JPH05100417A - Photosensitive and heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To provide the recording material enhanced in color development density and improved in storage stability of a non-image part, especially, in partition performance in the sensitive wavelength region of each photosensitive heat-sensitive layer of the recording material. CONSTITUTION:The photosensitive heat-sensitive recording material has each interlayer containing an ultraviolet absorber represented by formula I and/or a polymer containing it. In formula I, each of R1 and R3 is 1-20C alkyl or a group represented by formula II; R2 is H, 1-5C alkyl, or 6-20 deg.C aryl; in formula II R4 is H or 1-4C lower alkyl: A is -CONH-, -COO-, car phenylene; B is a divalent bonding group; and n is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light and heat sensitive recording material which can be used in the fields of recording papers for facsimiles, printers, etc., presentation films, medical recording films, print proofs, etc. The present invention relates to a light and heat sensitive recording material in which the fractionation property of each light and heat sensitive layer in the light sensitive wavelength region is improved.

[0002]

Recording materials using an electron-donating colorless dye and an electron-accepting compound are pressure-sensitive paper, thermal paper, photosensitive pressure-sensitive paper,
It is already well known as an electrically conductive recording paper and a thermal transfer. For example, British Patent 2140449 and US Patent 448.
0052, same 4436920, Japanese Patent Publication No. 60-2399.
2, JP-A-57-179836 and JP-A-60-12355.
6, the same 60-123557 and so on. However, the recording material using the electron-donating colorless dye and the electron-accepting compound has a drawback that the non-image area is recolored due to reheating after image recording. Has been done.

As a form of a recording material which solves these problems, (1) an attempt to microencapsulate a polymerizable composition and an electron-donating colorless dye, (2) an electron-donating colorless dye containing a photopolymerizable composition An attempt to use an electron-accepting compound or a photopolymerizable electron-accepting compound containing microcapsules and a photopolymerizable composition, (3) a capsule containing an electron-donating colorless dye, and a photopolymerizable composition Attempts and the like using an electron-accepting compound or a photopolymerizable electron-accepting compound have been devised. Attempts have been made to achieve multicolor using these. In the case of a multi-color recording material, for example, a multi-layer recording material including microcapsules containing electron-donating colorless dyes that develop different hues and a photocurable composition sensitive to light of different wavelengths in each layer Can be used. For example, a microcapsule containing an electron-donating colorless dye that develops cyan and a layer containing a photocurable composition that is sensitive to wavelength λ1 are provided on a support, and an electron-donating colorless dye that develops magenta is formed on the support. A layer containing a microcapsule containing C and a photocurable composition that is sensitive to wavelength λ2 is provided, and a microcapsule that contains an electron-donating colorless dye that develops a yellow color and a photocurable composition that is sensitive to wavelength λ3 are provided on the layer. It is configured by providing a layer containing the composition. However, it was difficult to separate the photosensitive wavelength range of each photosensitive layer. When a conventionally known photopolymerization initiator or a combination of a photopolymerization initiator / spectral sensitizer is used, the photosensitive wavelength region of each layer overlaps, and each layer is not photopolymerized independently. It was difficult. With respect to this point, there is an attempt to add an ultraviolet absorber to a photosensitive composition as disclosed in, for example, JP-A No. 61-24495 (or US Pat. No. 4,576,891). However, although this method shows improvement, the overlap in the photosensitive wavelength region is still large. That is, unless the fraction of the sensitive material layer that develops each color is sharp, color mixing occurs and the commercial value of the recording material is impaired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light and heat sensitive recording material having a high color density and improved storability in the non-image area, and especially to improve the fractionation property of each light and heat sensitive layer in the light sensitive wavelength region. To provide the recording material.

[0005]

The object of the present invention is to form a latent image on a photocurable composition by exposure, and a component involved in coloring or decoloring by heating moves in a light-sensitive material according to the latent image. At least two light and heat sensitive layers for forming a color image are provided, and an intermediate layer containing a UV absorber represented by the following general formula (I) and / or a polymer containing the same is provided between the light and heat sensitive layers. It is achieved by a light and heat sensitive recording material characterized by being provided. General formula (I)

[0006]

[Chemical 3]

In the formula, R1 and R3 are an alkyl group having 1 to 20 carbon atoms, or a group represented by the general formula (II), R2
Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. General formula (II)

[0008]

[Chemical 4]

In the formula, R4 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and A represents -CONH-,-
Represents a COO- or phenylene group, and B represents a divalent linking group. n represents 0 or 1. Preferred examples of R1 and R3 are alkyl groups having 1 to 16 carbon atoms, and particularly preferred examples are alkyl groups having 1 to 8 carbon atoms.
Further, among the compounds represented by the general formula (I), the melting point is 30 ° C.
It is preferably -100 to 100 ° C, particularly preferably 30 to 60 ° C.

Specific examples of the ultraviolet absorber according to the present invention include the following.

[0011]

[Chemical 5]

[0012]

[Chemical 6]

In the image according to the present invention, a photocurable composition is imagewise exposed and cured, and then uniformly heated to bring an electron-accepting compound into contact with an electron-donating colorless dye in the uncured portion to develop a color. Is obtained by In the present invention, there are at least two light and heat sensitive layers containing the above photocurable composition, and since the color hue of each layer is different and the photosensitive wavelength range of each layer is different, images of different colors are independently formed in each layer. Can be formed. One preferable constitution of the recording material according to the present invention is a photosensitive material containing a microcapsule containing an electron-donating colorless dye, an electron-accepting compound having a polymerizable ethylene group, and a photocurable composition having a photopolymerization initiator. It has at least two heat-sensitive layers, and a layer containing an ultraviolet absorber and / or a polymer thereof is provided on the support between the light- and heat-sensitive layers.

When a conventionally known photopolymerization initiator or a combination of photopolymerization initiator / spectral sensitizer is used, the photosensitive wavelength region of each layer is overlapped, but in the present invention, We have succeeded in eliminating this overlapping region by providing an intermediate layer containing a UV absorber and / or a polymer containing it between the light and heat sensitive layers to limit the light reaching the lower layer.

As a method of introducing the ultraviolet absorber into the intermediate layer, various conventionally known methods can be used. One is a so-called emulsification dispersion method in which an ultraviolet absorber is dissolved in a water-insoluble organic solvent, the solution is emulsified and dispersed in an aqueous dispersion medium containing a surfactant, and fine droplets are introduced into the intermediate layer. There is a method called. Another method is to introduce a polymer latex carrying an ultraviolet absorber into the intermediate layer. The polymer latex carrying the ultraviolet absorber can be obtained by a method known in the art. That is, specific examples of the step of dispersing an ultraviolet absorber in a polymer latex, and the curing and impregnating latex used by dispersing the latex are described in US Pat. No. 4,199,363, West German Patent Application (OLS) No. 2541274 and No. 254.
1230, JP-A-49-74538, 51-59.
No. 943, No. 54-32552, and various publications
ch Disclosure, Vol. 148,197
It is described in Item 14850, August 6th year. Suitable latexes include, for example, acrylic acid ester or methacrylic acid ester (eg, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoxyethyl methacrylate, etc.).
And an acid monomer (for example, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc.) copolymer latex is preferable. As an example, the UV absorber is dissolved in a water-insoluble volatile organic solvent and the solution is emulsified and dispersed in an aqueous dispersion medium containing a surfactant to form fine droplets, which are then mixed with a polymer latex. do it. Another method is to introduce a polymer latex containing an ultraviolet absorber monomer as a polymerization component into the intermediate layer.
Still another is to dissolve a polymer of an ultraviolet absorber pre-synthesized from an ultraviolet absorber monomer in a water-insoluble organic solvent and emulsify and disperse the solution in an aqueous dispersion medium containing a surfactant. There is also an emulsion dispersion method in which minute droplets are introduced into the intermediate layer. The most preferable method of introducing the ultraviolet absorber in the recording material of the present invention is to use a polymer synthesized from a polymerizable ultraviolet absorber from the viewpoint of preventing diffusion to the adjacent layer.
Examples include latex and polymer emulsion dispersions.

The UV absorber polymer which is soluble in a water-insoluble organic solvent is prepared by copolymerizing one or more copolymerizable monomers in a suitable solvent with a known polymerization initiator. can get. For details on radical polymerization and other techniques, see the book. For example, W. R. Sorens
on "Preparative Methods of
Polymer Chemistry ", J. Bra
ndrup "Polymer Handbook" (W
illey & Sons) etc. Examples of these copolymerization monomers include the following. (Meta)
Examples thereof include compounds having a polymerizable unsaturated bond selected from acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and crotonic acid esters. Specifically, for example, (meth) acrylic acid esters, for example, alkyl (meth) acrylate, or substituted alkyl (meth)
Acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate] -, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, t-octyl (meth) acrylate, chloroethyl (meth) acrylate -, Allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate
4-hydroxybutyl (meth) acrylate, 2,
2-Dimethyl-3-hydroxypropyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate
G, trimethylolpropane mono (meth) acrylate
G, pentaerythritol mono (meth) acrylate,
Benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate
, Furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, etc.]: aryl (meth) acrylate (eg phenyl (meth) acrylate, cresyl) (Meth) acrylate, naphthyl (meth) acrylate, etc.): (meth) acrylamides, for example (meth)
Acrylamide, N-alkyl (meth) acrylamide (as the alkyl group, for example, methyl group, ethyl group,
Examples include a propyl group, a butyl group, a t-butyl group, a heptyl group, an octyl group, an ethylhexyl group, a cyclohexyl group, a hydroxyethyl group and a benzyl group. ), N-aryl (meth) acrylamide (as the aryl group,
Examples include phenyl group, tolyl group, nitrophenyl group, naphthyl group and hydroxyphenyl group. ), N, N
-Dialkyl (meth) acrylamide (the alkyl group includes, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N-diaryl (meth) acrylamide (the Examples of the aryl group include phenyl group), N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, N-2-acetamidoethyl-N-. Acetyl (meth) acrylamide, N- (phenylsulfonyl) (meth) acrylamide, N- (p-methylphenylsulfonyl) (meth) acrylamide, etc .: Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, caprylic acid). Allyl, allyl laurate, allyl palmitate, Allyl thearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc., allyloxyethanol, etc .: vinyl ethers such as alkyl vinyl ethers (for example, hexyl group, octyl group, decyl group as the alkyl group) , An ethylhexyl group,
Methoxyethyl group, ethoxyethyl group, chloroethyl group, 1-methyl-2,2-dimethylpropyl group, 2-ethylbutyl group, hydroxyethyl group, hydroxyethoxyethyl group, dimethylaminoethyl group, diethylaminoethyl group, butylaminoethyl group , Benzyl group, tetrahydrofurfuryl group, etc.), vinyl aryl group
Ter (as the aryl group, for example, phenyl group, tolyl group, chlorophenyl group, 2,4-dichlorophenyl group,
Naphthyl group, anthranyl group, etc.); vinyl esters such as vinyl butyrate, vinyl isobutyrate
Vinyl acetyl acetate, vinyl diethyl acetate, vinyl valet, vinyl caproate, vinyl chloracetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate. -, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate,
Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .: Styrenes such as styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexyl) Styrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg methoxystyrene,
4-methoxy-3-methylstyrene, dimethoxystyrene, etc., halogenostyrene (for example, chlorostyrene,
Dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene,
Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.): Crotonic acid esters, for example, alkyl crotonic acid (eg, butyl crotonic acid, hexyl crotonic acid, glycerin monochromatic). Tone), etc .: Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): Dialkyls of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.): (meta ) Acrylonitrile and the like.

The electron-accepting compound having a polymerizable ethylene group according to the present invention is a phenol derivative having at least one polymerizable ethylene group and a phenolic hydroxyl group. JP-A-63-173682, methacryloxyethyl ester of benzoic acid having a hydroxy group and acryloxyethyl ester which can be synthesized by a similar synthetic method and JP-A-59-83693,
Nos. 60-141587 and 62-99190, esters of benzoic acid having a hydroxy group and hydroxymethylstyrene, hydroxystyrene described in European Patent 29323, and JP-A-62-16.
7077 and 62-16708, N-vinylimidazole complexes of zinc halides and 63-
Examples thereof include color former monomers described in No. 317558 and compounds represented by the following general formula (III).
General formula (III)

[0018]

[Chemical 7]

In the formula, X represents a hydrogen atom or a halogen atom, Y represents a monovalent group having a polymerizable ethylene group, and Z represents a hydrogen atom, an alkyl group, a hydroxyl group or an alkoxy group. In the formula, among the monovalent groups having a polymerizable ethylene group represented by Y, an aralkyl group having a vinyl group, an acryloyloxyalkyl group and a methacryloyloxyalkyl group are preferable.

Specific examples of the electron-accepting compound represented by the general formula (III) are shown below. 3-Chloro-4-hydroxybenzoic acid vinylphenethyl ester, 3-chloro-4-
Hydroxybenzoic acid vinyl phenylpropyl ester,
3-chloro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxyethyl) ester), 3-chloro-4-hydroxybenzoic acid- ( 6
-Methacryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (6-acryloyloxyhexyl) 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- (8-methacryloyloxyoctyl) ester, 3-chloro-4-hydroxybenzoic acid- (9-methacryloyloxynonyl) ester, 3-chloro -4-Hydroxybenzoic acid- (8-acryloyloxyoctyl) ester, 3-chloro-4
-Hydroxybenzoic acid- (9-acryloyloxynonyl) ester, 3-fluoro-4-hydroxybenzoic acid-
(2-acryloyloxyethyl) ester, 2,4-
Dihydroxy-6-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxy-5-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxy-3-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxy-3-chloro Vinyl benzyl benzoate,
2,4-Dihydroxy-6-phenylbenzoic acid vinyl bezyl ester, 2,4-dihydroxybenzoic acid vinylphenethyl ester, 2,4-dihydroxybenzoic acid vinylphenylpropyl ester, 2,4-dihydroxybenzoic acid vinylbenzyl ester, 2- Acryloyloxy-4-hydroxybenzoic acid- (2-acryloxyoxyethyl) ester, 2-methacryloyloxy-4-
Hydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 2,4-dihydroxybenzoic acid (2,3
-Bismethacryloyloxypropyl) ester, 2,
4-dihydroxybenzoic acid (2,3-bisacryloyloxypropyl) ester and the like can be mentioned.

These electron-accepting compounds may be used in combination with other non-polymerizable electron-accepting compounds. As the non-polymerizable electron accepting compound, a phenol derivative,
Examples include salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins, and metal complexes. Examples of these are JP-B-40-9309, JP-B-45-14039, JP-A-52-140483, and JP-A-48-51510.
JP-A-57-210886, JP-A-58-870
89, JP-A-59-112286, JP-A-60-17.
No. 6795, JP-A No. 61-95988, and the like. As an example of some of these, the phenolic compound is 2,2'-bis (4-hydroxyphenyl)
Propane, 1,1'-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1,1'-bis (3-chloro-4-hydroxyphenyl) 2-ethylbutane, 4,4'-sec-isooctylidene dipheno-
4,4'-sec-butylidene diphenol, 4,
There are 4'-isopentylidenephenol, benzyl p-hydroxybenzoate and the like. As salicylic acid derivative,
3-dodecylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (ter-octyl) salicylic acid, 3-dodecyl-5-methylsalicylic acid, 5-
α- (p-α-methylbenzylphenyl) ethylsalicylic acid, 3-α-methylbenzyl-5-ter-octylsalicylic acid, 3,5-dinonylsalicylic acid, 3-nonyl-5-ter-butylsalicylic acid, 4-dodecyl There are oxysalicylic acid, 3-α, α-dimethylbenzyl-6-methylsalicylic acid, 3,5-bis-α, α-dimethylbenzyl-6-methylsalicylic acid and the like, and zinc, aluminum and nickel salts thereof. When these electron-accepting compounds other than the present invention are used in combination, it is preferable to use the electron-accepting compound of the present invention in an amount of 50% by weight or more, preferably 70% by weight or more.

The photocurable composition according to the present invention may be used in combination with a polymerizable compound having at least one polymerizable ethylene group in the molecule. For example, acrylic acid and its salts, acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters,
Examples thereof include itaconic acid, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, aryl ethers and allyl esters. Among these, a polymerizable compound having a plurality of ethylenically unsaturated double bonds in the molecule is particularly preferable, and for example, acrylic ester of polyvalent alcohol such as trimethylolpropane or pentaerythritol. And methacrylic acid ester, and acrylate or methacrylate
Epoxy resin, acrylate or methacrylate
There are polyesters with terminal ends. Specific examples of particularly preferable compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate. And hexanediol-1,6-dimethacrylate and diethylene glycol dimethacrylate. Regarding the molecular weight of the polyfunctional monomer, about 10
0 to about 5000 are preferred, more preferably about 300
~ About 2000.

In addition to these compounds, for example, as a photocrosslinkable composition, vinyl cinnamate, polycinnamylidene vinyl acetate, a photosensitive resin having an α-phenylmaleimide group, and the like can be added. Further, in addition to these compounds, a thermal polymerization inhibitor can be added if necessary. The thermal polymerization inhibitor is added in order to prevent thermal polymerization of the photopolymerizable composition or polymerization over time, and thereby the chemical stability of the photopolymerizable composition during preparation and storage. Can be increased.

The photopolymerization initiator preferably used in the present invention is selected from the compounds capable of initiating photopolymerization of the electron-accepting compound having a polymerizable ethylene group or the compound having an ethylenically unsaturated double bond. It is possible to select one kind or a combination of two or more kinds of compounds. The following compounds can be mentioned as preferable specific examples of the photopolymerization initiator. Aromatic ketones: for example, benzophenone, 4,
4'-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimeraminobenzophenone, 4,4 '
-Dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-ter-butylanthraquinone, 2-
Methyl anthraquinone, xanthone, thioxanthone,
2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers: eg benzoin methyl ether.
Ter, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2,
4,5-triallyl imidazole dimer: eg 2-
(O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2-
(O-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5
-Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer;
And polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone and JP-A-53-133428, JP-B-57-1819, JP-B-57-6096, US The compounds described in the respective specifications of Japanese Patent No. 3615455,
S-triazine derivatives having a trihalogen-substituted methyl group described in JP-A-58-29803: for example, 2,
4,6-Tris (trichloromethyl) -S-triazine, 2-methoxy-4,6-bis (trichloromethyl)
Compounds such as -S-triazine, 2-amino-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine; and For example, JP-A-59-18
9340 Organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoimper oxide, benzoylperoxide, di-ter-butyldiper-oxyisophthalate, 2,5-dimethyl-2,5-di (benzoylper)
(Oxy) hexane, ter-butylperoxybenzoate, α, α′-bis (ter-butylperoxyisopropyl) benzene, dicumylperoxide, 3,
Compounds such as 3 ', 4,4'-tetra- (ter-butylperoxycarbonyl) benzophenone, and azinium salt compounds described in, for example, U.S. Pat. No. 4,743,530; and organic compounds described in, for example, European Patent No. 223587. Boron compound: For example, tetramethylammonium salt of triphenylbutylborate, tetrabutylammonium salt of triphenylbutylborate, tri (p-
Photopolymerization initiators known in the art such as tetramethylammonium salts of methoxyphenyl) butyl borate and iron allene complexes can be usefully used.

As the photopolymerization initiator system, a combination of two or more kinds of compounds is known, and a combination thereof can be used in the present invention. Examples of combinations of two or more compounds include 2,4
Combination of 5-triallyl imidazole dimer and mercaptobenzoxazole, U.S. Pat. No. 3,427,1.
Combination of 4,4'-bis (dimethylamino) benzophenone with benzophenone or benzoin methyl ether as described in US Pat.
No. 50 benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6-
A combination of (4'-methoxyphenyl) -triazole, a combination of dialkylaminobenzoic acid ester and quinmethylthioxanthone described in JP-A-57-23602, and JP-A-59-78339. 4,4′-bis (dimethylamino) benzophenone, benzophenone, and a polyhalogenated methyl compound may be combined. More preferred examples include a combination of 4,4′-bis (diethylamino) benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, and a combination of 4,4′-bis (diethylamino) benzophenone and 2 , 4,5-triallyl imidazole dimer combination.

Among these photopolymerization initiators, particularly preferred compounds include benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group, organic peroxides, azinium salt compounds and organic boron compounds. it can. The content of the photopolymerization initiator is preferably 0.01 to 20% by weight, based on the total weight of the photopolymerization composition,
And more preferably, it is 0.2 to 15% by weight, and the most preferable content is 5 to 10% by weight. If it is less than 0.01% by weight, the sensitivity is insufficient, and if it exceeds 10% by weight, an increase in sensitivity cannot be expected.

The recording material of the present invention may contain, in addition to the polymerizable electron-accepting compound and the photopolymerization initiator, a spectral sensitizing dye for adjusting its photosensitive wavelength. As the spectral sensitizing dye, various compounds known in the art can be used. Examples of the spectral sensitizing dye are the above-mentioned patents relating to the photopolymerization initiator and Research Disclosure.
e, Vol. 200, December 1980, Item 2
Reference can be made to pages 160 to 163 and the like of 0036 and “sensitizer” (Katsumi Tokumaru, Shin Okawara / edited by Kodansha 1987). Specific examples of the spectral sensitizing dye include, for example, JP-A-58-15503, 3-ketocoumarin compound, JP-A-58-40302, thiopyrylium salt, and JP-B-59-28328. In 60-53300, naphthothiazo-merocyanine compounds are disclosed in Japanese Patent Publication No.
1-9621, 62-3842, JP-A-59-8.
Nos. 9303 and 60-60104 disclose merocyanine compounds, respectively. With these spectral sensitizers, the spectral sensitivity of the photopolymerization initiator can be extended to the visible range. In the above example, the trihalomethyl-S-triazine compound is taken as the photopolymerization initiator,
You may combine with another photoinitiator. Spectral sensitizing dyes include keto dyes such as coumarin (including ketocoumarin and sulfonocoumarin) dyes, merostyryl dyes, oxonol dyes and myoxonol dyes, non-keto polymethine dyes, anthracene dyes,
Rhodamine dyes, acridine dyes, aniline dyes, azo dyes, non-ketopolymethine dyes such as cyanine, hemicyanine and styryl dyes are included.

The photopolymerizable composition used in the present invention further comprises a reducing agent such as an oxygen scavenger and a chain transfer agent of an active hydrogen donor, and a chain, as an auxiliary agent for further promoting the polymerization. It is also possible to use in combination with other compounds that accelerating the polymerization. Oxygen scavengers include phosphines, phosphonates, phosphites, stannous salts and other compounds that are easily oxidized by oxygen. For example, N-phenylglycine, trimethylbarbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N-2,4,6-pentamethylaniline and the like. Further, the following thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides and the like are also useful as the polymerization accelerator.

Examples of the electron-donating colorless dye according to the present invention include triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leuco-olamine compounds, rhodamine-lactam compounds, and tri- compounds. There are various compounds such as phenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds. Specific examples of the phthalides include US Reissue Patent Specification No. 23024 and US Patent Specification No. 34.
No. 9111, No. 3491112, No. 349111
No. 6 and No. 3509174, and specific examples of fluoranes are described in US Pat. No. 3,624,107 and No. 36277.
No. 87, No. 3641011, No. 3462828,
No. 3681390, No. 3920510, No. 3
No. 959571, specific examples of spiropyrans are US Pat. No. 3,971,808, and pyridine compounds and pyrazine compounds are US Pat. No. 3,775,424, No. 38.
No. 53869, No. 4246318, fluorene compounds and the like.

In particular, when used for a full color recording material,
Examples of magenta-coloring type electron-donating colorless dyes include US Pat. No. 4,800,149 and West German Patent Publication No. 2265.
No. 233, West German Patent Publication No. 2409112, Japanese Patent Application Nos. 63-333886, 63-256808, etc.
As a yellow-color type, US Pat. No. 4,800,418
No. 4775656, No. 4540790, No. 40
No. 25090, No. 4446321, No. 4365503
No. 4820841, No. 4598150, JP-A Nos. 62-288828, 62-288828, 6
3-251280, 63-251279, 63
No. 251278, No. 64-251279, and British Patent No. 1431493 are the cyan color-developing types.
JP-A-63-53542, JP-A-62-270662,
No. 63-113446, No. 63-112188, JP-A No. 1-213636, and European Patent Publication No. 8
The compounds described in No. 2822 and the like are useful.

The ratio of the electron-donating colorless dye and the electron-accepting compound used in the recording material according to the present invention is
1 to 100 with electron-accepting compound / electron-donating colorless dye
(Molar ratio) is preferable. Also, the amount of these used is 0.1 to 2 g / m 2 for the electron-donating colorless dye per color forming layer.
² preferably 0.2 to 1 g / m ² , the electron accepting compound is 0.2 to 20 g / m ^2, preferably 0.4 to 10 g
/ M ² used.

When the electron-donating colorless dye of the present invention is microencapsulated, it can be prepared by a method known in the art. For example, US Pat. Nos. 2,800,457 and 2,804.
Coacervation of hydrophilic wall-forming material as seen in No. 58
Method utilizing the application, U.S. Pat. No. 3,287,154,
British Patent No. 990443, Japanese Patent Publication No. 38-19574
No. 42-446, No. 42-771, interfacial polymerization method, U.S. Pat. No. 3,418,250, No. 36.
No. 60304, by polymer precipitation, US Pat. No. 3,796,669, using the isocyanate polyol wall material, US Pat. No. 3,914,511.
US Pat. Nos. 4,001,140, 4,087,376, and 40, using the isocyanate wall material found in U.S. Pat.
No. 89802, a method of using a wall-forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose, which uses a urea-formaldehyde type, urea formaldehyde-resorcinol type wall material, JP-B-36-
9168, in-situ method by polymerization of monomers found in JP-A-51-9079, British Patent No. 9528.
No. 07, 965074, electrolytic dispersion cooling method,
U.S. Pat. No. 3,111,407, British Patent No. 930422.
There is a spray-drying method etc. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall after emulsifying the core substance. As a method for producing the microcapsule wall of the present invention, the effect is great especially when the microencapsulation method by polymerizing the reactant from the inside of the oil droplet is used. That is,
Within a short period of time, it is possible to obtain capsules having a uniform particle size and excellent as a raw material, which is preferable as a recording material.

For example, when polyurethane is used as the capsule wall material, the polyvalent isosoate and, if necessary, the second substance (eg, polyol, polyamine) which reacts with it to form a capsule wall should be encapsulated. By mixing in an oily liquid, emulsifying and dispersing in water, and then raising the temperature, a polymer forming reaction occurs at the oil droplet interface to form a microcapsule wall. At this time, an auxiliary solvent having a low boiling point and a strong dissolving power can be used in the oily liquid. In this case, the polyvalent isocyanate used and the partner polyol and polyamine which react with it are described in US Pat.
281383, 3737695, 379326
No. 8, Japanese Patent Publication No. 48-40347, No. 49-24159.
JP-A-48-80191 and JP-A-48-84086, and they can be used. A water-soluble polymer can be used when making microcapsules. The water-soluble polymer is a water-soluble anionic polymer,
Either a nonionic polymer or an amphoteric polymer may be used. As the anionic polymer, natural or synthetic ones can be used, and examples thereof include those having a —COO—, —SO ₂ — group and the like. Specifically, natural anionic polymers include arabic gum, alginic acid, pectin, etc., and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated starch, sulfated cellulose. , Lignin sulfonic acid, etc. As synthetic products, maleic anhydride (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Nonionic polymers having carboxy-modified polyvinyl alcohol and the like include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of amphoteric compounds include gelatin. 0.01 to 10% by weight of these water-soluble polymers
Used as an aqueous solution of.

The size of the capsule used in the present invention is 80 μm.
m or less, and particularly preferably 20 μm or less from the viewpoint of storability and handleability. If the capsule is too small, the surface area for a certain solid content becomes large and a large amount of wall material is required. Therefore, 0.1 μm or more is preferable. The electron-donating colorless dye according to the present invention may be present in a solution state or a solid state in the microcapsules.
When a solvent is used in combination, the amount of the solvent used in the capsule is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the electron-donating colorless dye.

A natural oil or a synthetic oil can be used in combination as the solvent used in the present invention. Examples of these solvents include cottonseed oil, kerosene, paraffin, naphthene oil, alkylated biphenyl, alkylated ta-phenyl,
Chlorinated paraffins, alkylated naphthalenes and diallylethanes such as 1-phenyl-1-xylylethane, 1-phenyl-1-p-ethylphenylethane, 1,1'-ditolylethane, phthalates, phosphates, quenches. Acid ester, benzoic acid ester, alkylamide, fatty acid ester, trimesic acid ester, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate,
Examples include cyclohexanone. A volatile solvent may be used as an auxiliary solvent for dissolving the electron-donating colorless dye during microencapsulation. Examples of this type of solvent include ethyl acetate, butyl acetate, methylene chloride and the like.

When the recording material of the present invention is used as a multicolor coloring material, for example, a microcapsule containing an electron-donating colorless dye that develops different hues and a photocurable composition that is sensitive to light of different wavelengths are formed in each layer. An intermediate layer containing the ultraviolet absorber of the present invention and / or a polymer thereof is provided between the light and heat sensitive layers. The intermediate layer is mainly composed of a binder and an ultraviolet absorber, and may contain additives such as a curing agent and a polymer latex, if necessary. As the ultraviolet absorber, other than the one of the present invention, an ultraviolet absorber matched to the fractionation wavelength can be used. For example, a benzotriazole compound, an aminoallylidenemalonnitrile compound, a benzophenone compound, a cinnamic acid ester compound can be used. Compounds known in the art such as compounds and aminibutadiene compounds can be used. Although these UV absorbers are added to the intermediate layer, they may be added to the protective layer, the light and heat sensitive layer, the antihalation layer and the like, if necessary.

In the present invention, the dispersion of the photocurable composition and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer, but the water-soluble polymers which can be preferably used in the present invention are used. 25 ° C as a polymer
A compound soluble in water of 5% by weight or more is preferred,
Specifically, gelatin, gelatin derivatives, albumin,
Proteins such as casein, cellulose derivatives such as methyl cellulose and carboxymethyl cellulose, alginate
Da, sugar derivatives such as starches (including modified starch),
Synthesis of gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymer, polystyrene sulfonate, etc. Polymers can be mentioned. Of these, gelatin and polyvinyl alcohol are preferred.

As the binder used as necessary in the recording material according to the present invention, the above water-soluble polymer, polystyrene, polyvinyl formal, polyvinyl butyral,
Acrylic resin: for example, polymethylmethacrylate, polybutylacrylate, polymethylmethacrylate, polybutylmethacrylate and their copolymers, phenol resin, styrene-butadiene resin, ethylcellulose -
Solvent-soluble polymers such as epoxy resins and urethane resins, or polymer latexes thereof can be used.
Of these, gelatin and polyvinyl alcohol are preferred. In the recording material of the present invention, various surfactants may be used for various purposes such as coating aid, antistatic property, slip property improvement, emulsion dispersion, and adhesion prevention. Examples of the surfactant include nonionic surfactants such as saponin, polyethylene oxide, and polyethylene oxide derivatives such as alkyl ether of polyethylene oxide, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl sulfates. ester,
Anionic surfactants such as N-acyl-N-alkylitaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, and amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, If necessary, a cationic surfactant such as an aliphatic or aromatic quaternary ammonium salt can be used. Various additives can be added to the recording material of the present invention, if necessary, including the additives described above. For example, dyes, UV absorbers, plasticizers, optical brighteners, which prevent irradiation and halation,
Typical examples of matting agents, coating aids, curing agents, antistatic agents and slipperiness improving agents are Research Disclosure.
e, Vol. 176, December 1978, Item 1
7643, and Vol. 187, November 1979,
Item 18716.

The coating solution of the recording material of the present invention is constituted by adding the above-mentioned microcapsule dispersion, electron-accepting compound dispersion, photopolymerization initiator and various additives. This coating solution is applied on a desired support and dried. In the case of a multicolor recording material, an intermediate layer containing, for example, the ultraviolet absorber according to the present invention and / or a polymer thereof, and a light and heat sensitive layer are repeatedly provided on this light and heat sensitive layer. Further, it is preferable to provide a protective layer on the uppermost layer.

To apply the coating solution onto the support,
Doctor coater, rod coater, knife coater, roll coater coater, comma coater, river roll coater, transfer roll coater, gravure coater
It is possible to use a water, kiss roll coater, a carten coater, an extrusion coater or the like. As a coating method, Research Disclosure,
Vol. 200, December 1980, Item 200
You can refer to item 36. The thickness of the recording paper is 0.1μ
m to 50 μm is suitable. The support may be paper, paper
Supports such as tied paper, laminated paper, synthetic paper, transparent films such as polyethylene terephthalate film, polystyrene film, polycarbonate film, and metal plates such as aluminum, zinc, and copper. Examples of the support include those obtained by subjecting the surface of the support to various treatments such as surface treatment, undercoating and metal vapor deposition treatment. As a support, Research Disclosure, Vo
l. 200, December 1980, Item 20036
The support of item can also be referred to. If necessary, these supports may be provided with an antihalation layer on the front surface and a slip layer, an antistatic layer, a curl prevention layer, a pressure-sensitive adhesive layer or the like on the back surface according to the purpose.

The recording material of the present invention can record with high sensitivity by light in a wide range from ultraviolet light to visible light. As the light source, mercury lamp, xenon lamp, tungsten lamp,
Various lasers such as metal halide lamps, argon lasers, helium neon lasers, semiconductor lasers, LEs
A wide range of light sources such as D and fluorescent lamps can be used. As an image recording method, various exposure methods such as contact exposure of a document such as a lith film, enlargement exposure of a slide or a liquid crystal image, and reflection exposure using reflected light of the document can be used. When performing multicolor recording, image recording may be performed multiple times by using lights having different wavelengths. Light having different wavelengths can be obtained by changing the light source or the optical filter. It can also be obtained by directly printing an image with a thermal head. When the recording material of the present invention is imagewise exposed, it is subjected to a heat development treatment after the imagewise exposure. As a heating method in this heat development treatment, various conventionally known methods can be used. The heating temperature is generally 80 ° C to 200 ° C, preferably 100 ° C.
To 160 ° C. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute. The entire surface may be exposed after the heat development process to photo-cur the uncured portion. Examples of the present invention will be shown below, but the present invention is not limited thereto.

[0042]

Example 1). [Preparation of Electron Donor Colorless Dye Capsule Liquid] 3,3-bis (1-octyl-2-methylindole)
8.9 g of 3-yl) phthalide was dissolved in 16.9 g of ethyl acetate, and 20 g of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. .. Add this solution to 8
% Phthalated gelatin 41 g and 10% sodium dodecylbenzene sulfonate solution 1.4 g were added and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 71 g of a 2.9% triethylenepentamine aqueous solution were added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, a capsule liquid having an average particle size of 0.5 μm was obtained.

2). [Preparation of Emulsion of Photocurable Composition] 2-O-chlorophenyl-4,5-as a photopolymerization initiator
0.12 g of diphenylimidazole dimer and 7-diethylamino-4-methylcoumarin as a spectral sensitizing dye.
5 g of 3-chloro-4-hydroxybenzoic acid- (6-methacryloyloxyhexyl) ester was added to 12 g and 0.06 g of N-phenylglycine ethyl ester as an auxiliary agent for accelerating the polymerization, and 3 g of isopropyl acetate. This solution was added to a mixed solution of 13 g of a 13% gelatin aqueous solution and 0.8 g of a 2% nonylphenoxybutanesulfonic acid bis-2-ethylhexyl ester sodium salt aqueous solution, and a homogenizer (manufactured by Nippon Seiki Co., Ltd.) 1
The emulsion was emulsified at 0000 rpm for 5 minutes to obtain an emulsion of the photocurable composition.

3). [Preparation of Dispersion of Ultraviolet Absorber] 3-a. Preparation of Emulsion (A) of UV Absorber 7.5 g of UV absorber (13) and UV absorber (17)
A solution prepared by dissolving 2.4 g in 17.5 g of ethyl acetate was added to 1
Emulsion (A) of ultraviolet absorber was added to a mixed solution of 62 g of 5% gelatin aqueous solution and 1 g of 62% dodecylbenzene sulfonic acid aqueous solution, which was emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) for 5 minutes at 10,000 revolutions. Got

3-b. Ultraviolet absorbent emulsion (B) ~
Preparation of (E) 3-a. 3 except that 7.5 g of the ultraviolet absorbent (13) in Example 1 was replaced with the ultraviolet absorbents (5) and (14) to (16).
a. In the same manner as described above, the ultraviolet absorbent emulsion (B) ~
(E) was obtained. Below, the ultraviolet absorbers (13) to (1
The chemical structural formula of 7) is shown.

[0046]

[Chemical 8]

3-c. Preparation of Latex Dispersion Liquid (F) of UV Absorber (5) A solution of 0.26 g of UV absorber (5) in 3 g of ethyl acetate was mixed with 62 g of 15% gelatin aqueous solution and 1 g of 62% aqueous dodecylbenzenesulfonic acid solution. Add to the mixed solution and use a homogenizer (Nippon Seiki Co., Ltd.) to obtain 100
The emulsion was emulsified at 00 rpm for 5 minutes. This emulsion was mixed with 9.25 g of latex (X) for latex dispersion of ultraviolet absorber and 10
% Gelatin aqueous solution (25.5 g) and stirred to obtain a latex dispersion (F) of the ultraviolet absorber (5). The specific method for synthesizing the latex (X) for latex dispersion of the ultraviolet absorber will be described below.

[Synthesis Method of Latex (X) for Latex Dispersion of Ultraviolet Absorber] 400 ml of distilled water and 1 g of surfactant were placed in a flask and stirred at 80 ° C. in a nitrogen stream. To this, 1 g of potassium persulfate and 0.5 g of sodium bisulfite were added. Furthermore, a mixture of 79 g of butyl methacrylate, 20 g of butyl acrylate and 1 g of acrylic acid was added little by little to the mixture, and after addition of the total amount, 1 g of potassium persulfate was further added.
And 0.5 g of sodium bisulfite were added and stirred for 1 hour. The obtained solution was neutralized to pH 6 with a 1N caustic soda solution and filtered with a filter paper to obtain the desired latex (X).

3-d. Preparation of Latex (G) Solution of Ultraviolet Absorber (8) 200 ml of distilled water and 0.5 g of surfactant were placed in a flask and stirred at 80 ° C. in a nitrogen stream. In this, 0.5 g of potassium persulfate and 0.25 sodium bisulfite
g was added. In addition, UV absorber (8) 16
g, butyl acrylate 33 g, and acrylic acid 1 g were added little by little, and after the total amount was added, 0.5 g of potassium persulfate and 0.25 g of sodium bisulfite were added and stirred for 1 hour. The obtained solution was neutralized to pH 6 with a 1N caustic soda solution and filtered with a paper filter to obtain the desired latex (G).

3-e. Polymer of UV absorber (9)
Preparation of Dispersion Liquid (H) of (Y) A solution prepared by dissolving 7.5 g of polymer (Y) of ultraviolet absorber (9) and 2.4 g of ultraviolet absorber (17) in 17.5 g of ethyl acetate was added at 15%. The mixture was added to a mixed solution of 62 g of gelatin aqueous solution and 1 g of 62% dodecylbenzenesulfonic acid aqueous solution, and a homogenizer (manufactured by Nippon Seiki Co., Ltd.) was used for 10
The emulsion was emulsified at 000 rpm for 5 minutes to obtain a polymer dispersion (H) of an ultraviolet absorber. The specific method for synthesizing the polymer (Y) of the ultraviolet absorber (9) will be described below.

[Synthesis Method of Polymer (Y) of UV Absorber (9)] 7 g of UV absorber (9) and 3 g of benzyl methacrylate
And 30 ml of dioxane were placed in a flask and stirred at 80 ° C. in a nitrogen stream. V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.07 g / dioxane 1.5 ml was added thereto 3 times at intervals of 1 hour. Then react for 3 hours at a reaction temperature of 10
The temperature was raised to 0 ° C. and the mixture was stirred for 2 hours. The reaction solution was poured into methanol and the precipitate was collected by filtration to obtain a polymer of the ultraviolet absorber (9).
(Y) was obtained.

4). [Preparation of coating liquid for light and heat sensitive layer] 4 g of the electron-donating colorless dye capsule, 12 g of emulsion of the photosensitive composition and 12 g of 15% gelatin aqueous solution were mixed to prepare a coating liquid for light and heat sensitive layer.

5). [Preparation of coating liquid for intermediate layer] 5-a. Preparation of coating liquid for intermediate layer (1-1) 9 g of distilled water and 14 g of emulsion (A) of ultraviolet absorber and 2%
1.7 g of a hardener aqueous solution was mixed to prepare a coating liquid for the intermediate layer (1-1).

5-b. Preparation of Coating Liquid for Intermediate Layers (1-2) to (1-5) 14 g of the emulsion (A) of the ultraviolet absorber of 5-a was replaced with 14 g of emulsions (B) to (E) of the ultraviolet absorber, respectively. Intermediate layers (1-2) to (1-5) in the same manner as in 5-a except that
A coating solution was prepared.

5-c. Preparation of coating liquid for intermediate layer (1-6) Intermediate layer was prepared by mixing 9 g of distilled water, 14 g of latex dispersion (F) of ultraviolet absorber (5) and 1.7 g of 2% aqueous hardener solution. A coating solution for 1-6) was prepared.

5-d. Preparation of coating liquid for intermediate layer (1-7) Latex (G) 1 of 9 g of distilled water and ultraviolet absorber (8)
4 g and 1.7 g of a 2% hardener aqueous solution were mixed to form an intermediate layer (1-
A coating solution for 7) was prepared.

5-e. Preparation of coating liquid for intermediate layer (1-8) 9 g of distilled water, 14 g of polymer dispersion liquid (H) of ultraviolet absorber (9) and 1.7 g of 2% aqueous hardener solution were mixed to form an intermediate layer (1-8). ) Coating solution was prepared.

6). [Preparation of coating liquid for protective layer] 4.5 g of 10% gelatin aqueous solution, 4.5 g of distilled water and 2%
N-octylsulfonyl-N-propylglycine potassium salt aqueous solution 0.5 g and 2% triethylene glycol mono-p-nonylphenyl ether monosodium sulfobutyl ether aqueous solution 0.3 g and 2% N, N-bis (Vinylsulfonylacetyl) ethylenediamine aqueous solution 0.5 g and Syloid 72 (FUJI-DEVISON CHEM
ICHAL LTD. The coating liquid for the protective layer was prepared by mixing the above products in an amount such that the coating amount was 50 mg / m ² .

7). [Measurement of Required Coating Amount of Intermediate Layer and Transmission Spectrum: Evaluation (1)] Using a coating bar on a polyethylene terephthalate film having a thickness of 100 μm, the intermediate layer (1-
The coating liquids for 1) to (1-8) were applied and dried to prepare intermediate filter sheets (1-1) 'to (1-8)'. Using the uncoated film as a reference, the transmission spectra of these filter sheets were measured using a self-recording spectrophotometer MPS-2000 manufactured by Shimadzu Corporation. By changing the coating thickness, the 10% rising point of the transmission spectrum,
Intermediate filter-sheet (1-1) ', (1-3)'-
(1-5) 'is about 390 nm, and the intermediate filter sheets (1-2)' and (1-6) '-(1-8)' are about 370 nm.
The coating amount was determined when it was set to be nm. Further, the wavelength width from the 10% rising point to the 90% rising point of the transmission spectrum was examined. The results are shown in Table 1.
In Table 1, the maximum absorption wavelength in the solution spectrum in dimethylformamide and the wavelength at the bottom 10% point on the long-wave side of the absorption spectrum are measured and shown.

[0060]

[Table 1]

Examples 1 to 4 and Comparative Example 1 A coating solution for a light and heat sensitive layer was coated on a support similar to the one described above using a coating bar so that the dry weight of the coating layer was 8 g /
It was coated so as to have a surface area of m ² and dried at 30 ° C. for 10 minutes.
On this layer, coating solutions (1-2), (1-6) for intermediate layer
(1-8) and (1-5) were applied so that the dry weights were the values shown in Table 1 and dried in the same manner, and the coating solution for the protective layer was further applied onto the coating bar. The coating layer was applied so that the dry weight of the coating layer was 2 g / m ² , and dried in the same manner to obtain samples of Examples and Comparative Examples.

8). [Evaluation of Photosensitivity: Evaluation (2)] A step wedge (density difference of 0.1
5, High density mercury lamp of 2000W (Dainippon Screen printer-) through 2000W through density step number 1 to 15, Fuji Step Guide P, Fuji Photo Film Co., Ltd.
P627GA) for 100 seconds. After that, the photosensitivity after heating for 5 seconds on a hot plate at 120 ° C. is the number of step wedge steps corresponding to a density of about 10% of the color density of the positive type recording material when not exposed, and the results are shown in Table 2. Table 2 shows that the larger the number of steps, the higher the photosensitivity.

[0063]

[Table 2]

As is clear from Table 2, when the ultraviolet absorber of the present invention is used, the rise of the transmission region of the transmission spectrum of the intermediate layer is sharp in any case, and the photosensitivity of the recording material using this is high. It turns out to be expensive.

Example 5 Polyester film filled with white pigment (Toray Industries, Inc.)
Lumira E-60 (100 μm in thickness) was coated with a light- and heat-sensitive coating liquid (yellow-coloring) using a coating bar so that the dry weight of the coating layer was 8 g / m ² , and 3
It was dried at 0 ° C for 10 minutes. On top of this layer the middle layer (1-
1) was applied and dried to a dry weight of 1.0 g / m ² , and then a light and heat sensitive coating solution (magenta color development) was applied and dried to a dry weight of 8 g / m ² , and this layer The intermediate layer (1-2) is coated and dried so that the dry weight is 2.4 g / m ² , and the light- and heat-sensitive coating solution (cyan color development) is dried on the layer at a dry weight of 8 g / m 2. Coating solution is dried to ² and coating solution for the protective layer is coated on top of it.
Was coated so that the dry weight of the coating layer was 2 g / m ² , and dried at 30 ° C. for 10 minutes to obtain a sample of Example 5.

Examples 6 to 8 The intermediate layer (1-2) of 2.4 g / m ² was added to the intermediate layers (1-6) to
(1-8) Samples of Examples 6 to 8 were obtained in the same manner as in Example 5 except that 2.4 g / m ² was used.

Comparative Example 2 1.0 g / m ² of the intermediate layer (1-1) was added to the intermediate layer (1-3).
In place of 5.4 g / m ² , further 2.4 g of the intermediate layer (1-2)
A sample of Comparative Example 2 was obtained in the same manner as in Example 5, except that / m ² was replaced with 2.5 g / m ² of the intermediate layer (1-5).

The samples of Examples and Comparative Examples thus obtained were provided with a lith film on which an image for yellow was developed and an optical filter for blocking light of 410 nm or less (SC-41 filter: manufactured by Fuji Photo Film Co., Ltd.). Through 2000W
It was exposed to ultraviolet light from a high-frequency lighting high-pressure mercury lamp (printer P627GA manufactured by Dainippon Screen Co., Ltd.). Next, a magenta image-developed lith film and 365 nm-4
Exposed with the light of a mercury lamp through an interference filter that transmits only the light of 00 nm, and further through a lith film that has developed an image for cyan and an interference filter that transmits only the light of 340 nm to 365 nm through the light of the mercury lamp. And got a latent image. Then, it heated with a 120 degreeC hotplate for 5 seconds. At this time,
The minimum exposure required for each layer to obtain an image (evaluation 3), the maximum color density of each color when exposed under that condition (evaluation 4), and the minimum exposure required for each layer is 4 times each. Then, the maximum color density (evaluation 5) of each color was obtained when the exposure amount was given and the overexposure was performed. The resolution was visually evaluated with respect to these exposure amounts. The results are shown in Table 3.

[0069]

[Table 3]

As is apparent from Table 3, Example 5 using the ultraviolet absorber of the present invention and / or the polymer containing the same was used.
At ~ 8, not only is the photosensitivity high, but there is little overlap in the spectral sensitivity range of each light and heat, and there is almost no decrease in the maximum color density of each color even when overexposure is four times the proper exposure. It can be seen that the color balance and the resolution are good without being seen.

[0071]

When the light and heat sensitive recording material of the present invention is used, an image having a high color density and improved storability in the non-image area can be obtained.

Claims (3)

[Claims] 1. A light- and heat-sensitive layer in which a latent image is formed on a photocurable composition by exposure, and a component relating to color development or decolorization by heating moves in a light-sensitive material according to the latent image to form a color image. A photosensitive layer having at least two layers, and an intermediate layer containing a UV absorber represented by the following general formula (I) and / or a polymer containing the UV absorber is provided between the light and heat sensitive layers. Thermosensitive recording material. General formula (I): In the formula, R1 and R3 are alkyl groups having 1 to 20 carbon atoms, or a group represented by the general formula (II), R2 is a hydrogen atom,
Alkyl group having 1 to 5 carbon atoms, or 6 carbon atoms
Represents an aryl group of 20. General formula (II): In the formula, R4 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, A represents -CONH-, -COO- or phenylene group, and B represents a divalent linking group. n
Represents 0 or 1. 2. The light and heat sensitive recording material according to claim 1, wherein the ultraviolet absorber is dispersed in the form of fine particles. 3. The photocurable composition according to claim 1, wherein at least one of the components involved in the coloring or decoloring is encapsulated in a microcapsule, and the one component is an electron-donating colorless dye. A photosensitive composition containing an electron-accepting compound having a polymerizable ethylene group and a photopolymerization initiator.