the polymerization reaction, a reducing agent or a chain transfer agent such as an oxygen scavenger (Oxygen Scavenger) or a chain transfer agent of an active hydrogen donor is further used as an auxiliary agent. Other compounds that accelerate the polymerization can be added. Examples of the oxygen scavenger include phosphine, phosphonate, phosphite, primary silver salt, and other compounds easily oxidized by oxygen. Specifically, N-phenylglycine, trimethylparbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N-
2,4,6-Pentamethylaniline acid may be mentioned. Further, thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, azides and the like are also useful as the polymerization accelerator.

The photopolymerizable composition of the present invention can be preferably used in the recording material of the present invention described later. Since the photopolymerizable composition of the present invention contains the compound having the structure represented by the general formula (I) of the present invention, the recording material has high sensitivity and excellent storage stability due to the steric protection effect. Can be obtained.

(Recording Material) The recording material of the present invention has a recording layer provided on a support, and further has other layers as required. (Recording Layer) The recording layer contains the photopolymerizable composition of the present invention, a color-forming component A, and a color-forming component B that reacts with the color-forming component A to form the color-forming component A, and further, if necessary. And contains other components. The above-mentioned photopolymerizable composition of the present invention means at least a photopolymerizable composition containing a compound having a structure represented by the general formula (I) of the present invention. When the color-forming component A is an electron-donating dye precursor, the color-forming component B may not be newly contained, and the compound having the structure represented by the general formula (I) of the present invention may be added to the color-forming component B. Can also be used as

(Color-forming component A and color-forming component B) The color-forming component A and the color-forming component B that reacts with the color-forming component A to form the color-forming component A are both substantially colorless and excellent when untreated. Has transparency. At least one of the color-forming component A and the color-forming component B is preferably encapsulated in a microcapsule from the viewpoints of stability before recording, fog prevention, image resistance, and the like, and they are mutually heated and / or pressurized. It is preferable to have a property of exhibiting a color by contact with.

The combination of the two components (color-forming component A and color-forming component B) constituting such a recording layer is as follows:
(T) is preferably used (in the following examples, the former is the coloring component A and the latter is the coloring component B).

(A) A combination of an electron-donating dye precursor and an electron-accepting compound. (Here, the electron-accepting compound may also serve as the photopolymerizable composition) (a) A combination of a diazonium salt compound and a coupling component (hereinafter appropriately referred to as "coupler"). (C) A combination of an organic acid metal salt such as silver behenate and silver stearate and a reducing agent such as protocatechuic acid, spiroindane and hydroquinone. (D) A combination of long-chain fatty acid iron salts such as ferric stearate and ferric myristate with phenols such as tannic acid, gallic acid and ammonium salicylate. (E) Organic acid heavy metal salts such as nickel, cobalt, lead, copper, iron, mercury, and silver salts such as acetic acid, stearic acid, and palmitic acid, and alkali metals or alkalis such as calcium sulfide, strontium sulfide, and potassium sulfide. A combination with an earth metal sulfide, or a combination of the organic acid heavy metal salt with an organic chelating agent such as s-diphenylcarbazide and diphenylcarbazone. (F) Combination of heavy metal sulfates such as silver, lead, mercury and sodium sulfates with sulfur compounds such as sodium tetrathionate, sodium thiosulfate and thiourea. (G) an aliphatic ferric salt such as ferric stearate,
In combination with an aromatic polyhydroxy compound such as 3,4-hydroxytetraphenylmethane.

(H) A combination of an organic acid metal salt such as silver oxalate or mercury oxalate and an organic polyhydroxy compound such as polyhydroxy alcohol, glycerin or glycol. (K) A combination of a ferric acid salt of ferric acid such as ferric pelargonate and ferric laurate with a thiocecilcarbamide or isothiocecilcarbamide derivative. A combination of an organic acid lead salt such as (co) lead caproate, lead pelargonate, lead behenate and a thiourea derivative such as ethylenethiourea or N-dodecylthiourea. (A) A combination of a higher aliphatic heavy metal salt such as ferric stearate and copper stearate, and zinc dialkyldithiocarbamate. (C) A compound that forms an oxazine dye such as a combination of resorcin and a nitroso compound. (S) A combination of a formazan compound with a reducing agent and / or a metal salt. (C) A combination of a protected dye (or leuco dye) precursor and a deprotecting agent. (So) A combination of an oxidative color former and an oxidant. (T) A combination of phthalonitriles and diiminoisoindolines. (Combination formed by phthalocyanine.) (H) Combination of isocyanates and diiminoisoindolines (combination formed by colored pigment). (T) A combination of a pigment precursor and an acid or a base (a combination formed by a pigment).

Among these, as a combination of the two components of the color forming component A and the color forming component B constituting the recording layer,
(A) a combination of an electron-donating dye precursor and an electron-accepting compound, (a) a combination of a diazonium salt compound and a coupler, (c) a combination of an organic metal salt and a reducing agent, and (c)
It is preferred to use a combination of a protected dye (or leuco dye) precursor and a deprotecting agent.

Next, it is preferably contained in the recording layer,
Combinations of the above compositions (a), (b), (c), and (c)
Will be described in detail below. (A) Combination of electron-donating dye precursor and electron-accepting compound The electron-donating dye precursor preferably used in the present invention is not particularly limited as long as it is substantially colorless. It has the property of developing colors by donating electrons or by accepting protons such as acids.
For example, phthalide compounds, fluoran compounds, thiazine compounds, leuco auramine compounds, rhodamine lactam compounds, spiropyran compounds, pyridine compounds, pyrazine compounds, fluorene compounds and the like can be preferably mentioned.

Examples of the phthalide compound include:
US Reissue Patent No. 23,024, US Patent No. 3,49
No. 1,111, No. 3,491,112, No. 3,4
91,116 and 3,509,174, and the compounds described in JP-A-3,509,174 are specifically mentioned. Specifically, 3,3-bis (p
-Dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-diethylaminophenyl) -3-
(1-Ethyl-2-methylindol-3-yl) 4-azaphthalide, 3,3-bis (1-octyl-2-methylindol-3-yl) phthalide and the like can be mentioned.

Examples of the fluoran compound include, for example, US Pat. Nos. 3,624,107 and 3,62.
7,787, 3,641,011, and 3,4
No. 62,828, No. 3,681,390, No. 3,
920,510 and 3959,571 are mentioned, and specific examples thereof include 2- (dibenzylamino) fluorane, 2-anilino-3-methyl-6-diethylaminofluorane and 2-anilino. -3-methyl-6
-Dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-
Cyclohexylaminofluorane, 2-anilino-3-
Chlor-6-diethylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6- N-methyl-N
-Tetrahydrofurfurylaminofluorane, 2-anilino-3-methyl-6-biperidinoaminofluorane,
2- (o-chloroanilino) -6-diethylaminofluorane, 2- (3,4-dichloroanilino) -6-diethylaminofluorane and the like can be mentioned.

Examples of the thiazine compound include:
Examples thereof include benzoyl leucon methylene blue and p-nitrobenzyl leuco methylene blue. Examples of the leuco auramine-based compound include 4,4′-bis-
Dimethylaminobenzhydrin benzyl ether, N-
Examples thereof include halophenyl-leuco auramine and N-2,4,5-trichlorophenyl leuco auramine.

Examples of the rhodamine lactam compound include rhodamine-B-anilinolactam and rhodamine-
(P-Nitrile) lactam and the like can be mentioned. Examples of the spiropyran compound include, for example, US Pat.
No. 1,808, specifically, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran 3,3′-dichloro-spiro-dinaphthopyran, 3-benzylspiro- Dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo)
Examples include spiropyran and 3-propyl-spiro-dibenzopyran.

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

The content of the electron-donating dye precursor is preferably 0.1 to 5 g / m ^{2 in the} recording layer,
0.1 to 3 g / m ² is more preferable. The content is
If it is less than 0.1 g / m ² , the color density may be insufficient, while if it exceeds 5 g / m ² , the coating suitability may deteriorate.

When the electron-donating dye precursors used are the electron-donating dye precursors capable of developing cyan, magenta, and yellow hues, the recording material of the present invention is a full-color recording material. Can be used. As the cyan, magenta, and yellow coloring dyes, the dyes described in US Pat. No. 4,800,149 can be used. Further, as an electron-donating dye precursor for yellow color development, US Pat.
It is possible to use those described in No. 00,148,
As the electron-donating dye precursor for cyan color development, the dyes described in JP-A-63-53542 can be used.

Examples of the electron-accepting compound which develops a color by acting on the electron-donating dye precursor include hydroxybenzoic acid and
Preferable examples include ester compounds, phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, pentonite, novolac resins, metal-treated novolac resins, and metal complexes.

Specifically, JP-A-4-226455,
JP-A-63-173682, JP-A-59-83693,
No. 60-141587, No. 62-99190, European Patent No. 29323, JP-A No. 62-167077, No. 6
No. 2-16708, No. 63-317558, Japanese Patent Publication No. 4
0-9309, JP-B-45-14039, JP-A-5-
2-140483, JP-A-48-51510, JP-A-57-210886, JP-A-58-87089,
JP-A-59-112286, JP-A-60-176795
And those described in JP-A No. 61-95988. Moreover, the electron-accepting compound may have a polymerizable group.

The electron-accepting compound is preferably used in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on 1 part by weight of the electron-donating dye precursor used. Is more preferably used. If the amount is less than 0.1 part by weight, the color density may be insufficient, while 3
If it exceeds 0 parts by weight, the sensitivity may be lowered or the coating suitability may be deteriorated.

(A) Combination of a diazonium salt compound and a coupler The above-mentioned diazonium salt compound is one which develops a desired hue by a coupling reaction with a coupler which is a coupling component which will be described later. It is a photodecomposable diazonium salt compound that decomposes when exposed to light in the range and no longer has the ability to develop color even when a coupling component is present. The hue in this coloring system is determined by the azo dye formed by the reaction of the diazonium salt compound and the coupler. Therefore, the maximum absorption wavelength (coloring hue) can be easily controlled by changing the chemical structure of the diazonium salt compound or the coupler (positions and types of substituents, etc.). Can be obtained.

Examples of the photodecomposable diazonium salt compound preferably used in the present invention include aromatic diazonium salt compounds represented by the following formula. Ar-N ₂ ⁺ X ^- wherein, Ar represents a substituted or unsubstituted aryl group, X ^-
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, An amino group, a heterocyclic group, a cyano group, a nitro group, a halogen atom, etc. are mentioned, and these substituents may be further substituted.

As Ar, an aryl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenyl group, a 2-methylphenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-butoxyphenyl group and a 2-butoxyphenyl group. (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, 4 -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 −
Examples include butoxyphenyl group and 4- (N-benzyl-N-methylamino) -2-dodecyloxycarbonylphenyl group.

Further, these groups may be further substituted with an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a heterocyclic group, a halogen atom or the like.

The diazonium salt compound preferably used in the present invention preferably has 12 or more carbon atoms in the compound, a water solubility of 1% or less, and an ethyl acetate solubility of 5% or more.

Specific examples of the diazonium salt compound that can be preferably used in the recording material of the present invention are shown below, but the present invention is not limited thereto.

[0132]

[Chemical 16]

[0133]

[Chemical 17]

[0134]

[Chemical 18]

[0135]

[Chemical 19]

[0136]

[Chemical 20]

[0137]

[Chemical 21]

In the present invention, the diazonium salt compounds may be used alone or in combination of two or more depending on various purposes such as hue adjustment.

The content of the diazonium salt compound is preferably 0.01 to 3 g / m ^{2 in the} recording layer, more preferably 0.02 to 1.0 g / m ² . If it is less than 0.01 g / m ² , sufficient color developability cannot be obtained, and if it exceeds 3 g / m ² , the sensitivity is lowered and it is necessary to prolong the fixing time, which is not preferable.

As the coupler for coupling reaction with the diazonium salt compound, any coupler can be used as long as it can form a dye by coupling with the diazonium salt compound in a basic atmosphere and / or a neutral atmosphere. Depending on various purposes such as hue adjustment, one type may be used alone, or two or more types may be used in combination.

As the coupler, Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G, but a non-diffusible one having a hydrophobic group called a ballast group or a polymerized one is preferable. Examples of the couplers preferably used in the present invention include:
Examples of cyan couplers include naphthol-based couplers and phenol-based couplers. US Pat. No. 2,369,92
No. 9, No. 2,772, 162, No. 2, 801, 171
Issue 2, Issue 2,895,826, Issue 3,446,622
Issue 3, Issue 3,758,308, Issue 3,772,002
Issue 4,052,212, Issue 4,126,396
Nos. 4,146,396 and 4,228,233
Issue 4, Issue 4,254,212, Issue 4,296,199
No. 4,496,200, 4,327,173
No. 4,433,999, 4,334,011
No. 4,433,011, No. 4,427,767
No. 4,451,559, 4,690,889
No. 4,775,616, West German Patent Publication 3,32
9,729, European Patents 121,365A, 249,
The couplers and the like described in each specification of No. 453A, JP-A No. 61-42,658 and the like can be mentioned. Examples of magenta couplers include imidazole [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 and pyrazolo [1,5-
b] [1,2,4] triazoles and the like.

In addition, a pyrazolotriazole coupler having a branched alkyl group directly bonded to the 2-position, 3-position or 6-position of a pyrazolotriazole ring as described in JP-A-61-65,245; -65,246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, and an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147,254. Pyrazoloazole couplers and pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in European Patent (Publication) Nos. 226,849 and 294,785, and others, US Pat. No. 432, No. 3,725,067,
4,310,619, 4,351,897, 4,556,630, EP 73,636, JP-A-55-118,034, 60-35,730,
60-43,659, 60-185,951,
61-72,238, International Publication W088 / 0479
5 and Research Disclosure No. 242
20, same No. 20. Examples thereof include couplers described in 24230. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 3,973,968, 4,022,620, 4,248,961, 4,314,023, and US Pat. 4,326,024, 4,401,752, 4,511,649, European Patent 249,473A, JP-B-58-10,739.
No., British Patent Nos. 1,425,020 and 1,476,7
Examples thereof include couplers described in No. 60 and the like.

Typical examples of polymerized dye-forming couplers include US Pat. Nos. 3,451,820 and 4,0.
80, 211, 4,367,282, 4,40
9,320, 4,576,910, European Patent 34
No. 1,188A, British Patent No. 2,102,137 and the like. Further, a so-called active methylene compound having a methylene group next to a carbonyl group can also be mentioned. In addition, Japanese Patent Application No. 9-260336 and Japanese Patent Application No. 9-2
No. 71395, etc. can also be mentioned, and they can be appropriately selected and used within the range that meets the purpose of the present invention. Further, the coupler may have a polymerizable group.

For details, see JP-A-4-201283, JP-A-7-223367, JP-A-7-223368, JP-A-7-323660, and JP-A-5-278608.
JP-A-5-297024, JP-A-6-18669,
It is described in JP-A-6-18670 and JP-A-7-316280. In addition, Japanese Patent Application No. 8-027095 and Japanese Patent Application No. 8-0270 previously filed by the applicant of the present application.
No. 96, Japanese Patent Application No. 8-030799, Japanese Patent Application No. 8-126
No. 10, Japanese Patent Application No. 8-132394, Japanese Patent Application No. 8-358
No. 755, Japanese Patent Application No. 8-358756, Japanese Patent Application No. 9-06
Reference can also be made to those described in 9990 and the like.

The amount of the coupler added is preferably 0.02 to 5 g / m ² in the recording layer, and more preferably 0.1 to 4 g / m ² from the viewpoint of the effect. . If the amount added is less than 0.02 g / m ² , the color developability may be poor, while if it exceeds 5 g / m ² , the coating suitability may deteriorate.

The coupler compound is preferably used in the range of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 1 part by weight of the diazonium salt compound. If it is less than 0.1 part by weight, sufficient color development cannot be obtained, and if it exceeds 20 parts by weight, the coating suitability is deteriorated, which is not preferable.

The coupler compound can be used by adding a water-soluble polymer together with other components and solid-dispersing it with a sand mill or the like, but it can also be used as an emulsion by emulsifying with a suitable emulsification aid. . here,
The method of solid dispersion or emulsification is not particularly limited, and a conventionally known method can be used.
For details of these methods, see JP-A-59-1908.
86, JP-A-2-141279, and JP-A-7-171.
45.

In the present invention, for the purpose of accelerating the coupling reaction, if desired, organic compounds such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines and morpholines are used. A base can be used.

Examples of these organic bases 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, morpholines such as 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, N-
(3-phenoxy-2-hydroxypropyl) piperidine, piperidines such as 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 can be mentioned. These organic bases may be used alone or in combination of two or more.

These are described in JP-A-57-123086,
JP-A-60-49991 and JP-A-60-94381, and Japanese Patent Application Nos. 7-228731 and 7-28731.
No. 235157 and Japanese Patent Application No. 7-235158.

The amount of the organic base used is not particularly limited, but it is 1 to 1 mol of the diazonium salt.
It is preferably used in the range of 30 mol.

Further, for the purpose of promoting the color forming reaction, a color forming auxiliary agent can be added. Examples of the color forming aid include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, sulfonamide compounds and the like. These compounds have a function of lowering the melting point of the coupler compound or the basic substance, or improving the heat permeability of the microcapsule wall,
It is considered that a high color density can be obtained.

(C) Combination of Organic Metal Salt and Reducing Agent Specific examples of the organic metal salt include silver laurate and
Silver salts of long-chain aliphatic carboxylic acids such as silver myristate, silver palmitate, silver stearate, silver arachiate or silver behenate; such as benzotriazole silver salt, benzimidazole silver salt, carbazole silver salt or phthalazinone silver salt Silver salt of organic compound having imino group; Silver salt of sulfur-containing compound such as s-alkylthioglycolate; Silver salt of aromatic carboxylic acid such as silver benzoate and silver phthalate; Silver sulfonate such as silver ethanesulfonate Silver salt of sulphinic acid such as silver o-toluenesulfinate; silver salt of phosphoric acid such as silver phenylphosphate; silver barbiturate; silver saccharinate; silver salt of salicylaldoxime; or any of these. A mixture of Of these, long-chain aliphatic carboxylic acid silver salts are preferable, and silver behenate is more preferable. Also, behenic acid may be used with silver behenate.

Examples of the reducing agent include those disclosed in JP-A-53-102.
It can be appropriately used based on the description in JP-A No. 0, page 227, lower left column, line 14 to page 229, upper right column, line 11.
Among them, mono, bis, tris or tetrakisphenols, mono or bisnaphthols, di or polyhydroxynaphthalenes, di or polyhydroxybenzenes, hydroxymonoethers, ascorbic acid, 3-pyrazolidones, pyrazoline acids, pyrazolones , Reducing sugars, phenylenediamines, hydroxylamines, reductones, hydrooxamines, hydrazides, amidoximes, N-hydroxyureas and the like are preferably used. Among the above, aromatic reducing agents such as polyphenols, sulfonamide phenols, and naphthols are particularly preferable.

(C) Protected dye (or leuco dye)
A combination of a precursor and a deprotecting agent A protected dye (or leuco dye) precursor is a dye precursor capable of forming a color upon contact with a base, and has the following general formula (1)
And a dye precursor (2) represented by the following general formula (2).

General Formula (1): Ar—N (—L) -Cp In the above formula, Ar represents an aromatic ring or a heterocycle which may have a substituent, Cp represents a coupler residue, and L represents Represents a protecting group which can be deprotected with a base.

General Formula (2): Ar—N (—L ¹ ) —Cp-L ^{2 In the} above formula, Ar represents an aromatic ring or a heterocycle which may have a substituent, and Cp is a coupler residue. the stands, L ₁ represents a a protective group which can be deprotected with a base, the L ₂ is protecting group to be deprotected after leaving group or L ₁ desorbing after the L ₁ is deprotected is deprotected Represent

A in the general formulas (1) and (2)
Examples of r include groups represented by the following structural formula (4).

Embedded image Structural formula (4):

In the above structural formula (4), R ¹¹ represents NR ¹³ R ¹⁴ or OR ¹⁵ , R ¹³ and R ¹⁴ represent a hydrogen atom, an alkyl group or an aryl group, and R ¹⁵ represents H, COR ¹⁶ , C
O ₂ R ¹⁶ , SO ₂ R ¹⁶ , CONR ¹⁷ R ¹⁸ , alkyl or aryl, R ¹⁶ represents an alkyl, aryl or heterocyclic group, and R ¹⁷ represents H, alkyl, aryl or a heterocyclic group.

R ¹³ and R ¹⁴ are hydrogen atoms,
Alkyl having 1 to 30 carbons and aryl having 6 to 20 carbons are preferable, and specifically, for example, hydrogen, methyl, ethyl,
Examples thereof include propyl, butyl, octyl, octadecyl, hydroxyethyl, methanesulfonylaminoethyl, phenoxyethyl, cyanoethyl, benzoyloxyethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl and benzyl. NR ¹³ R ¹⁴ is R ¹³ and R ¹⁴ ,
It may form a ring which may contain a hetero atom such as O, S and N, or may form a ring together with the phenyl ring substituted with NR ¹³ R ¹⁴ .

R¹⁵Is a hydrogen atom or 1 to 1 carbon atoms
40 COR¹⁶, CO₂R¹⁶, SO ₂R¹⁶, CONR¹⁷
R¹⁸, Alkyl and aryl are preferred, and specifically
For example, hydrogen atom, methyl, ethyl, octyl, benzyl
Ru, phenyl, acetyl, benzoyl, ethoxycarbo
Nyl, phenylsulfonyl, dibutylaminocarbonyl
Etc.

In the structural formula (4), R ¹¹ is preferably NR ¹³ R ¹⁴ . In the structural formula (4), R ¹² is a hydrogen atom,
It represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfonylamino group, an acylamino group, an alkoxycarbonyl group, a carbamoyl group or a sulfamoyl group, and among them, an alkyl group, an alkoxy group, an acylamino group and a hydrogen atom are preferable. Further, R ¹² is preferably located at the meta position of R ^{11 in} the formula (4).

As Ar in the general formulas (1) and (2), pyridine which may have a substituent,
Thiazole, furan, oxazole, pyrimidine and the like are also preferable. Examples of the substituent include an amino group, a dialkylamino group, an alkylamino group, an acylamino group, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group and a sulfamoyl group. The alkyl group contained in Ar may be saturated, unsaturated, or cyclic.

In the present invention, the alkyl group, aryl group and heterocyclic group may further have a substituent, and such a substituent is an alkyl group, an aryl group, a hydroxy group, a nitro group, a cyano group or a halogen group. , Alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, alkylamino group, dialkylamino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, carbamoyl group, sulfamoyl group , Alkylthio groups, arylthio groups and heterocyclic groups.

Cp in the general formula (1) represents a so-called 4-equivalent coupler residue, while Cp in the general formula (2) represents
p represents a so-called 4-equivalent coupler residue or 2-equivalent coupler residue. As these couplers, all known couplers can be used.

Examples of the coupler include Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G, but a non-diffusible one having a hydrophobic group called a ballast group or a polymerized one is preferable. Examples of couplers preferably used in the present invention include cyan couplers such as naphthol couplers,
There are phenol-based couplers and the like, and US Pat.
929, 2,772,162, 2,801,1
71, 2,895,826, 3,446,62
No. 2, No. 3,758,308, No. 3,772,002
Issue 4,052,212, Issue 4,126,396
Nos. 4,146,396 and 4,228,233
Issue 4, Issue 4,254,212, Issue 4,296,199
No. 4,496,200, 4,327,173
No. 4,433,999, 4,334,011
No. 4,433,011, No. 4,427,767
No. 4,451,559, 4,690,889
No. 4,775,616, West German Patent Publication 3,32
9,729, European Patents 121,365A, 249,
Examples thereof include couplers described in JP-A No. 453A and JP-A No. 61-42,658. Examples of magenta couplers include imidazole [1,2-b] pyrazoles described in US Pat. No. 4,500,630 and US Pat. No. 4,540,6.
No. 54, etc., pyrazolo [1,5-b] [1,2,
4] Triazoles and the like can be mentioned.

In addition, a pyrazolotriazole coupler having a branched alkyl group directly bonded to the 2-position, 3-position or 6-position of a pyrazolotriazole ring as described in JP-A-61-65,245; -65,246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, JP-A-61-147,254.
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A No. 296,861 and an alkoxy group or an aryloxy group at the 6-position as described in European Patent (Publication) Nos. 226,849 and 294,785. And other pyrazolotriazole couplers, and US Pat. Nos. 3,061,432 and 3,725,067
Issue 4,310,619, Issue 4,351,897
No. 4,556,630, European Patent 73,636.
JP-A-55-118,034 and 60-35,7.
30, No. 60-43, 659, No. 60-185, 9
51, 61-72,238, International Publication W088 /
04795 and Research Disclosure N
o. 24220, No. 24220. Examples thereof include couplers described in 24230. As a yellow coupler, for example,
U.S. Pat. Nos. 3,933,501 and 3,973,96
No. 8, No. 4,022,620, No. 4,248,961
Issue No. 4,314,023 Issue No. 4,326,024
Issue No. 4,401,752, No. 4,511,649
No., European Patent 249,473A, Japanese Patent Publication No. 58-10,
739, British Patents 1,425,020, 1,47
Examples thereof include couplers described in No. 6,760.

Typical examples of polymerized dye-forming couplers include US Pat. Nos. 3,451,820 and 4,0.
80, 211, 4,367,282, 4,40
9,320, 4,576,910, European Patent 34
No. 1,188A, British Patent No. 2,102,137 and the like. In addition, those described in Japanese Patent Application No. 9-260336, Japanese Patent Application No. 9-271395 and the like can be mentioned.

[0170] L in the general formula (1), and, as the L ₁ in the general formula (2), for example the following structural formulas (5) to
Examples include those represented by (10).

[0171]

Embedded image Structural formula (5)

In the structural formula (5), X is O, S or SO.₂
Or represents a single bond, R^{twenty one}And R ^{twenty two}Is a hydrogen atom, al
Represents kill, alkoxy, aryl or EWG. Na
EWG is an electron-withdrawing group, and more specifically
Is a substituent having a positive Hammett σ value, such as a halogen
Atom, sulfamoyl, sulfonamide, alkoxy
Ci, carbonyl, sulfonyl and the like (the same applies hereinafter).

[0173]

Embedded image Structural formula (6)

In the structural formula (6), R ²³ and R ²⁴ represent a hydrogen atom, an alkyl group or an aryl group. R ²⁴ and E
WG and WG may form a ring together, and as an example of the structural formula (6) in the ring-formed state,

[0175]

[Chemical 25] Etc.

[0176]

Embedded image Structural formula (7)

In the structural formula (7), Y is CO or SO.
₂ , R ²⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heterocycle, and C represents an aryl group or a heterocyclic group (for example, a phenyl group, a naphthyl group, a pyridyl group, a thienyl group or a pyrrole group).

[0178]

Embedded image Structural formula (8)

In the structural formula (8), Y is CO or SO.
₂ , R ²⁶ represents the same as R ²⁵ in the structural formula (7).

Structural formula (9): --CH ₂ --NHSO ₂ R
^{27 In the} structural formula (9), R ²⁷ is R ²⁵ in the structural formula (7).
Represents the same thing as.

[0181]

Embedded image Structural formula (10)

In the above structural formula (10),

[Chemical 29] Represents an aryl group in which a heterocycle is condensed. As an example of the structural formula (10),

[Chemical 30] Etc.

When Cp in the general formula (2) is a 2-equivalent coupler residue, the general formula (2) is represented by the following general formula (2-
It is represented by 1).

[0184]

[Image Omitted]: General formula (2-1)

An example of L ²¹ will be given below.

[Chemical 32]

In the above structural formula, R ³¹ , R ³² , R ³³ and R
³⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group or an amide group, and R ³¹ and R ³² are bonded to each other. It may form a ring structure (in this case, it may be saturated or unsaturated). Further, R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ each independently represent a hydrogen atom, an alkyl group or an aryl group.

When Cp in the general formula (2) is a coupler residue having 4 equivalents, the general formula (2) is represented by the following general formula (2-2).

[0188]

[Chemical 33] In the above structural formula, L ²² represents a protecting group that is deprotected after L ¹ is deprotected, and Cp represents a 4-equivalent coupler residue.

Specific examples of L ²² include protecting groups for nitrogen atom and oxygen atom, such as acyl, alkylsulfonyl, arylsulfonyl, formyl, alkyloxycarbonyl and the like.

Hereinafter, the dye precursor (1) represented by the general formula (1) (1, 3, 7, 8, 12, 14, in the following specific examples,
15, 16, 18, 19, 20, 21, 23, 26, 2
7 and 28) and the dye precursor (2) represented by the general formula (2) (2, 4, 5, 6, 9, 1 in the following specific examples).
0, 11, 13, 17, 22, 24 and 25).

[0191]

[Chemical 34]

[0192]

[Chemical 35]

[0193]

[Chemical 36]

[0194]

[Chemical 37]

[0195]

[Chemical 38]

[0196]

[Chemical Formula 39]

[0197]

[Chemical 40]

In order to ensure sufficient transparency of the recording material, in the recording layer, (a) a combination of an electron-donating dye precursor and an electron-accepting compound, or (a) a diazonium compound and a coupler. It is preferred to use a combination.

(Microencapsulation) A method of microencapsulating the color forming component A or the color forming component B will be described. A conventionally known method can be used as a method for microencapsulation. For example, US Patent No. 2
A method utilizing coacervation of the hydrophilic wall-forming material described in No. 8000457 and No. 28000458, US Pat. No. 3,287,154, British Patent No. 990443,
Japanese Examined Patent Publication No. 38-19574, No. 42-446, No. 42
-771 and other interfacial polymerization methods, U.S. Pat. No. 3,418.
No. 250, No. 3660304, polymer precipitation method, US Pat. No. 3,796,669 method using isocyanate polyol wall material, US Pat.
Method using the isocyanate wall material described in 914511, US Pat. Nos. 4,001,140 and 4,087,376.
Urea-formaldehyde-based and urea-formaldehyde-resorcinol-based wall forming materials described in U.S. Pat. No. 4,089,802, and methods using wall forming materials such as melamine-formaldehyde resin and hydroxybrobil cellulose described in US Pat. No. 4,025,455. , Shokoku Sho 36
-9168, in situ method by polymerization of monomers described in JP-A-51-9079, British Patent No. 9528.
Nos. 07 and 965074, the electrolytic dispersion cooling method, and the spray drying method described in U.S. Pat. No. 3,111,407 and British Patent No. 930422.

The method of microencapsulation is not limited to these, but in the recording material of the present invention, in particular, the color-forming component A is prepared by dissolving or dispersing it in a hydrophobic organic solvent which is the core of the capsule. The oil phase thus prepared is mixed with an aqueous phase in which a water-soluble polymer is dissolved, emulsified and dispersed by a means such as a homogenizer, and then heated to cause a polymer forming reaction at the oil droplet interface, and a microscopic substance It is preferable to adopt an interfacial polymerization method for forming a capsule wall. That is, a capsule having a uniform particle size can be formed within a short period of time, and a recording material having excellent raw storability can be obtained.

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

Examples of the water-soluble polymer include gelatin, polyvinylpyrrolidone, polyvinyl alcohol and the like.

For example, when polyurethane is used as the capsule wall material, a polyisocyanate and a second substance (for example, polyol or polyamine) which reacts with the polyisocyanate to form a capsule wall are used as a water-soluble polymer aqueous solution (aqueous phase) or By mixing in an oil medium (oil phase) to be encapsulated, emulsifying and dispersing these, and then heating, a polymer forming reaction occurs at the oil droplet interface, and a microcapsule wall can be formed.

Examples of the above polyisocyanates and the polyols and polyamines that react with the polyisocyanates include US Pat. Nos. 3,281,383, 3,773,695 and 3,7932.
No. 68, Japanese Patent Publication Nos. 40-40347, 49-2415.
9, JP-A-48-80191 and JP-A-48-84086.
It is possible to use those described in the issue.

In the present invention, when the microcapsules containing the color-forming component A are prepared, the color-forming component A to be encapsulated is
It may exist in a solution state or in a solid state in the capsule. In the case of encapsulating the color-forming component A in a solution state, the color-forming component A may be encapsulated in a state of being dissolved in a solvent. In this case, the solvent is 1 to 500 parts by weight with respect to 100 parts by weight of the color-forming component A. It is preferably used in the range of parts by weight.

When the solubility of the color-forming component A to be encapsulated in the solvent is poor, a low-boiling solvent having a high solubility can be supplementarily used. 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, as the aqueous phase to be used, an aqueous solution in which a water-soluble polymer is dissolved is used, and after the above oil phase is added, emulsification and dispersion are carried out by a means such as a homogenizer. Uniformly and easily, and acts as a dispersion medium for stabilizing the emulsified and dispersed aqueous solution.
Here, in order to more uniformly emulsify and stabilize the dispersion,
A surfactant may be added to at least one of the oil phase and the water phase. As the surfactant, a well-known emulsifying surfactant can be used. When adding a surfactant,
The amount of the surfactant added is 0.1 to 5 relative to the weight of the oil phase.
Weight% is preferable, and 0.5-2 weight% is more preferable.

As the surfactant to be contained in the aqueous phase, an anionic or nonionic surfactant which does not cause precipitation or aggregation by acting on the protective colloid is preferably selected and used. You can Preferred surfactants include, for example, sodium alkylbenzene sulfonate,
Examples thereof include sodium alkylsulfate, dioctyl sulfosuccinate sodium salt, and polyalkylene glycol (eg, polyoxyethylene nonylphenyl ether).

As described above, the water-soluble polymer to be contained as a protective colloid in the water phase mixed with the oil phase may be appropriately selected from known anionic polymers, nonionic polymers and amphoteric polymers. it can.

As the anionic polymer, both natural and synthetic ones can be used. For example, --CO
O -, - SO ₂ - include those having a group. Specifically, natural products such as arabic gum, alginic acid, and bectin; semi-synthetic products such as carboxymethylcellulose, gelatin derivatives such as phthalated gelatin, sulfated starch, sulfated cellulose, ligninsulfonic acid; maleic anhydride (hydrolyzed) (Including compounds), acrylic acid-based (methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, carboxy-modified polyvinyl alcohol, and other synthetic products.

Examples of the nonionic polymer include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of the amphoteric polymer include gelatin. Of these, gelatin, gelatin derivatives and polyvinyl alcohol are preferable. The water-soluble polymer is used as a 0.01 to 10 wt% aqueous solution.

All components including the color-forming component contained in the recording layer are solid-dispersed by means of a sand mill or the like together with, for example, a water-soluble polymer, a sensitizer and other color-forming auxiliaries. Although it can be used, it is previously dissolved in a high boiling organic solvent that is sparingly soluble or insoluble in water, and then mixed with a polymer aqueous solution (aqueous phase) containing a surfactant and / or a water soluble polymer as a protective colloid. However, it is more preferable to use it as an emulsified dispersion emulsified with a homogenizer or the like. In this case, a low boiling point solvent may be used as a dissolution aid, if necessary. Further, all the components including the above-mentioned color forming component can be separately emulsified and dispersed, or can be mixed in advance and then dissolved in a high boiling point solvent and emulsified and dispersed. The preferred emulsified dispersed particle size is 1
μm or less.

The emulsification is carried out by a means used for ordinary fine particle emulsification such as high speed stirring and ultrasonic dispersion of an oil phase containing the above-mentioned components and an aqueous phase containing a protective colloid and a surfactant, for example, a homogenizer, a Manton Gory. , An ultrasonic disperser, a dissolver, a Keddy mill, and the like can be easily used. After emulsification, in order to accelerate the capsule wall forming reaction, the emulsion is heated at 30 to 70 ° C.
Warm to. Further, during the reaction, in order to prevent the aggregation of the capsules with each other, it is necessary to add water to reduce the collision probability of the capsules and to perform sufficient stirring.

A dispersion for preventing aggregation may be added again during the reaction. Generation of carbon dioxide gas is observed with the progress of the polymerization reaction, and the end of the generation can be regarded as the approximate end point of the capsule wall forming reaction. Usually, the microcapsules containing the target dye can be obtained by reacting for several hours.

The average particle size of the microcapsules used in the recording material of the present invention 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 for a certain solid content becomes large and a large amount of wall agent is required. Therefore, the average particle diameter is preferably 0.1 μm or more.

(Other Components) The other components of the recording layer are shown below for the purpose of improving the fastness of an image to light and heat or reducing yellowing due to light after fixing. Known antioxidants and the like can be used. Examples of the antioxidant include European Patent No. 223739, No. 309401, No. 309402, No. 310551, No. 310552, No. 459416, and German Patent No. 3435443, JP-A-54-485.
35, 62-262047, 63-1.
No. 13536, No. 63-163351, No. 2-262654, No. 2-71262, No. 3-121449, No. 5-611.
66, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,27.
Examples thereof include those described in Japanese Patent No. 5 publication.

As the above-mentioned other components, various known additives already used in heat-sensitive recording materials and pressure-sensitive recording materials can be used in the recording layer. Specific examples of these antioxidants include JP-A-60-1073.
No. 84, No. 60-107383, No. 60-1.
No. 25470, No. 60-125471, No. 6
0-125472, 60-287485, 60-287486, 60-28748.
No. 7, gazette 60-287488, gazette 61-16.
No. 0287, No. 61-185483, No. 61
-2111079 gazette, the same 62-146678 gazette,
62-146680, 62-146679, 62-282885, 63-0511.
74, 63-89877, 63-88.
No. 380, No. 63-088831, No. 63-
No. 203372, No. 63-224989, No. 63-251282, No. 63-267594, No. 63-182484, JP-A No. 1-2392.
No. 82, No. 4-291685, No. 4-291.
684, 5-1888687, 5-18
No. 8686, No. 5-110490, No. 5-1
The compounds described in JP-A-108437, JP-A-5-170361, JP-B-48-043294, JP-A-48-033212 and the like can be mentioned.

Examples of the binder used in the recording layer include known water-soluble polymer compounds and latexes. Examples of the water-soluble polymer compound include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch derivatives, casein, acacia, gelatin, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, polyvinyl. Alcohol, epichlorohydrin modified polyamide, isobutylene-maleic salicylic anhydride copolymer, polyacrylic acid, polyacrylic acid amide and the like and modified products thereof, and the like, and latexes include styrene-butadiene rubber latex and methyl acrylate-butadiene. Examples thereof include rubber latex and vinyl acetate emulsion.

In the recording layer, known organic and inorganic pigments can be used as the other components. Specifically, kaolin, calcined kaolin, talc, wax stone,
Diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, amorphous silica, colloidal silica, calcined stone ko, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, micro Examples thereof include balloons, urea-formalin fillers, polyester particles, and cellulose fillers.

In the recording layer, as the other components, known waxes, antistatic agents, defoamers, conductive agents, fluorescent dyes, surfactants, ultraviolet absorbers and precursors thereof, etc.
Various additives can be contained.

(Formation of Recording Layer) The recording layer is formed by applying a recording layer coating solution on a support and drying. Solvents that can be used for the recording layer coating liquid include water; methanol, ethanol, n-propanol,
Alcohols such as isopropanol, n-butanol, sec-butanol, methyl cellosolve, 1-methoxy-2-propanol; halogenated solvents such as methylene chloride, ethylene chloride; ketones such as acetone, cyclohexanone, methyl ethyl ketone; methyl cellosolve acetate, ethyl acetate , An ester such as methyl acetate; toluene; a single substance such as xylene; and a mixture of two or more thereof. Of these, water is particularly preferable.

To apply the coating liquid for the recording layer onto a support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a curtain coater, An extrusion coater or the like can be used.

As a coating method, "Research Disclosure, Vol. 200" (December 1980, I.
It can be applied with reference to tem 20036 XV). The layer thickness of the recording layer is 0.1 to 50 μm.
Is preferable, and 5-35 μm is more preferable.

(Support) As the support, all paper supports used for conventional pressure-sensitive paper, thermal paper, dry or wet diazo copying paper, etc. can be used. In particular,
Preferable examples include acid paper, neutral paper, coated paper, plastic film laminated paper obtained by laminating plastic such as polyethylene on paper, synthetic paper, plastic film such as polyethylene terephthalate and polyethylene naphthalate. When a transparent material is used as the support, light irradiation in the latent image forming step or the fixing step can be performed from the support surface side of the recording material. The support may contain various additives such as a fluorescent whitening agent and a pigment.

(Other Layers) <Protective Layer> In the recording material of the present invention, a protective layer may be provided as the other layer on the recording layer. The protective layer may be laminated in two or more layers if necessary. Materials used for the protective layer include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch,
Modified starch, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, gelatins, gum arabic, casein, styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate, isobutylene-maleic anhydride copolymer Water-soluble polymer compound such as combined hydrolyzate, polyacrylamide derivative, polyvinylpyrrolidone, sodium polystyrene sulfonate, sodium alginate, etc., and styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, vinyl acetate Examples include latexes such as emulsions.

The water-soluble polymer compound in the protective layer may be crosslinked to further improve the storage stability, and a known crosslinking agent may be used as the crosslinking agent.
Specifically, water-soluble initial condensates such as N-methylol urea, N-methylol melamine, and urea-formalin, dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic cross-linking agents such as boric acid and borax, polyamide epichlorohydrin, etc. Is mentioned. The protective layer may be electron beam cured. The protective layer further comprises a known pigment,
Metal soaps, waxes, surfactants, optical brighteners, ultraviolet absorbers and the like can also be used. The coating amount of the protective layer is preferably ^{0.2~5g / m 2, 0.5~2g / m} 2
Is more preferable. The film thickness is preferably 0.2 to 5 μm, more preferably 0.5 to 2 μm.

<Backcoat Layer> The recording material of the present invention comprises
In order to correct the curl balance of the support and to prevent the penetration of chemicals etc. from the back side, as the other layer,
A back coat layer may be provided. The back coat layer can be provided in the same manner as the protective layer, and it is also possible to form a label by combining release paper on the back surface via an adhesive layer.

<Intermediate Layer> When a plurality of recording layers having different hues are laminated on the support, the recording material of the present invention contains a filter dye between the monochromatic recording layers constituting the recording layer. An optional intermediate layer can be provided. The intermediate layer is mainly composed of a binder, and may contain additives such as a curing agent, a polymer latex, mica and an ultraviolet absorber, if necessary. When the filter dye is used, it can be selected from the spectral sensitizing dyes, but a compound having the same light absorption wavelength as the spectral sensitizing dye in the upper layer of each intermediate layer is used to form a clear image. It is preferable because it is possible. The filter dye is emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method to obtain a desired layer,
In particular, it can be added in the intermediate layer.

In the oil-in-water dispersion method, the boiling point is 175 ° C.
After dissolving the filter dye in a single solution of either the above high boiling point solvent or a low boiling point solvent of 30 to 160 ° C, or a mixed solution of both, water, an aqueous gelatin solution or polyvinyl is prepared in the presence of a surfactant. Finely dispersed in an aqueous solvent such as an alcohol aqueous solution. Examples of the high boiling point solvent include the solvents described in US Pat. No. 2,322,027. Further, as the high boiling point solvent and the auxiliary solvent, the same solvent as the solvent used in the production of the microcapsules can be used.

The dispersion may be accompanied by phase inversion, and the auxiliary solvent may be removed or reduced by distillation, Nudel water washing, ultrafiltration or the like, and then used for coating. Specific examples of the latex for polymer dispersion step, curing and impregnation include US Pat. No. 4,199,383, West German Patent Application (OLS) Nos. 2,541,274 and 2,54.
1,230, JP-A-49-74538, 51-5.
9943, 54-32552 and "Research Disclosure, Vol. 148" (August 1976,
Item 14850) and the like.

Examples of the above-mentioned latex include acrylic acid esters or methacrylic acid esters such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate; acrylic acid, 2-acrylamido-2-methylpropane sulfone. Copolymerized latices of acid monomers such as acids are preferred.

<Antihalation Layer, etc.> It is also possible to provide a layer containing a polymer which reduces oxygen permeability, such as gelatin or PVA, between the support and the recording layer. By forming such a layer,
It is possible to prevent photo-oxidation fading of the image. Furthermore, it is possible to provide a so-called antihalation layer between the support and the recording layer, or in the case of a transparent support, on the opposite side of the recording layer. Also in this case, it is preferable to use an antihalation layer that can be bleached with light or heat from the viewpoint of improving the whiteness of the background. In the case of bleaching with light, for example, a combination of a dye and a boron compound can be used, and in the case of bleaching with heat, for example, a method of bleaching the dye by coloring with a base or a nucleophile can be used.

When the recording material of the present invention is used as a recording material for full color, it is generally constituted by laminating a plurality of recording layers of different hues on a support, and each recording layer is composed of
Microcapsules containing a color-forming component A or the like that develops different hues and color-forming components B and the like are contained, but these may be contained in a single layer (of course, a micro-layer). The ingredients inside and outside the capsule may be reversed.). When these recording materials are irradiated with light,
Due to the difference in the wavelength of the light source, it is exposed to light to form a multicolor image.

When a plurality of photopolymerization initiators having different absorption wavelengths are used, a latent image corresponding to light of each wavelength is formed. Therefore, the color-forming components that generate different hues (for example, yellow, magenta, and cyan) correspond to the respective absorption wavelengths (they may have the same color, complementary colors, or other color relationships). When used in combination, it can be used as a recording material for multiple colors, especially for full color.
The photopolymerization initiator and the color-forming component may correspond to each other and may be separated into separate layers for color separation, or may be mixed into a single layer. When they are mixed in a single layer, it is preferable to encapsulate both in microcapsules. By mixing them in a single layer, a recording material for multi-color, particularly full-color, can be easily manufactured.

(Image Recording Method) The recording material of the present invention can be used in a conventionally known image recording method. less than,
A suitable image recording method using the recording material of the present invention will be described. In the recording material of the present invention, the recording layer is imagewise irradiated with light that the dye absorbs and that the borate compound does not absorb, and the polymerizable compound is polymerized by radicals generated when the light is irradiated. A latent image forming step of forming a latent image by applying heat and / or pressure to the entire surface of the recording layer to react the color forming component A and the color forming component B to make the latent image visible, An image can be formed by passing through.

At this time, if the recording material is such that the recording layer contains a plurality of organic dyes, a multicolor image can be easily obtained, and if the hues of the organic dyes are three primary colors of yellow, magenta and cyan. A full-color image can be easily obtained. The absorption wavelength of the dye that can be selected to form a multicolor image can be selected from a wide range from ultraviolet to near infrared, and the resulting image has less color mixture.

The image recording process will be described in detail.
In the latent image forming step, when light is irradiated, radicals are generated from the photopolymerization initiator. This radical polymerizes the polymerizable compound. As the polymerizable compound, a compound having a structure represented by the general formula (I) of the present invention, a color forming component B having a polymerizable group, a capsule oil having a polymerizable group, the radical existing outside the capsule A polymerizable compound or the like, which is or at least one of these
One polymerizes. Then, during heating or pressurization in the visualization step, the contact between the color forming component A and the color forming component B is prevented. That is, only the unexposed portion develops color due to the contact of the color forming component A and the color forming component B.

The wavelength of the light source may be appropriately selected from a wide range from ultraviolet to near infrared depending on the spectral sensitizing dye to be used and the spectral sensitizable photopolymerization initiator. As the light source, a semiconductor laser, LED, xenon light, fluorescent lamp, mercury lamp or the like can be used. It is also possible to use a light source having two or more kinds of wavelengths depending on the organic dye used. The light irradiation is usually performed from the recording layer side of the recording material, but when a transparent support is used as the recording material, the light irradiation can be performed from the support side surface.

The amount of light for forming a latent image may be a relatively small amount because it is sufficient to initiate the polymerization of the radically polymerizable compound. Therefore, there is an excellent merit that a large amount of light is not required for image writing, an inexpensive light source can be adopted, and high-speed image writing is possible. The heat and / or pressure applied to the entire surface of the recording layer in the visualization step may be conditions sufficient to break the microcapsules or allow the substance to permeate the capsule wall. Alternatively, conditions such as pressure and time may be appropriately set depending on the material of the capsule wall of the microcapsule, and the heating temperature is 50 to 250.
C. is preferable, and 70 to 150.degree. C. is particularly preferable. When heat is applied to the entire surface of the recording layer, the heat source that can be used for heating is a heat roller, a heat sensitive head, a heat stamp,
Examples include near infrared rays (laser) and infrared rays (laser). When pressure is applied to the entire surface of the recording layer, a pressure roller, a pressure pen, or the like may be used as a pressure method.

The image thus formed is further
It is preferable that the recording layer is subjected to a fixing step of irradiating the entire surface with light. The dye originally used as the spectral sensitizing dye in the recording layer is further exposed to light to be bleached by radicals from the photoradical generator, and the whiteness of the background (exposed portion in the latent image forming step) is improved. Further, there is also an excellent effect that the polymerizable compound remaining without being polymerized is also polymerized by the light in the fixing step, and the image is more firmly fixed.

At this time, light having a wavelength of 300 to 1000 nm may be irradiated, and light having absorption wavelengths of both the dye and the photoradical generator may be irradiated. As the light source, all of the commonly used ones such as laser, xenon light, fluorescent lamp, mercury lamp and the like can be used. Of course, the light source in this case is not for writing in an imagewise manner, but for irradiating the entire surface of the recording layer of the recording material. There is no obstacle to cost reduction and speedup.

[0242]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

[Example 1] (Preparation of electron-donating colorless dye-encapsulating microcapsule liquid (I)) 16.9 g of ethyl acetate was added to magenta-coloring electron-donating colorless dye (1) 8 represented by the following structural formula. Dissolve 9 g and 20 g of capsule wall material (trade name "Takenate D-110N" manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of capsule wall material (trade name "Millionate MR200" manufactured by Nippon Polyurethane Industry Co., Ltd.) Was added. The obtained solution is
The mixture was added to a mixed liquid of 42 g of 8% phthalated gelatin and 1.4 g of 10% sodium dodecylbenzene sulfonate solution, and then emulsified and dispersed at a temperature of 20 ° C. to obtain an emulsion. Next, 14 g of water and 72 g of a 2.9% tetraethylenepentamine aqueous solution were added to the obtained emulsion, and the mixture was stirred at 6
After heating at 0 ° C. for 2 hours, an electron donating colorless dye-encapsulated microcapsule liquid (I) having an average particle diameter of 0.5 μm and having the electron donating colorless dye (1) as a core was prepared.

[0244]

[Chemical 41]

(Preparation of Photopolymerizable Composition Emulsion (I)) The photopolymerizable composition emulsion (I) comprises the following borate compound-containing liquid (A) and dye-containing liquid (B). <Preparation of borate compound-containing liquid (A)> 0.5 g of a borate compound (Compound No. 1) represented by the following structural formula,
2.5 g of tricresyl phosphate was dissolved in 4.5 g of isopropyl acetate (solubility in water: about 4.3%), and this solution was represented by the following structural formula with 7.8 g of a 15% gelatin aqueous solution. 0.4 g of 10% aqueous solution of surfactant (1)
Added to a mixed solution of 3.7 g of water and water, Nippon Seiki Co., Ltd.
A borate compound-containing liquid (A) was prepared by emulsifying for 5 minutes at a rotation speed of 10,000 rpm using a homogenizer manufactured by K.K.

[0246]

[Chemical 42]

<Preparation of Dye-Containing Liquid (B)> 0.498 g of a spectral sensitizing dye represented by the following structural formula, and an auxiliary agent (1) of the following structural formula (1) 0. 498g,
Isopropyl acetate (solubility in water about 4.3%) 5.25
42 g of an electron-accepting compound (1) represented by the following structural formula and having a polymerizable group in a mixed solution with g and 2 shown below.
42 g of the functional monomer compound (1) was added.

[0248]

[Chemical 43]

[0249]

[Chemical 44]

[0250]

[Chemical formula 45]

The obtained solution was used as a 15% gelatin aqueous solution 1
09.1 g and a 2% aqueous solution of the above surfactant (1) 0.1.
8 g and 2% of the surfactant (2) represented by the following structural formula
It was added to a mixed solution with 4.0 g of an aqueous solution, and was emulsified for 5 minutes at a rotation speed of 10,000 rpm using a homogenizer manufactured by Nippon Seiki Co., Ltd. to prepare a dye-containing solution (B).

[0252]

[Chemical formula 46]

(Preparation of coating liquid (I) for light and heat sensitive recording layer)
Electron-donating colorless dye-encapsulated microcapsule liquid (I)
2 g and 2.25 g of the borate compound-containing liquid (A)
And 7.36 g of the above dye-containing solution (B) were mixed with 0.41 g of a 15% gelatin aqueous solution to prepare a coating solution (I) for a light and heat sensitive recording layer.

(Preparation of coating liquid for protective layer) 8.8 g of 18% gelatin aqueous solution, 7.0 g of distilled water, 0.4 g of 2% aqueous solution of surfactant (3) represented by the following structural formula, A 2% aqueous solution of a surfactant (4) represented by the following structural formula 1.2
g, 2% vinyl sulfone compound (hardening agent) aqueous solution 8.8 g, and 20% polyacrylic acid (trade name "Jurimer AC10LA" manufactured by Nippon Pure Chemical Co., Ltd.) 1.8 g were mixed and protected. A layer coating solution was prepared.

[0255]

[Chemical 47]

(Preparation of Light and Heat Sensitive Recording Material) A polyester film (“Lumirror E-68L” manufactured by Toray Industries, Inc.) filled with a white pigment is coated on the support having a thickness of 100 μm to prepare the coating solution for the light and heat sensitive recording layer ( I) was coated using a coating bar so that the solid coating amount of the light and heat sensitive recording layer was 6 g / m ² , and dried. A light- and heat-sensitive recording material was obtained by coating the above-prepared coating solution for a protective layer on the layer using a coating bar so that the solid coating amount of the protective layer was 2 g / m ² and drying. It was made.

The light- and heat-sensitive recording material was formed into a step wedge-like image shape with a maximum irradiation energy of 15 mJ / cm ² using a semiconductor laser beam having a wavelength of 657 nm from the protective layer side so that the irradiation energy was sequentially changed. Exposed. The recording material on which the latent image is formed by the exposure is 1
After heating for 5 seconds on a hot plate at 20 ° C., the recording material was heated to 58 ° C.
The entire surface of the light and heat sensitive recording layer of the above recording material was irradiated with light for 30 seconds on a high-intensity Sharkasten of 000 lux.
As a result, a step wedge-shaped image was obtained in which the color was vividly colored and the whiteness of the background was high.

(Evaluation of Sensitivity) Sensitivity corresponds to the same exposure amount in the wedge image of the material in one step.
The energy difference between the irradiation energy of this step and the energy required to form the background portion of the material (energy to form the background portion-irradiation energy in the above step) was measured and calculated to be used as an index of sensitivity. . Therefore, the smaller the value of sensitivity, the higher the sensitivity. The results are shown in Table 17.

[Examples 2-3, Comparative Example 1] In the preparation of the dye-containing liquid (B) of Example 1, instead of the bifunctional monomer compound (1), the polyfunctional monomer compound ( Using (2) to (3), the light and heat sensitive recording materials of Examples 2 to 3 were produced in the same manner as in Example 1, and the sensitivity was evaluated in the same manner, and the results are shown in Table 17. For the comparative example, in the preparation of the dye-containing liquid (B), 83 g of the electron-accepting compound (1) represented by the above structural formula and having a polymerizable group.
Was used in the same manner as above to prepare and evaluate the light and heat sensitive recording material of Comparative Example 1.

[0260]

[Table 17]

From Table 17, it was found that the recording material comprising the photopolymerizable composition containing the compound having the structure represented by the formula (I) of the present invention had high sensitivity. On the other hand, it was proved that the compound of Comparative Example 1 had low sensitivity.

[0262]

The recording material using the photopolymerizable composition of the present invention is excellent in sensitivity and storability by containing the compound having the structure represented by the general formula (I).

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yuichi Fukushige             200, Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 2H096 AA30 BA05 EA02 EA04 FA10                       GA55 LA30                 2H123 AC04 AC12

Claims (4)

[Claims] 1. A photopolymerizable composition containing a compound having a structure represented by the following general formula (I) and a photopolymerization initiator on a support, a color-forming component A, and a reaction with the color-forming component A. A recording material comprising a recording layer containing a color-forming component B that causes the color-forming component A to develop. [Chemical 1] [In the general formula (I), X ¹ and X ² each independently represent a hetero atom or a halogen atom. R ^a and R ^b are each independently
It represents a hydrogen atom, a halogen atom, a cyano group or an organic residue. Here, X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure. ] 2. The color-forming component A is an electron-donating dye precursor, and the color-forming component B is an electron-accepting compound.
The recording material described in. 3. The recording material according to claim 1, wherein the color forming component A is a diazonium salt compound, and the color forming component B is a coupler compound. 4. The recording material according to claim 1, wherein the color forming component A is a protected dye (or leuco dye) precursor, and the color forming component B is a deprotecting agent.