JP2002322207A - Photopolymerizable composition and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition and a recording material having a high sensitivity and excellent decolorizing property. SOLUTION: This photopolymerizable composition comprises a polymerizable compound having an ethylenic unsaturated bond and radical generators represented by the general formula (1) [wherein S represents a light-absorbing part having >=1,000 absorption coefficient in longer wavelength area than 300 nm; A represents an active part generating radical by interaction with photo- excited S: L represents a connecting group for connecting S to A] and the general formula (2) [wherein Ra<1> , Ra<2> , Ra<3> and Ra<4> represent each independently an aliphatic group, aromatic group, a heterocyclic group or Si(Ra<5> )(Ra<6> )-Ra<7> ; Ra<5> , Ra<6> and Ra<7> represent each independently an aliphatic group or aromatic group; G<+> represents a group capable of forming a cation]. This recording material comprises the photopolymerizable composition and a coloring component A and a coloring B having a part colored by reaction with the coloring component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photopolymerizable composition and a recording material, and more particularly, to an ink, a color filter, a hologram, a proof, a sealant, and an adhesive having a high degree of ring and excellent decoloration. The present invention relates to a photopolymerizable composition and a recording material that can be suitably used in a wide range of fields, such as an agent, lithographic printing, resin letterpress, and photoresist.

[0002]

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

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

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

As described above, a recording material using a photopolymerizable composition can record an image in a completely dry system without using a developer or the like, and is environmentally friendly in that no waste is generated. Very preferred. By the way, when an image is recorded on a photosensitive recording material, it is advantageous if an inexpensive infrared laser or blue to red light can be used in addition to UV light and short-wave visible light. However, a recording material using a photopolymerizable composition is sensitive to ultraviolet light, but is not sensitive to visible light to infrared light, or the sensitivity is not sufficient even when exposed, and as a result, In many cases, the formed image becomes unclear or the contrast between the image area and the non-image area is low, so that higher sensitivity is desired. for that reason,
In these recording materials, spectral sensitizing dyes are usually used for the purpose of increasing the sensitivity to light used for image recording (writing). In general, it is known that, after a recorded image is obtained, light that can be absorbed by the spectral sensitizing dye is irradiated again to photodecompose the dye and decolor the hue exhibited by the dye. However, the color erasing property may not be sufficiently obtained in some cases, and there are problems such as a decrease in the clarity and contrast of an image portion due to a partial residual color, and a long time for color erasing.

In addition, as one of means for increasing the sensitivity of a photopolymerizable composition, Japanese Patent Application Laid-Open No. 2-63054 discloses the use of a radical initiator in which a light absorbing portion and a radical generating portion are connected. Proposed. Such an initiator is advantageous in that electron transfer or energy transfer occurs efficiently after light absorption, and an initiator radical is easily generated. However, in the case of a photopolymerizable composition or a recording material using the photopolymerizable composition that requires whiteness, when the above-described radical initiator is used, sufficient decoloration of the light absorbing portion is obtained. Therefore, there is a problem that the whiteness of the background is insufficient.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a photopolymerizable composition having high sensitivity and excellent decoloration properties, and a recording medium. It is to provide materials.

[0008]

The above objects can be achieved by providing the following photopolymerizable composition and recording material. (1) A photopolymerizable composition comprising at least a polymerizable compound having an ethylenically unsaturated bond and a radical generator represented by the following general formulas (1) and (2).

[0009]

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In the general formula (1), S represents a light absorbing portion having an absorption coefficient of 1000 or more in a wavelength region longer than 300 nm, and A represents an active portion that interacts with the photoexcited S to generate a radical. L represents a linking group linking S and A.

[0011]

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In the general formula (2), Ra ¹ , Ra ² , Ra ³ ,
Ra ⁴ is each independently an aliphatic group, an aromatic group, a heterocyclic group,
Or Si (Ra ⁵ ) (Ra ⁶ ) —Ra ⁷ , wherein Ra ⁵ ,
Ra ⁶ and Ra ⁷ each independently represent an aliphatic group or an aromatic group. G ⁺ represents a group capable of forming a cation. (2) In the radical generator represented by the general formula (1), S is a cationic dye residue, a nonionic dye residue, a condensed polycyclic aromatic compound residue, a condensed polycyclic heteroaromatic compound residue, or aromatic. The photopolymerizable composition according to the above (1), which is a ketone compound residue. (3) In the radical generator represented by the general formula (1), S represents a cyanine dye residue, a hemicyanine dye residue, a merocyanine dye residue, a hemioxonol dye residue, a squarium dye residue, an acridinium dye residue, (1) or (1) or (1) or (1) a coumarin dye residue or a residue of anthracene, phenanthrene, pyrene, benzophenone, thioxanthone, anthraquinone, naphthoquinone, acridone, fluorenone, acridine, carbazole, phenothiazine, or a derivative thereof. The photopolymerizable composition according to 2). (4) having a recording layer on a support, wherein the recording layer comprises a color-forming component A, a color-forming component B having a portion that reacts with the color-forming component A to form a color, and (1) to (3). And a photopolymerizable composition according to any one of (1) to (4).

(5) The recording material as described in (4) above, wherein at least one of the polymerizable compounds having an ethylenically unsaturated bond is a coloring component B. (6) The above (4), wherein the polymerizable compound having an ethylenically unsaturated bond is a color-suppressing compound having a site for suppressing the reaction between the color-forming components A and B in the same molecule. The recording material described. (7) The recording material according to any one of the above (4) to (6), wherein the generation component A is included in a microcapsule. (8) a first recording layer that is sensitive to light having a center wavelength λ ₁ , a second recording layer that is sensitive to light having a center wavelength λ ₂ and develops a color different from that of the first recording layer,. _The above (4) to (4) to (4) to (4), which have a multilayer structure in which the first, second,... The recording material according to any one of (7).

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Photopolymerizable composition] (Radical generator) First, the radical generator used in the present invention will be described. In the present invention, since the radical generators represented by the general formulas (1) and (2) are used in combination, higher sensitivity and sufficient decoloring property are obtained as compared with the case where the radical generators are used alone, and the whiteness of the background portion is improved. I do. General formula (1)
S represents a light absorbing portion having an absorption coefficient of 1000 or more in a wavelength region longer than 300 nm, and A represents photoexcited S.
Represents an active part that generates a radical by interacting with, and L represents a linking group that links S and A. A light absorbing portion S having an absorption coefficient of 1000 or more in a long wavelength region of 300 nm or more.
Examples of the compound containing are various dyes, condensed polycyclic aromatic compounds, condensed polycyclic heteroaromatic compounds, and aromatic ketone compounds. The light absorbing part means a residue excluding the bonding part between the compound containing the light absorbing part S and L.

The dye is preferably a cationic dye or a nonionic dye. Cationic dyes are those in which quaternary ammonium is present in the color conjugated system of dye molecules.
Specific examples include, but are not limited to, cyanine dyes, hemicyanine dyes, triarylmethane dyes, styryl dyes, diallylmethane dyes, and fluoran dyes. Further, the nonionic dye is a dye having no counter anion and represents a dye which does not form a salt with the anion. Specific examples include merocyanine dyes, oxonol dyes, coumarin dyes, azo dyes, azomethine dyes, styryl base dyes, stilbene dyes, hemioxonol dyes, dyes having a vinyl ketone bond, quinone dyes, phthalocyanine dyes, and the like. It is not limited to. Among the above dyes, cyanine dyes, hemicyanine dyes, merocyanine dyes, coumarin dyes, and hemioxonol dyes are preferred in terms of high sensitivity.

Examples of the condensed polycyclic aromatic compound include anthracene, phenanthrene, pyrene and the like, and derivatives thereof. Examples of the condensed polycyclic heteroaromatic compound include acridine, carbazole, phenothiazine and the like. These derivatives are mentioned. Examples of the aromatic ketone compound include ketone compounds such as benzophenone, thioxanthone, anthraquinone, naphthoquinone, acridone, and fluorenone, and derivatives thereof. Also, cationic dye residue, nonionic dye residue,
The condensed polycyclic aromatic compound residue, the condensed polycyclic heteroaromatic compound residue, and the aromatic ketone compound residue may be substituted with a substituent. Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, an alkoxycarbonyl group having 30 or less carbon atoms (eg, a methoxycarbonyl group, an ethoxycarbonyl group) Benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbon atom 3
An acylaminosulfonyl group having 0 or less, an alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), an alkylthio group having 30 or less carbon atoms (for example,
A methylthio group, an ethylthio group, a dodecylthio group, etc.), an aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), a nitro group, having 30 or less carbon atoms. Alkyl group, alkoxycarbonyloxy group, aryloxycarbonyloxy group,

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

In the general formula (1), A represents photoexcited S
Represents an active part that generates a radical by interacting with Active part A that interacts with photoexcited S to generate radicals
Examples of the compound having the following are onium compounds such as bisimidazole compounds, diphenyliodonium, hydroxyalkyl ketones, and triphenylsulfonium salts; trichloromethyl-substituted-S-triazine compounds; N-phenylglycine; and amines such as triethanolamine and hydrazine. , Triphenylphosphine, phosphorus compounds such as tri-n-butylphosphine, sulfinic acids such as sodium P-toluenesulfinate, sulfonates such as methyl P-toluenesulfonate, oxazole, oxadiazole, imidazole and the like. Heterocyclic compounds, enolate compounds such as dimedone, tin compounds such as tributylbenzyltin, and pyridinium salts such as 1-methoxy-4-carbomethoxypyridinium tetrafluoroborate Te is "Research Disclosure" Vol.20
0, December 1980, Item 20036), allylthiourea, oxime esters, borate compounds such as triphenyl-n-butyl borate, and the like. The active part refers to a residue excluding a bond between L and a compound having an active part A that generates a radical by interacting with photoexcited S.

L in the general formula (1) represents a divalent linking group or a single bond. As the divalent linking group represented by L,
It is preferable that it is composed of atoms or atomic groups containing at least one of carbon, nitrogen, sulfur and oxygen.
Preferably, an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group (eg, phenylene, naphthylene), an alkynylene group (eg, ethenylene, propenylene), an alkynylene group (eg, nitinylene, propynylene), amide Group, ester group, sulfonamide group, sulfonate group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (R
a)-(Ra represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.), heterocycle 2
Valence group (for example, 6-chloro-1,3,5-triazine-
2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group) and a divalent linking group having 1 or more and 20 or less carbon atoms. It is. These divalent linking groups may be further substituted, and examples of the substituent include those described above as the substituent of the aromatic ketone compound residue.

As the divalent linking group or single bond represented by L, more preferably, an alkylene group having 1 to 20 carbon atoms (eg, methylene, ethylene, propylene, butylene), or a carbon atom having 6 to 20 carbon atoms. 1 carbon atom composed by combining one or more of an arylene group (eg, phenylene, naphthylene) and an alkynylene group having 2 to 20 carbon atoms (eg, ethenylene, propenylene)
A divalent linking group of 20 or more or a single bond is exemplified. Hereinafter, specific examples of the compound represented by Formula (1) are shown, but the invention is not limited thereto.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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Next, the general formula (2) used in the present invention
The radical generator represented by is described.

[0029]

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In the general formula (2), Ra ¹ , Ra ² , Ra ³ ,
Ra ⁴ is each independently an aliphatic group, an aromatic group, a heterocyclic group,
Or Si (Ra ⁵ ) (Ra ⁶ ) —Ra ⁷ , wherein Ra ⁵ ,
Ra ⁶ and Ra ⁷ each independently represent an aliphatic group or an aromatic group. G ⁺ represents a group capable of forming a cation. R _a
^{If 1} to R _a ⁴ represents an aliphatic group, as the aliphatic group,
For example, an alkyl group, a substituted alkyl group, an alkenyl group,
Substituted alkenyl group, alkynyl group, substituted alkynyl group,
Examples thereof include an aralkyl group and a substituted aralkyl group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group and a substituted aralkyl group are preferable, and an alkyl group and a substituted alkyl group are particularly preferable. Further, the aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

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

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

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

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

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

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

[0037] The case where R _a ¹ ~R _a ⁴ represents an aromatic group an alkyl group, as the aromatic group, for example, an aryl group, and a substituted aryl group. The number of carbon atoms in the aryl group is preferably from 6 to 30, and more preferably from 6 to 20. The preferred range of the number of carbon atoms in the aryl portion of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, and a β-naphthyl group. Examples of the substituent of the substituted aryl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

[0038] If R _a ¹ ~R _a ⁴ represents a heterocyclic group, the heterocyclic group, a heterocyclic group having a substituent, an unsubstituted heterocyclic group. Examples of the substituent of the heterocyclic group having a substituent group, include the same substituents as substituents exemplified in the case where R _a ¹ ~R _a ⁴ is a substituted aryl group. Among them, R _a ¹
The heterocyclic group to R _a ⁴ each represents a furan ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring,
A heterocyclic group containing a nitrogen atom, a sulfur atom, or an oxygen atom such as a pyridine ring is preferable.

R_a ¹~ R_a ^FourIs -Si (R_a ^Five) (R_a ⁶) -R_a ⁷To
When represented, R_a ^Five, R_a ⁶And R_a ⁷Are independently fat
Represents an aromatic group or an aromatic group. The aliphatic group and the aromatic group are represented by R_a ¹
~ R _a ^FourHas the same meaning as the aliphatic group and the aromatic group represented by
The same applies to preferred examples.

[0040] In the general formula ^{_{(2), R a 1,}} R a 2, R a 3,
And 2 or more of R _a ⁴ is connected directly or via a substituent, may form a ring. When forming a ring,
As the ring, any ring selected from the following rings (C1) to (C3) is preferable, and among them, the ring (C2) is preferable.

[0041]

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

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[0043] Among the aforementioned general formula (2) organoboron compounds represented by, in view of its R _a ¹ to R preferably has at least one of alkyl groups of _a ^4, improvement in sensitivity and preservability And a triarylalkyl-type organoboron compound in which one is an alkyl group and the other three are aryl groups are more preferred. In particular, when an acidic compound is used in the photopolymerizable composition or the recording material, a triarylalkyl-type organic boron compound in which an aryl group is substituted with an electron-withdrawing group is preferable. More preferably, the total of Hammet (σ) values of the groups (electron-withdrawing groups) is +0.36 to +2.58. As the electron-withdrawing group, a halogen atom and a trifluoromethyl group are preferable, and a fluorine atom and a chlorine atom are more preferable.

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

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

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

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

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

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

A specific example of the organoboron compound represented by the general formula (2) is described in US Pat. No. 3,567,453.
No. 4,343,891, JP-A-62
JP-A-143044, JP-A-62-150242, JP-A-9-188684, JP-A-9-188
No. 685, JP-A-9-188686, JP-A-9-188710, JP-B8-9643,
The compounds described in JP-A-11-269210 and the compounds exemplified below are exemplified. The organic boron compound may be used in combination with a radical generator described below.
However, the organic boron compound used in the present invention is not limited to this.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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The radical generator represented by the general formula (1) is used for the polymerizable compound of the photopolymerizable composition.
0.01-20% by mass is preferred, and 0.1-10% by mass
Is more preferred. Further, the content of the radical generator represented by the general formula (2) is preferably 0.01 to 20% by mass, and preferably 0.1 to 1% by mass based on the polymerizable compound of the photopolymerizable composition.
0 mass% is more preferable. Further, the total amount of the compounds represented by the general formulas (1) and (2) is preferably 0.01 to 20% by mass, and preferably 0.1 to 10% by mass based on the polymerizable compound of the photopolymerizable composition. % Is more preferred. However, the preferred range varies depending on the type of the “polymerizable compound” used in combination, and is not limited thereto.

(Polymerizable Compound Having Ethylenic Unsaturated Bond) The photopolymerizable composition of the present invention may be a polymerizable compound having an ethylenically unsaturated bond (hereinafter, sometimes referred to as “polymerizable compound”). )). The polymerizable compound is a polymerizable compound having at least one ethylenically unsaturated double bond in a molecule, and the polymerizable compound is not particularly limited and may be appropriately selected according to the purpose. For example, acrylic acid derivatives such as acrylic acid esters and acrylamides, acrylic acid and its salts, methacrylic acid esters and methacrylic acid derivatives such as methacrylamides, methacrylic acid and its salts, maleic anhydride, and maleic acid Examples include esters, itaconic acid, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and the like.

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

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

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

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

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

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

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

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

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

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

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

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

[0070] Polybutadienes and polyisoprenes and their copolymers are known. Examples of suitable comonomers are olefins such as ethylene, propene, butene and hexene, (meth) acrylate, acrylonitrile, styrene or vinyl chloride. Polymers having (meth) acrylate groups in the side chains are likewise known. For example, it can be obtained as a reaction product of a novolak-based epoxy resin with (meth) acrylic acid, or a homo- or copolymer of vinyl alcohol or (meth) acrylic acid with its hydroxyalkyl derivative esterified with Or a homo- or copolymer of (meth) acrylate esterified with hydroxyalkyl (meth) acrylate.

The polymerizable compound may be a compound having a site exhibiting another function in its structure, depending on the use of the photopolymerizable composition. When used as a material, the material may have a part that promotes a coloring reaction of a coloring component constituting an image part or a part that suppresses coloring. These will be described later.

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

Further, in the photopolymerizable composition of the present invention,
In addition to the compound of the general formula (1), a spectral sensitizing dye usually added to the photopolymerizable composition can be appropriately added. As the spectral sensitizing dye, a known cationic dye,
Neutral or anionic dyes can be used. Specific examples of the spectral sensitizing dye include “Research Disclosure, Vol. 200, December, 1980, I.
tem 20036 ”and“ sensitizers ”(p. 160-p. 16)
3, Kodansha; Katsumi Tokumaru, Shin Ogawara / ed., 1987).

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

Further, “Chemistry of Functional Dyes” (1981)
Year, CMC Publishing Co., p.393-p.416) and "Colorants"
(60 [4] 212-224 (1987)). Specific examples thereof include a cationic methine dye, a cationic carbonium dye, a cationic quinone imine dye, a cationic indoline dye, and a cationic styryl. Dyes.

The spectral sensitizing dyes include coumarin (including ketocoumarin or sulfoncoumarin) dyes, merostyril dyes, oxonol dyes, hemioxonol dyes and other keto dyes; non-ketopolymethine dyes, triarylmethane dyes, xanthene dyes Non-keto dyes such as dyes, anthracene dyes, rhodamine dyes, acridine dyes, aniline dyes, and azo dyes; Ketopolymethine dyes include quinone imine dyes such as azine dyes, oxazine dyes, thiazine dyes, quinoline dyes, and thiazole dyes.

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

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

[0079] The photopolymerizable composition of the present invention may also contain a binder. In particular, it is convenient when the photopolymerizable composition is a liquid or a viscous substance. The content of the binder is 5 to 95 with respect to the total solid content.
% By mass is preferable, and 10 to 90% by mass is more preferable.
Most preferred is 15 to 85% by weight. The choice of the binder depends on the field of application and the properties required for that field, such as the developing capacity in aqueous or organic solvent systems, adhesion to substrates and sensitivity to oxygen.

As the binder, about 5000 to 2
000000, preferably 10,000 to 1,000,000
Is desirable. For example, acrylate and methacrylate homo- or copolymers (eg, methyl methacrylate / ethyl acrylate / methacrylic acid copolymers, poly (alkyl methacrylate), poly (alkyl acrylate), etc.), cellulose esters or cellulose ethers (eg, cellulose acetate, cellulose) Acetobutyrate, methylcellulose, ethylcellulose, etc.), polyvinyl butyral, polyvinyl formal, cyclized rubber, polyether (eg, polyethylene oxide, polypropylene oxide, polytetrahydrofuran), polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, polyvinyl chloride, Vinylidene chloride / vinylidene copolymer, copolymer of vinylidene chloride and acrylonitrile, methyl methacrylate Rate, vinyl acetate, polyvinyl acetate, copoly (ethylene / vinyl acetate), polycaprolactam, poly (hexamethylene adipamide), polyester (eg, poly (ethylene glycol terephthalate), poly (hexamethylene glycol succinate), etc. ), Polyamide, polyurea and the like.

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

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

Other examples of additives include those described in
-269210.

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

As described above, by using the compound represented by the general formula (I) as the spectral sensitizing dye, an image can be formed with high sensitivity not only when using ultraviolet light but also when using visible light to infrared light. Since the compound itself can be formed, and the compound itself has excellent decoloring properties, an image without residual color due to the dye component can be obtained.

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

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

Thereafter, when heat is applied to the entire surface of the light- and heat-sensitive recording material, the microcapsules shift to a material-permeable state, and the color-forming component B in the non-light-irradiated portion penetrates into the microcapsules (and / or the color-forming component). A is released outside the microcapsule), and the color-forming component A and the color-forming component B react to form a color only in the non-light-irradiated portion. On the other hand, in the light irradiation section,
Since the photopolymerizable composition is in a cured and fixed state by a polymerization reaction, both the color-forming components A and B are immobilized and cannot come into contact with each other, and do not develop color in the light-irradiated portion. Thereafter, by exposing the photosensitive and heat-sensitive recording material over the entire surface, the unpolymerized region is also polymerized (fixed), and the dye component contained in the photopolymerizable composition can be erased.

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

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

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

Hereinafter, the components used in the recording material of the present invention will be described. (Photopolymerizable composition) The photopolymerizable composition includes 1) a polymerizable compound having an ethylenically unsaturated bond (polymerizable compound), 2) a compound of general formula (1), and 3) a general formula ( It contains the organoboron compound represented by 2), and if necessary, 4) may contain other components. In the recording material of the present invention, the above-mentioned photopolymerizable composition of the present invention is used. Is used. When irradiating the photopolymerizable composition with light,
The spectral sensitizing dye absorbs light and interacts with the radical generator, and the radical generator generates a radical. The radicals cause the polymerizable compound to undergo radical polymerization and cure to form an image.

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

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

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

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

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

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

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

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

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

[0102]

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

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

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

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

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

When using the above-mentioned electron-donating dye precursor,
An electron-accepting compound is used as a coloring component B for coloring the electron-donating dye precursor. Examples of the electron-accepting compound include phenol derivatives, which are known from heat-sensitive paper and pressure-sensitive paper.
Examples thereof include salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolak resins, metal-treated novolak resins, and electron accepting compounds such as metal complexes.
Specifically, Japanese Patent Publication No. 40-9309, Japanese Patent Publication No. 45-1
No. 4039, JP-A-52-140483, JP-A-48
JP-A-51510, JP-A-57-210886, JP-A-58-87089, JP-A-59-11286, JP-A-60-176799, JP-A-61-95988, and the like.

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

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

In the recording material of the first embodiment, the color-forming component B also functions as a polymerizable compound having an ethylenically unsaturated bond. Therefore, at least one of the polymerizable compounds of the recording material of the first embodiment is an electron-accepting compound, and the electron-accepting group and an ethylenically unsaturated bond (hereinafter, referred to as “polymerizable group”) .). As the coloring component B in this case, for example,
3-halo-4-hydroxybenzoic acid described in JP-A-226455, methacryloxyethyl ester, acryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682, and 59-83693.
Nos. 60-141587 and 62-99190, esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene, hydroxystyrenes described in EP 29323, JP-A-62-167077,
Examples thereof include compounds that can be synthesized with reference to the zinc halide N-vinylimidazole complex described in JP-A-62-1708 and the electron-accepting compound described in JP-A-63-317558.

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

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

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

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

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

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

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

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

When an electron-donating dye precursor is used as the color-forming component A and an electron-accepting compound is used as the color-forming component B, the content of the electron-donating dye precursor in the recording layer is preferably from 0.05 to 0.05%. 5 g / m ² is preferred,
1-3 g / m < ² > is more preferable. The amount of the electron accepting compound used is preferably 0.5 to 20 parts by mass, and more preferably 3 to 20 parts by mass, based on 1 part by mass of the electron donating colorless dye used.
-10 parts by mass is more preferred. If the amount is less than 0.5 part by mass, a sufficient color density may not be obtained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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[0140]

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[0141]

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

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

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

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

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

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

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

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

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

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

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

[0154] As the photopolymerizable monomer D _1, specifically, acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydride Maleic esters; itaconic acid, itaconic esters; styrenes; vinyl ethers; vinyl esters; N-vinyl heterocycles;
Allyl esters and the like can be mentioned.

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

[0156] As the photopolymerizable monomer D ₁ is preferably one a molecular weight of from about 100 to about 5000, about 3
More preferably, the number is from about 2000 to about 2000.

When the photopolymerizable monomer D1 is used as the polymerizable color-suppressing compound, the amount of the photopolymerizable monomer D1 used may be ₁ % by mass of the electron-donating compound used in combination with the coupler compound having no polymerizable group. Parts
It is preferably from 10 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass. If the amount is less than 0.1 parts by mass, a latent image may not be formed in the exposure step,
If the amount exceeds the parts by mass, the color density may decrease.

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

[0159] As the photopolymerizable monomer D _2, for example, styrene sulfonylamino acid, vinyl benzyloxy phthalate, beta-methacryloxy ethoxy salicylic acid zinc, beta-acryloxy ethoxy salicylic acid zinc, vinyloxy ethyl oxybenzoate, beta -Methacryloxyethylorselinate, β-acryloxyethylorselinate, β-methacryloxyethoxyphenol, β-acryloxyethoxyphenol, β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate , Hydroxystyrenesulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p-hydroxybenzoate, methacryloxymethylphenol, acryloyl Shi-methyl phenol,
Methacrylamidopropanesulfonic acid, acrylamidopropanesulfonic acid, β-methacryloxyethoxy-dihydroxybenzene, β-acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β
-Methacryloxypropanecarboxylic acid,

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

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

[0162] As the polymerizable coloring inhibiting compounds, when using the photopolymerizable monomer D _2, as the amount thereof, the coupler compound 1 part by weight for use in combination with the coupler compound free of polymerizable group On the other hand, 0.1
It is preferably from 10 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass. If the amount is less than 0.1 part by mass, a latent image may not be formed in the exposure step, and if it exceeds 10 parts by mass, the color density may decrease.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. Example 1 (Examples 1 to 6) As shown in Table 1 below, a photopolymerizable composition having the following composition was prepared using the compound represented by the general formula (1) and the organoboron compound represented by the general formula (2). did. [Composition of photopolymerizable composition]-Pentaerythritol tetraacrylate-1.41 g-Benzyl methacrylate / methacrylic acid-1.29 g (molar ratio: 73/27 Polymer) ・ Methyl ethyl ketone 12 g ・ Propylene glycol monomethyl ether acetate 8.62 g ・ Compound of general formula (1) (see Table 1 below) 1 × 10 ^-4 mol ・ Organic boron compound shown below (see Table 1) ・ ・ ・ ・ ・ ・ ・ 6 × 10 ^-4 mol ・ Methanol ・ ・ ・ ・... 6 g The structures of borates (1) and (2) (organic boron compounds) in Tables 1 and 2 below are shown below.

[0182]

Embedded image

Each of the prepared photopolymerizable compositions was
2 μm on polyethylene terephthalate film
And dried at 100 ° C. for 5 minutes. The following protective layer coating solution (1) was further applied thereon to a thickness of 1 μm, and dried at 100 ° C. for 2 minutes to prepare photosensitive materials (1) to (6) of the present invention.

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

(Comparative Examples 1 to 6) In Examples 1 to 6,
Photopolymerizable compositions (7) to (1) were prepared in the same manner as in Examples 1 to 6, except that the organoboron compound of the general formula (2) was not added.
2) was obtained.

<Image formation and evaluation> The prepared photopolymerizable compositions (1) to (6) of the present invention and the photopolymerizable compositions (7) to (12) of the comparative examples were each subjected to a vacuum printing apparatus. Exposure was performed using Exposure to the photosensitive material is performed using a step wedge (density step 0.15, density step number 1 to 15 steps, "Fuji Step Guide P" (manufactured by Fuji Photo Film Co., Ltd.) and "S
C38 filter ”(a sharp cut filter that cuts light below 380 nm; Fuji Photo Film Co., Ltd.)
)), And irradiating light with a 500 W xenon lamp (made by Ushio) for 10 seconds.
After the exposure, each of the photosensitive materials was developed using a developer having the following composition.

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

As a result of the above-mentioned development, the amount of exposure to the region corresponding to the high step number of the step wedge was small, so that the photopolymerizable composition in this region eluted into the developing solution and the polyethylene terephthalate (PET) surface was exposed. For the photosensitive material of each example, the photopolymerizable composition was completely eluted and PET
The area where the surface was exposed was examined, and the step number (clear step number) of the step wedge corresponding to the area having the highest exposure was obtained. The higher the determined number of steps, the higher the sensitivity of the photosensitive material. The results are shown in Table 1 below. In addition, when the photopolymerizable composition was eluted into the developer over all the exposed areas due to low sensitivity, the result was indicated as "flow" in the table.

The numbers (No.) in the column of the compound of the general formula (1) in Table 1 below are the same as those of the exemplified compound No. described above. Is equivalent to Hereinafter, the same applies to Table 2.

[0190]

[Table 1]

From the results shown in Table 1, the photopolymerizable compositions (1) to (6) of the present invention using the compound of the general formula (1) and the organoboron compound represented by the general formula (2) are as follows: High sensitivity was obtained. On the other hand, the photopolymerizable compositions (7) to (1) of Comparative Examples which did not use the organoboron compound defined in the present invention.
In 2), as high sensitivity as the photopolymerizable compositions (1) to (6) of the present invention could not be obtained.

(Example 7) <Preparation of microcapsule solution containing electron-donating colorless dye> (1-a) Preparation of microcapsule solution containing electron-donating colorless dye (1) The following electron donor was added to 16.9 g of ethyl acetate. Dissolves 8.9 g of a water-soluble colorless dye (1), and further as an encapsulating agent,
"Takenate D-110N" (manufactured by Takeda Pharmaceutical Co., Ltd.)
20 g and 2 g of "Millionate MR200" (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. This solution was added to a mixture of 42 g of 8% phthalated gelatin and 1.4 g of a 10% sodium dodecylbenzenesulfonate solution.
It was emulsified and dispersed at ℃ to obtain an emulsion. Water 14 was added to the obtained emulsion.
g and 72 g of 2.9% tetraethylenepentamine aqueous solution
The mixture was heated to 60 ° C. with stirring, and after 2 hours, the electron-donating colorless dye (1) was encapsulated in the core.
A μm microcapsule solution was obtained.

[0193]

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<Preparation of Emulsion of Photopolymerizable Composition> (2-a) Preparation of Emulsion of Photopolymerizable Composition The compound of the aforementioned general formula (1) (Exemplary Compound No. 1; Table 2 below) 0.05 g), 0.3 g of the borate (1) (organic boron compound) and 0.0 g of the following polymerization aid (1)
5 g and 4.2 g of the following polymerizable electron-accepting compound (1)
Was added and stirred and dissolved.

[0195]

Embedded image

This solution was added to an 8% aqueous gelatin solution (13 g).
0.8 g of a 2% aqueous solution of the following surfactant (1):
% Of the following surfactant (2) aqueous solution (0.8 g), and emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 10,000 rpm for 5 minutes to obtain an emulsion of the photopolymerizable composition. Obtained.

[0197]

Embedded image

<Preparation of Coating Solution for Recording Layer> (3-a) Preparation of Coating Solution for Recording Layer The electron-donating colorless dye (1) 4 g of a capsule solution, 12 g of an emulsion of a photopolymerizable composition, and 15 % Gelatin aqueous solution 1
2 g were mixed to prepare a coating solution for a recording layer.

<Preparation of Coating Solution (2) for Protective Layer> (4-a) Preparation of Coating Solution (2) for Protective Layer 4.5 g of a 10% gelatin aqueous solution, 4.5 g of distilled water,
0.5 g of a 2% aqueous solution of the following surfactant (3), 0.3 g of a 2% aqueous solution of the following surfactant (4), 0.5 g of a 2% aqueous solution of the following hardener (1), and “Syloid 72 ”(F
UJI-DEVICE CHEMICAL LTD.
Was mixed with 1 g of “Snowtex N” to give a coating amount of 50 mg / m ² to prepare a coating solution (2) for a protective layer.

[0200]

Embedded image

<Support> Thickness 100 filled with white pigment
μm white polyester film (“Lumirror E68
L ", manufactured by Toray Industries, Inc.) as a support. The coating solution for a recording layer was applied onto the support using a coating bar so that the dry weight of the coating layer was 6 g / m ^2, and dried at 30 ° C. for 10 minutes. The protective layer coating solution (2) was applied thereon using a coating bar so that the dry weight of the applied layer was 2 g / m ² ,
After drying for a minute, a light and heat sensitive recording material (a) of the present invention was obtained.

Examples 8 to 12 Except that the compound of the general formula (1) (Exemplified Compound No. 1) and the organic boron compound (borate 1) used in Example 7 were changed as shown in Table 2 below, In the same manner as in Example 7, photosensitive and heat-sensitive recording materials (b) to (f) of the present invention were obtained.

Comparative Examples 7 to 12 Photosensitive and heat-sensitive recording materials (g) to (l) were obtained in the same manner as in Examples 7 to 12, except that no organic boron compound was used.

<Image formation and evaluation> The light- and heat-sensitive recording materials (a) to (f) of the present invention and the light- and heat-sensitive recording materials (g) to (l) of the comparative examples were each manufactured by using a vacuum printing apparatus. Then, light was irradiated for 30 seconds with a 500 W xenon lamp through a step wedge and an SC38 filter to form a latent image. After that, each light and heat sensitive recording material is
When heated on a hot plate at 125 ° C. for 15 seconds, magenta color development occurs when the electron-donating colorless dye (1) reacts with the polymerizable electron-accepting compound (1) in the unexposed areas. No color density was reduced or no color formation occurred in the section. The area where color development did not occur was examined, and the step number (clear step number) of the step wedge corresponding to the area with the least exposure amount was obtained. The higher the determined number of steps, the higher the sensitivity of the light and heat sensitive recording material. The results are shown in Table 2 below. When the sensitivity was low and coloring occurred at all stages, "solid" was indicated in the table.

Further, after exposing for 10 minutes under a fluorescent lamp (30000 lux), yellow and yellow were measured with a transmission Macbeth densitometer.
The density of the magenta and cyan background portions was measured. The better the decoloring property of the contained organic dye by the exposure, the lower the fog density of the background. The results are shown in Table 2 below.

[0206]

[Table 2]

From the results shown in Table 2 above, the light- and heat-sensitive recording materials (a) to (f) of the present invention using the compound of the general formula (1) and the organoboron compound of the general formula (2) have high sensitivity. And a clear and high-contrast image could be formed. On the other hand, in the photosensitive and heat-sensitive recording materials (g) to (l) of Comparative Examples in which the organic dye specified in the present invention was not used, high sensitivity was not obtained and the decoloring property was poor.

[0208]

Since the photopolymerizable composition and the recording material of the present invention use the compound of the general formula (1) and the organic boron compound of the general formula (2), they have high sensitivity. Excellent in decoloration, high whiteness of the background after recording.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03F 7/004 521 G03F 7/004 521 7/028 7/028 G03H 1/02 G03H 1/02 F term (reference) 2H025 AA00 AA01 AB02 AB03 AB09 AB13 BC31 BC83 BH04 CA00 CA41 DA10 FA39 2H048 CA04 CA09 CA12 CA13 CA14 2K008 AA04 DD13 4J011 PA09 PA28 PA29 PA33 PA69 PB25 PB40 PC08 QA02 QA03 QA06 QA07 QA09 QB19 QB01 SA08 UA08

Claims (8)

[Claims] 1. A photopolymerizable composition comprising at least a polymerizable compound having an ethylenically unsaturated bond and a radical generator represented by the following general formulas (1) and (2). Embedded image In the general formula (1), S represents a light absorbing portion having an absorption coefficient of 1000 or more in a wavelength region longer than 300 nm, A represents an active portion that interacts with photoexcited S to generate a radical, Represents a linking group linking S and A. Embedded image In the general formula (2), Ra ¹ , Ra ² , Ra ³ , and Ra ⁴ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, or Si (Ra
⁵⁾ represents ^{(Ra 6) -Ra 7, Ra} 5, Ra 6, Ra
⁷ each independently represents an aliphatic group or an aromatic group. G ⁺
Represents a group capable of forming a cation. 2. In the radical generator represented by the general formula (1), S is a cationic dye residue, a nonionic dye residue, a condensed polycyclic aromatic compound residue, a condensed polycyclic heteroaromatic compound residue, or The photopolymerizable composition according to claim 1, which is an aromatic ketone compound residue. 3. In the radical generator represented by the general formula (1), S represents a cyanine dye residue, a hemicyanine dye residue, a merocyanine dye residue, a hemioxonol dye residue, a squarium dye residue, and an acridinium dye residue. Group,
Coumarin dye residue, or anthracene, phenanthrene, pyrene, benzophenone, thioxanthone, anthraquinone, naphthoquinone, acridone, fluorenone,
2. The residue of acridine, carbazole, phenothiazine, or a derivative thereof.
Or the photopolymerizable composition according to claim 2. 4. A recording layer having a recording layer on a support, wherein the recording layer has a coloring component A, and a coloring component B having a site that reacts with the coloring component A to form a color. Item 3
And a photopolymerizable composition according to any one of the above. 5. The recording material according to claim 4, wherein at least one of the polymerizable compounds having an ethylenically unsaturated bond is a coloring component B. 6. The color-suppressing compound having an ethylenically unsaturated bond and having a site for suppressing the reaction between the color-forming components A and B in the same molecule. Recording material described in 1. 7. The recording material according to claim 4, wherein the generating component A is encapsulated in a microcapsule. 8. A first recording layer sensitized to light having a center wavelength λ ₁ , a second recording layer sensitized to light having a center wavelength λ ₂ and developing a color different from that of the first recording layer,... the sensitized to light of a wavelength lambda _i 1, the second, ..., and claim 4 having a first (i-1) a multilayer structure are laminated in this order on the recording layer of the i coloring in the recording layer different from the color of the The recording material according to claim 7.