JP2693040B2 - Photosensitive and thermosensitive recording materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive or heat-sensitive recording material which can be used for color or black and white proofing, second original drawing, copier, fax and the like.

[0002]

2. Description of the Related Art The prior art will be described below by taking a color proof as an example for the sake of convenience.
The same can be said for other fields. There are various types of color proofs, but each has its own drawbacks.
One of the typical methods of color proof is an overlay method. In this method, a multi-color image is reproduced by superimposing films having images of respective colors, and it is inevitable to see the image through the film, and the image quality deteriorates. In addition, there is a surprint method as a method for obtaining a multicolor image on one sheet. In this method, a multicolor image is obtained by sequentially superimposing images of each color on one support.
For example, Chromalin (Dupont), Match Print (3M), Color Art (Fuji Photo Film), etc. are known, but all require four photosensitive films corresponding to each color, and waste is generated. I do. Further, a color paper method is known as a method of forming a color image on one photosensitive sheet. In this method, a film original is brought into close contact with color paper, exposed using each color filter, and wet developed to obtain a color image.
Fine checkers (Fuji Photo Film) and consensus (Konica) are known. In this method, since the photosensitive area of the color paper is in the visible area, a dark room or an exposure apparatus having a dark room is required for handling, and maintenance management of the developer is required. These methods require a plurality of sheets, transfer sheets, waste such as toner is generated,
There are some drawbacks, such as difficulty in handling in a bright room and the need for a developing system using a developing solution, and improvement is required.

The following system has been proposed as a system that does not have these disadvantages. That is, a latent image is formed on the photocurable composition by exposure, and components related to color development or decolorization are diffused in the photosensitive material according to the latent image by heating to form a color image. Using a heat-sensitive recording material, exposing the photosensitive recording material through an image document, causing photo-curing in an exposed portion to form a latent image, and then heating the recording material to form an uncured portion. By using a color image forming method characterized by forming a visible image by diffusing a part relating to color development or decoloring, a completely dry system free of waste can be realized. There are several types of recording materials to be used in this method, and this is a characteristic method as a black and white image recording method. However, this method is particularly useful when used as a color recording material. As a specific recording material, for example, a recording material disclosed in Japanese Patent Laid-Open No. 52-89915 is known. This is achieved by separating two components of a two-component thermosensitive color recording material, for example, an electron-accepting compound and an electron-donating colorless dye, inside and / or outside or on both sides of a microcapsule containing a photocurable composition. This is the arranged recording material. However, in the case of this recording material, even if the photocurable composition in the microcapsules is sufficiently cured, the color development of the cured portion cannot be sufficiently suppressed, so that the non-image portion is slightly colored, and the contrast tends to be poor. There is. As a more preferable recording material having no coloring in the non-image area, for example, as disclosed in JP-A-61-123838, a photopolymerizable composition comprising a vinyl monomer having an acidic group and a photopolymerization initiator is disclosed. There is known a recording material in which a layer containing a substance, a separating layer, and a layer composed of an electron-donating colorless dye are laminated. In the case of this recording material, the non-image portion, that is, the thermal curing property of the acidic group in the portion cured by the photopolymerized portion is almost eliminated, so that the non-image portion is not colored, but the coloring density is slightly low. As a method for obtaining a negative image in the same manner, for example, there is a method disclosed in JP-A-60-119552. This method uses a photopolymerizable composition comprising a monomer or prepolymer for bleaching a dye and a photopolymerization initiator, and a recording material in which a dye bleached by the monomer or the prepolymer is present in isolation. This recording material also has the same disadvantages as the above-mentioned recording material. As the most preferable recording material overcoming the coloring of the non-image area and the low image density, Japanese Patent Application No. 1-224 filed by the present applicant is proposed.
There is a recording material described in No. 930. In this recording material, one of the two components of the two-component type thermosensitive color recording material is encapsulated in a microcapsule, and the other component is used as a curable compound of a photocurable composition, or the other component is used as a photocurable composition. And a recording material arranged outside the microcapsule. As a recording material for a negative image using the same concept, there is a recording material described in Japanese Patent Application No. 2-19710 of the present applicant. An electron-accepting compound, a photopolymerizable composition containing a polymerizable vinyl monomer and a photopolymerization initiator are arranged outside the microcapsules, and a layer containing a microcapsule containing an electron-donating colorless dye is provided. This is a recording material.

In order to perform color recording with these photosensitive recording materials, basically, a recording material having a plurality of photosensitive layers having mutually different photosensitive wavelengths and different coloring hues may be used. As a more preferable example of the multicolor recording material, Japanese Patent Application No. 1-224930.
And Japanese Patent Application No. 2-19710. For example, it has a plurality of photosensitive layers that are sensitive to light of different wavelengths and develop different hues, and, as a layer configuration from the exposure light source side to the support side of the recording material,
First photosensitive layer sensitive to light of center wavelength λ1, center wavelength λ
An intermediate layer that absorbs the light of 1
, A second photosensitive layer that develops a color different from that of the first photosensitive layer, ..., An intermediate layer that absorbs light having a center wavelength λi−1, first, second, ... , And the i-th photosensitive layer that develops a color different from that of the (i-1) -th photosensitive layer, at least two photosensitive layers are laminated on the support, and the central wavelength λ1 <λ2 <. ··· A multicolor recording medium characterized by being <λi. Here, i is an integer of 2 or more.

While these recording materials have a wide variety of applications, they are most commonly used in reflective imaging to form an image on a white paper support. Since these light-sensitive and heat-sensitive recording materials form an image by optical recording, they can be expected to give an image of high resolution in principle. Since the light-sensitive and heat-sensitive recording materials having a heat-sensitive layer give images with poor resolution and unevenness, improvement has been desired. One method for improving this poor resolution and unevenness is to use a support laminated with a polyolefin such as polyethylene or polypropylene. The photosensitive / thermosensitive recording material according to the present invention has a high temperature, for example 120%. It is necessary to carry out heat development at 5 ° C. for 5 seconds. At this time, the laminated polyethylene or polypropylene cannot withstand this heat development temperature, and deformation occurs with the recording layer placed, causing the recording layer to wavy or tough. There is also a method of improving poor resolution and unevenness by using a synthetic paper well known in the art, but it also deforms during heat development so that it cannot be used as a recording material. Further, when a paper support or a laminated paper is used, fog occurs when a latent image is formed by exposure and then heat development is long, so that improvement has been demanded.

[0006]

An object of the present invention is to provide a completely dry black-and-white or color photosensitive / thermosensitive photosensitive recording material which does not generate unnecessary waste and does not require the use of a developing solution or the like. Another object of the present invention is to provide a photosensitive / thermosensitive recording material capable of giving a high-resolution image. Furthermore,
It is an object of the present invention to provide a light- and heat-sensitive recording material capable of giving a clear and even image. Furthermore, it is another object of the present invention to provide a recording material that is free from deformation during heat development. Furthermore, even if the time from exposure to heat development is long, fog does not occur and a photosensitive image that gives a clear image can be obtained.
It is to provide a heat-sensitive recording material.

[0007]

The inventors of the present invention have earnestly studied, and as a result, as a result, the above-mentioned object was to form a latent image on the photocurable composition outside the microcapsules by exposure, and to heat the electron-accepting compound. characterized but that the photosensitive and heat-sensitive layer for forming an image by coloring the electron-donating colorless dye in the microswitch capsule in accordance with the latent image, is provided on at least one surface of a support filled with a white pigment to the polyester And the exposure
The present invention has been completed by finding out what is achieved by the heat-sensitive recording material.

As a concrete example of the recording material according to the present invention, for example, an electron-accepting portion and a polymerizable vinyl monomer portion are provided outside the microcapsules described in Japanese Patent Application No. 1-224930. A recording material having a layer containing a photopolymerizable composition containing a compound in the same molecule and a photopolymerization initiator and microcapsules containing an electron-donating colorless dye can be mentioned. When this recording material is exposed to light, the exposed portions of the photopolymerizable composition outside the microcapsules are polymerized to form a latent image.
When heated, the electron-accepting compound diffuses in the light-sensitive material according to the latent image, and the electron-donating colorless dye in the microcapsules is colored to form a positive-contrast image with good contrast. Further, a negative image can be formed by using the same method according to the recording material of the present invention. A specific example of this method is, for example, Japanese Patent Application No. Hei 2-1971.
A microcapsule containing an electron-accepting compound, a polymerizable vinyl monomer and a photopolymerization initiator, and an electron-donating colorless dye in addition to the microcapsule described in No. 0 specification; A recording material coated with a layer containing When this recording material is exposed to light, the exposed portions of the photopolymerizable composition outside the microcapsules are polymerized to form a latent image, and then, when heated, the electron-accepting compound in the polymerized portion is sensed according to the latent image. It is possible to form a negative image with good contrast by diffusing in the material and coloring the electron-donating colorless dye in the microcapsules.

As described above, using various methods,
By "exposure is a recording material of the present invention is a latent image formed on the photo-curable composition is outside the microcapsules, a colorless electron-donating in Ma microcapsules according to the electron-accepting compound by heating the latent image A photosensitive / thermosensitive layer for forming an image by coloring a dye is provided on at least one surface of a support in which a white pigment is filled in polyester.
A heat-sensitive recording material "can be prepared. The photosensitive / thermosensitive layer used for these recording materials is not limited to the above-described configuration, but can have various configurations depending on purposes. Further, the recording material used in the present invention is a monochromatic so-called B /
A W recording material or a multicolor recording material may be used. In the case of a multicolor recording material, for example, the configuration of a multilayer recording material including in each layer a microcapsule containing an electron-donating colorless dye that develops a different hue and a photocurable composition sensitive to light of a different wavelength. Can be used. For example, a layer containing a microcapsule containing an electron-donating colorless dye that develops cyan and a photocurable composition that is sensitive to wavelength λ1 is provided on a support, and an electron-donating colorless dye that develops magenta is formed on the support. A layer containing a microcapsule containing a photocurable composition sensitive to wavelength λ2 is provided, and a microcapsule containing an electron-donating colorless dye that develops yellow and a photocurable composition sensitive to wavelength λ3 are provided thereon. It is possible to use a constitution in which a layer containing a substance is provided, a constitution in which an intermediate layer is further provided between each layer, and a constitution in which an ultraviolet absorber is contained in this intermediate layer. In the case of a multicolor recording material, it is particularly preferable that the intermediate layer contains an ultraviolet absorber. As its constitution, for example, a layer containing microcapsules containing an electron-donating colorless dye that develops cyan and a photocurable composition that is sensitive to wavelength λ1 is provided on a support, and a layer having a wavelength of λ1 An intermediate layer containing an ultraviolet absorber that absorbs short-wave light is provided, and a layer containing microcapsules containing an electron-donating colorless dye that develops magenta and a photocurable composition that is sensitive to wavelength λ2 is provided on the intermediate layer. Is provided, an intermediate layer containing an ultraviolet absorber that absorbs light having a wavelength shorter than λ2 is provided thereon, and microcapsules containing an electron-donating colorless dye that develops yellow and light that is sensitive to wavelength λ3 are provided thereon. There is a structure in which a layer containing a curable composition is provided, and a protective layer is further provided thereon.

The electron-accepting and polymerizable vinyl monomer mainly used in the positive recording material of the present invention may be any compound containing an electron-accepting group and a vinyl group in the molecule. Examples of such a compound include methacryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682, acryloxyethyl ester which can be synthesized by a similar synthesis method, and JP-A-59-83693. Nos. 60-141587 and 62-99190, esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene, hydroxystyrenes described in EP 29323 and JP-A-62-167077. 62-167
Various compounds can be used which can be synthesized with reference to an N-vinylimidazole complex of zinc halide described in JP-A-08-0808, a developer monomer described in JP-A-63-317558, and the like.

Specific examples include, for example, styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid,
β-methacryloxyethoxysalicylate, 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-hydroxyethoxycarbonylphenol, β-methacryloxyethyl-p-
Hydroxycinnamate, β-acryloxyethyl-p
-Hydroxycinnamate, 3,5-distyrenesulfonic 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-methacrylic acid Roxyethylaminosulfonylsalicylic acid, N, N'-di-β-
Acryloxyethylaminosulfonylsalicylic acid and the like, and metal salts thereof such as zinc salt can be preferably used.

As the photopolymerization initiator suitably used for the recording material of the present invention, one or a combination of two or more compounds can be selected from the compounds capable of initiating the photopolymerization of the vinyl monomer. . Preferred specific examples of the photopolymerization initiator include the following compounds.
Aromatic ketones: for example, benzophenone, 4,4'-
Bis (dimethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, -Methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers: for example, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2 , 4,5-Triarylimidazole dimer: for example, 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-53-13.
No. 3428, JP-B-57-1819, JP-B-57-6
No. 096, U.S. Pat. No. 3,615,455, and S-triazine derivatives having a trihalogen-substituted methyl group described in JP-A-58-29803: for example, 2,4,6-tris (trichloro Methyl) -S-
Triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6-bis (trichloromethyl) -S-triazine, 2- (P-methoxystyryl) -4,6 -Bis (trichloromethyl)
Compounds such as -S-triazine; And organic peroxides described in, for example, JP-A-59-189340: for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditertiary butyl diperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxybenzoate, α,
α'-bis (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 3,3 ',
Compounds such as 4,4'-tetra- (tert-butylperoxycarbonyl) benzophenone. And azinium salt compounds as described, for example, in U.S. Pat. No. 4,743,530; and organoboron compounds as described, for example, in EP 0 223 587: for example the tetramethylammonium salt of triphenylbutyrate borate, the tetrabutylammonium salt of triphenylbutyrate borate ,
Tetramethylammonium salt of tri (P-methoxyphenyl) butyrate borate and the like; and other photopolymerization initiators well known in the art such as diaryliodonium salts and iron allene complex can be usefully used.

As the photopolymerization initiator system, a combination of two or more compounds is known, and these combinations can also be used in the recording material of the present invention. Examples of combinations of two or more compounds include 2,4,5-
Combination of triarylimidazole dimer with mercaptobenzoxazole and the like, combination of 4,4'-bis (dimethylamino) benzophenone with benzophenone or benzoin methyl ether described in U.S. Pat. No. 3,427,161, U.S. Pat. No. 4,239,850 Of benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6- (4'-methoxyphenyl) -triazole described in
No. 7-23602, a combination of dialkylaminobenzoic acid ester and dimethylthioxanthone, and JP-A-59-78339, 4,4'-bis (dimethylamino) benzophenone, benzophenone and a polymethyl halide compound. Can be mentioned. More preferred examples include a combination of 4,4′-bis (diethylamino) benzophenone and benzophenone,
Examples include a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, and a combination of 4,4′-bis (diethylamino) benzophenone and 2,4,5-triarylimidazole dimer. Particularly preferable compounds among these photopolymerization initiators include benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group, organic peroxides, azinium salt compounds and organic boron compounds. The content of the photopolymerization initiator is preferably 0.01 to 20% by weight, and more preferably 0.1% by weight, based on the total weight of the photopolymerizable composition.
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,
If it exceeds 10% by weight, no increase in sensitivity can be expected.

The photocurable composition of the recording material of the present invention may contain, in addition to the polymerizable vinyl monomer 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 include the above-mentioned patents relating to the photopolymerization initiator, and Research Diss.
Closure, Vol. 200, December 1980,
Item 20036, pages 160-163 of "Sensitizers" (Katsumi Tokumaru and Shin Okawara / ed. Kodansha 1987) can be referred to. Specific examples of spectral sensitizing dyes include, for example, 3-ketocoumarin compounds in JP-A-58-15503, thiopyrylium salts in JP-A-58-40302, and JP-B-59-28328. And naphthothiazole merocyanine compounds are disclosed in JP-B-61-9621 and JP-B-62-3842.
And JP-A-59-89303 and JP-A-60-60104 each disclose a merocyanine compound. These spectral sensitizers can extend the spectral sensitivity of the photopolymerization initiator to the visible range. In the above example, a trihalomethyl-S-triazine compound is used as a photopolymerization initiator, but may be combined with another photopolymerization initiator. Examples of the spectral sensitizing dye include coumarin (including ketocoumarin or sulfoncoumarin) which is a keto dye, merostyril dye, oxonol dye and hemioxonol dye, non-ketopolymethine dye which is a non-keto dye, anthracene dye, rhodamine dye, Examples include acridine dyes, aniline dyes and azo dyes, and cyanine, hemicyanine and styryl dyes as non-ketopolymethine dyes.

The photopolymerizable composition of the recording material of the present invention further contains a reducing agent such as an oxygen scavenger as an auxiliary agent for further promoting the polymerization.
And a chain transfer agent of an active hydrogen donor, and other compounds that promote polymerization in a chain transfer manner. Oxygen scavengers that have been found to be useful are phosphines, phosphonates, phosphites, stannous salts, and other compounds that are readily 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, lophin dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, etc. are also useful as polymerization accelerators.

An electron-accepting compound is preferably used in the photopolymerizable composition of the negative recording material used in the present invention. In addition, the electron-accepting compound can be added to the photocurable composition in the positive recording material, if necessary, and the coloring density is improved by the addition. Examples of the electron-accepting compound include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolak resins, metal-treated novolak resins, and metal complexes. These examples are shown in JP-B-40-9.
No. 309, JP-B-45-14039, JP-A-52-1
No. 40483, JP-A-48-51510, JP-A-57
-210886, JP-A-58-87089, JP-A-59-112286, JP-A-60-176795, JP-A-61-95988 and the like. To illustrate some of these, as phenolic compounds,
2'-bis (4-hydroxyphenyl) propane, 4-
t-butylphenol, 4-phenylphenol, 4-
Hydroxydiphenoxide, 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-isooctylidenediphenol, 4,4 ′ -Sec-butylidene diphenol, 4-tert-octylphenol,
4-p-methylphenylphenol, 4,4'-methylcyclohexylidenephenol, 4,4'-isopentylidenephenol, benzyl p-hydroxybenzoate and the like. Salicylic acid derivatives include 4-pentadecylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (tert-octyl) salicylic acid,
-Octadecylsalicylic acid, 5-α- (p-α-methylbenzylphenyl) ethylsalicylic acid, 3-α-methylbenzyl-5-tert-octylsalicylic acid, 5-tetradecylsalicylic acid, 4-hexyloxysalicylic acid, 4-cyclohexyloxy Salicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid, 4
Pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid and the like, and zinc, aluminum,
There are calcium, copper and lead salts. When these electron-accepting compounds are used in combination, an electron-donating colorless dye of 5 to 1000
It is preferred to use wt%.

For the photocurable composition of the negative recording material used in the present invention, a monomer having at least one vinyl group in the molecule can be used. For example, acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, itaconic esters; styrenes;
Vinyl ethers; vinyl esters; N-vinyl heterocycles; aryl ethers; allyl esters and the like can be used. Among these, a monomer having a plurality of vinyl groups in the molecule is particularly preferable, for example, an acrylate or methacrylate of a polyhydric alcohol such as trimethylolpropane or pentaerythritol; and an acrylate or methacrylate-terminated epoxy resin; Examples include acrylate or methacrylate terminated polyester. Specific examples of particularly preferable compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate and diethylene glycol diacrylate. Methacrylate and the like. The molecular weight of the polyfunctional monomer is about 100 to
About 5000 is preferred, and more preferably about 300 to about 2000.

In addition to these compounds, as a photocrosslinkable composition, for example, polyvinyl cinnamate, polycinnamylidene vinyl acetate, a photocurable composition having an α-phenylmaleimide group and the like can be added. Further, these photocrosslinkable compositions may be used as photocurable components.

Further, in addition to these compounds, a heat polymerization inhibitor can be added to the photocurable composition as needed. The thermal polymerization inhibitor is added to prevent the thermal polymerization of the photocurable composition and the polymerization with time, so that the chemical stability during preparation and storage of the photocurable composition can be improved. Can be increased. As an example of the thermal polymerization inhibitor, p
-Methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t- Butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine and the like can be mentioned. The preferable addition amount of the thermal polymerization inhibitor is 0.1 based on the total weight of the photocurable composition.
001-5% by weight, and more preferably 0.01-
1% by weight. If it is less than 0.001% by weight, the thermal stability is poor, and if it exceeds 5% by weight, the sensitivity is lowered. The photocurable composition may be encapsulated in microcapsules. The photocurable composition of the recording material of the present invention may be encapsulated and used in microcapsules, if necessary. For example, they can be encapsulated in microcapsules with reference to European Patent No. 0223587 and the above patent.

The electron-donating colorless dye relating to the recording material of the present invention is a conventionally known triphenylmethanephthalide compound, fluorane compound, phenothiazine compound,
Various compounds such as an indolylphthalide compound, a leuco-olamine compound, a rhodamine lactam compound, a triphenylmethane compound, a triazene compound, a spiropyran compound, and a fluorene compound can be used. Specific examples of phthalides are US reissue patent specification No. 2
3,024, U.S. Pat. No. 3,491,111
Issue No. 3,491,112 Issue 3,491,11
No. 6, and No. 3,509,174, and specific examples of fluoranes are U.S. Pat. Nos. 3,624,107, 3,627,787, 3,641,011, and No. 3,462,828, No. 3,681,390,
Nos. 3,920,510 and 3,959,571
No. 3, specific examples of spirodipyrans are described in U.S. Pat.
No. 971,808, pyridine compounds and pyrazine compounds are described in U.S. Pat.
No. 853,869, No. 4,246,318, and specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989.

Some of these are shown as triarylmethane compounds, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3
3-bis (p-dimethylaminophenyl) phthalide, 3
-(P-Dimethylaminophenyl) -3- (1,3-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, etc. There are 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like as diphenylmethane compounds, and xanthene The system compounds include rhodamine-B-anilinolactam, rhodamine-
(P-nitrino) lactam, 2- (dibenzylamino)
Fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-
6-N-ethyl-N-isoamylaminofluoran, 2
-Anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-anilino-3-
Methyl-6-N-ethyl-N-isobutylaminofluoran, 2-anilino-6-dibutylaminofluoran,
2-anilino-3-methyl-6-N-methyl-N-tetrahydrofurfurylaminofluorane, 2-anilino-
3-methyl-6-piperidinoaminofluoran, 2-
There are (o-chloroanilino) -6-diethylaminofluoran, 2- (3,4-dichloroanilino) -6-diethylaminofluoran, and the like. Examples of the thiazine-based compound include benzoyl leucon methylene blue and p-nitrobenzyl leucomethylene blue. And spiro-based compounds such as 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran 3,3′-dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, and 3-methyl-naphthopyran; Methoxy-benzo) -spiropyran, 3-propyl-spiro-dibenzopyran and the like. In particular, when used in a full-color recording material, U.S. Pat. No. 4,800,149 is used as an electron-donating colorless dye for cyan, magenta, and yellow, and U.S. Pat. And the like as a cyan color developing type disclosed in JP-A-63-5354.
No. 2 etc. can be referred to.

When the electron-donating colorless dye of the recording material of the present invention is microencapsulated, it can be prepared by a method known in the art. For the encapsulation of the electron-donating colorless dye in the recording material of the present invention, a method known in the art can be used. For example, US Pat. Nos. 2,800,457 and 2,800.
Method utilizing a coacervation of hydrophilic wall forming material as found in US Pat.
4, British Patent No. 990443, Japanese Patent Publication No. 38-195
74, 42-446, 42-771, interfacial polymerization methods, methods by polymer precipitation as seen in U.S. Pat. Nos. 3,418,250 and 3,660,304, isocyanates seen in U.S. Pat. No. 3,796,669. Method Using Polyol Wall Materials, US Patent 391
US Pat. Nos. 4,001,140 and 4,087,376, using the isocyanate wall material found in 4511.
No. 4,089,802, a method using a urea-formaldehyde system, a urea-formaldehyde-resorcinol-based wall forming material, a method using a wall forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose found in US Pat. No. 4,025,455, In-situ by polymerization of monomers found in JP-B-36-9168 and JP-A-51-9079.
The electrolytic dispersion cooling method found in British Patent Nos. 952807 and 965074; U.S. Pat. No. 3,111,407;
There is a spray drying method and the like found in British Patent No. 930422. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall after emulsifying the core substance.

As a method of forming the microcapsule wall of the recording material of the present invention, the effect is particularly large when the microencapsulation method by polymerizing the reactant from the inside of the oil droplet is used. That is, it is possible to obtain a capsule having a uniform particle size in a short time, and which is preferable as a recording material having excellent raw preservability. For example, when polyurethane is used as a capsule wall material, a polyisocyanate and optionally a second substance (for example, polyol, polyamine) which reacts with it to form a capsule wall are mixed in an oily liquid to be encapsulated and emulsified in water. By dispersing and then raising the temperature, a polymer forming reaction occurs at the oil drop interface to form a microcapsule wall. At this time, an auxiliary solvent having a low boiling point and strong dissolving power can be used in the oily liquid. In this case, the polyisocyanate to be used and the polyol and polyamine to be reacted therewith are described in US Pat. No. 328.
1383, 3737695 and 3793268
No. 48/40347 and 49-24159.
JP-A-48-80191 and JP-A-48-84086, and they can also be used.

As the polyvalent isocyanate, for example, m
-Phenylene diisocyanate, p-Phenylene diisocyanate, 2,6-Tolylene diisocyanate, 2,
4-Tolylene diisocyanate, naphthalene-1,4-
Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4- Diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene
Diisocyanates such as 1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, and cyclohexylene-1,4-diisocyanate; 4,4 ′, 4 ″ -triphenylmethane triisocyanate; Triisocyanates such as toluene-2,4,6-triisocyanate;
4'-dimethyldiphenylmethane-2,2 ', 5,5'
A tetraisocyanate such as tetraisocyanate, an adduct of hexamethylene diisocyanate and trimethylolpropane, an adduct of 2,4-tolylenediisocyanate and trimethylolpropane, an adduct of xylylenediisocyanate and trimethylolpropane, tolylenediisocyanate and hexane There are isocyanate prepolymers, such as adducts of triols.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, and hydroxypolyalkylene ethers. JP-A-60-
The following polyols described in 49991 are also used. Ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl -1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,
5-pentanediol, 1,4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-phenylpropylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol Pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4-di (2-hydroxyethoxy) benzene,
Condensation products of aromatic polyhydric alcohols such as resorcinol dihydroxyethyl ether and alkylene oxides, p-xylylene glycol, m-xylylene glycol, α, α′-dihydroxy-p-diisopropylbenzene, 4,4′-dihydroxy. -Diphenylmethane,
Examples thereof include 2- (p, p'-dihydroxydiphenylmethyl) benzyl alcohol, an adduct of bisphenol A with ethylene oxide, and an adduct of bisphenol A with propylene oxide. The polyol is preferably used in such a manner that the ratio of the hydroxyl group is 0.02 to 2 mol with respect to 1 mol of the isocyanate group.

As the polyamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, amine adducts of epoxy compounds and the like can be mentioned. Polyvalent isocyanates can also react with water to form polymeric substances.

When making the microcapsules, a water-soluble polymer can be used, and the water-soluble polymer may be any of water-soluble anionic polymers, nonionic polymers and amphoteric polymers. As the anionic polymer, either a natural polymer or a synthetic polymer can be used. For example, -COO
-, - it includes those having a group such as - SO _2. Specific anionic natural polymers include arabic gum, alginic acid, pectin and the like, and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfonic acid and the like.
In addition, as synthetic products, maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers And carboxy-modified polyvinyl alcohol. Examples of the nonionic polymer 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 average particle size of the capsule used in the recording material of the present invention is 20 μm or less, and particularly preferably 5 μm or less from the viewpoint of resolution. On the other hand, if the capsule is too small, the surface area for a certain solid content becomes large, and a large amount of a wall material is required. Therefore, the thickness is preferably 0.1 μm or more.

The electron-donating colorless dye according to the recording material of the present invention may be present in the microcapsules in a solution state or in a solid state. When the electron-donating colorless dye is present in a solution state, it may be encapsulated in a state where the electron-donating colorless dye is dissolved in a solvent. At this time, the amount of the solvent is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the electron-donating colorless dye. As a solvent used at the time of encapsulation, a natural oil or a synthetic oil can be used in combination. Examples of these solvents include, for example, cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes and 1-
Phenyl-1-xylylethane, 1-phenyl-1-p
Diarylethanes such as ethylphenylethane and 1,1'-ditolylethane; Phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphate ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (for example, acetyl citric acid) Tributyl), benzoic acid esters (octyl benzoate), alkylamides (eg, diethyl laurylamide), fatty acid esters (eg, dibutoxyethyl succinate,
Dioctyl acetate), trimesates (eg, tributyl trimesate), lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone,
β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like.

A volatile solvent may be used together with another solvent as an auxiliary solvent for dissolving the electron-donating colorless dye at the time of microencapsulation. Examples of this type of solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

In the recording material of the present invention, it is preferable to add a matting agent in the protective layer. Examples of the matting agent include silica, magnesium oxide, barium sulfate, strontium sulfate, inorganic compounds such as silver halide and polymethyl methacrylate, polyacrylonitrile, polymer particles such as polystyrene, carboxy starch, corn starch,
There are starch particles such as carboxynitrophenyl starch, and those having a particle diameter of 1 to 20 μm are preferable. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. Examples of silica particles include F
UJI-DEVISON CHEMICAL LTD.
Made of Syloid AL-1, 65, 72, 79, 74, 4
04, 620, 308, 978, 161, 162, 24
4,255,266,150 etc. are preferable. The addition amount of the matting agent is preferably from ² to 500 mg / m ² , particularly preferably from 5 to 100 mg / m ² .

In the recording material of the present invention, it is preferable to use a curing agent in combination with each layer of the recording material of the present invention such as a light-sensitive / heat-sensitive layer, an intermediate layer and a protective layer. In particular, it is preferable to use a curing agent in the protective layer to reduce the tackiness of the protective layer. As the hardener, for example, a "gelatin hardener" used in the production of photographic light-sensitive materials is useful, and examples thereof include aldehyde compounds such as formaldehyde and glutaraldehyde, and the reactive agents described in US Pat. No. 3,635,718 and others. Compounds having a halogen, compounds having a reactive ethylenic unsaturated bond described in US Pat. No. 3,635,718, etc., aziridine compounds described in US Pat. No. 3,017,280, US Pat. No. 30915
37, other epoxy compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane such as dihydroxydioxane and dichlorodioxane, or vinyl sulfones described in US Pat. No. 3,642,486 and US Pat. No. 3,687,707. ,
Vinyl sulfone precursors described in U.S. Patent No. 3,841,872, ketovinyls described in U.S. Patent No. 3,640,720, or chromium alum, zirconium sulfate, boric acid, and the like can be used as an inorganic curing agent. A particularly preferred compound among these curing agents is 1,3,5-triacroyl-hexahydro-
s-Triazine, 1,2-bisvinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamide)
It is a compound such as ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenimino-s-triazine and boric acid. The addition amount is preferably 0.5-5% by weight based on the binder.

In addition, colloidal silica may be added to the protective layer in order to reduce its tackiness. As colloidal silica, for example, Snowtex 20, Snowtex 30, Snowtex C, Snowtex O, Snowtex N and the like manufactured by Nissan Chemical Industries, Ltd. are preferable. The addition amount is preferably 5-80% by weight based on the binder. The protective layer may contain a fluorescent whitening agent for improving the whiteness of the recording material of the present invention or a blue dye as a bluing agent.

In the case of a multicolor recording material of the recording material used in the present invention, for example, a microcapsule containing an electron-donating colorless dye that develops a different hue and a photocurable composition that is sensitive to light of different wavelengths are provided in each layer. An intermediate layer containing an ultraviolet absorber may be provided between the light-sensitive and heat-sensitive layers by using the constitution of a multi-layered recording material containing the same. The intermediate layer mainly consists of a binder and an ultraviolet absorber, and may contain additives such as a curing agent and a polymer latex as needed. As the ultraviolet absorber, compounds known in the art such as a benzotriazole compound, a cinnamic acid ester compound, an aminoarylidenemalon nitrile compound, and a benzophenone compound can be used.

The ultraviolet absorber used in the recording material of the present invention can be emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method and added to a desired layer, particularly an intermediate layer. In the oil-in-water dispersion method, a high boiling point organic solvent having a boiling point of, for example, 175 ° C. or higher, and a so-called auxiliary solvent having a boiling point of, for example, 30 ° C. or higher and 160 ° C. or lower are dissolved in a single liquid or a mixed liquid of both, and then the surfactant Finely dispersed in an aqueous medium such as water or an aqueous gelatin solution or an aqueous polyvinyl alcohol solution in the presence of the agent. Examples of high boiling organic solvents are described in U.S. Pat.
No. 027, etc. Further, as specific examples of the high boiling point organic solvent and the auxiliary solvent, the same solvents as those used in the above-mentioned encapsulation can be preferably used. Also,
Dispersion may involve phase inversion and, if necessary, the co-solvent may be removed or reduced, such as by distillation, Nudel rinsing or ultrafiltration, before use in coating.

The process, effect and specific example of latex for impregnation of latex dispersion method are described in US Pat. No. 4,199,36.
3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, JP-A-49-745.
Nos. 38, 51-59943, 54-32552 and Research Disclosure, V.
ol. 148, August 1976, Item 14850
And so on. Suitable latexes include, for example, acrylic acid esters or methacrylic acid esters (eg, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, etc.) and acid monomers (eg, acrylic acid, 2-acrylamide). Copolymerized latex of (2-methylpropanesulfonic acid, etc.) is preferable.

As the ultraviolet absorber most preferably used in the recording material of the present invention, there is an ultraviolet absorber having a structure hardly diffused into the adjacent layer, for example, a polymer or latex copolymerized with the ultraviolet absorber. Examples of such an ultraviolet absorber include, for example, EP 127,819, JP-A-59-68731, JP-A-59-26733, and JP-A-59-26733.
No. 23344, British Patent No. 2,118,315, JP-A-58-111942, U.S. Pat. No. 4,307,184.
Nos. 4,202,836 and 4,202,834
Nos. 4,207,253 and 4,178,303
And JP-A-47-560 can be referred to. These ultraviolet absorbers are added to the intermediate layer, but may be added to the protective layer, the photosensitive / thermosensitive layer, the antihalation layer, etc., if necessary.

In the recording material of 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, which is preferably used in the recording material of the present invention. The water-soluble polymer that can be used is preferably a compound soluble in water at 25 ° C. in an amount of 5% by weight or more. Specifically, proteins such as gelatin, gelatin derivatives, albumin and casein, and cellulose derivatives such as methylcellulose and carboxymethylcellulose. , Sugar alginate, sugar derivatives such as starches (including modified starch), gum arabic and polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, vinyl acetate-polyacrylic acid copolymer Polymer saponification product, polystyrene sulfone Synthetic polymer of the salt, and the like.
Among these, gelatin and polyvinyl alcohol are preferred.

In the recording material of the present invention, the protective layer, the photosensitive
As the binder of each layer of the recording material such as the heat sensitive layer and the intermediate layer, the above water-soluble polymer and polystyrene, polyvinyl formal, polyvinyl butyral, acrylic resin: for example, polymethyl acrylate, polybutyl acrylate,
Solvent-soluble polymers such as polymethylmethacrylate, polybutylmethacrylate, their copolymers, phenol resins, styrene-butadiene resins, ethylcellulose, epoxy resins, urethane resins and the like or polymer latexes thereof can be used. Among these, gelatin and polyvinyl alcohol are preferred.

Various surfactants may be used in each layer of the light- and heat-sensitive recording material of the present invention 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, polyethylene oxide derivatives such as alkyl ether of polyethylene oxide, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N Anionic surfactants such as -acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylenalkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, aliphatic or Cationic surfactants such as aromatic quaternary ammonium salts can be used as needed.

Various additives can be added to the recording material of the present invention, if necessary, including the additives described above. For example, typical examples of dyes, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents and slipperiness improving agents that prevent irradiation and halation are Research Disclosure,
Vol. 176, December 1978, Item 176
43, and Vol. 187, November 1979,
Item 18716.

The coating solution for the photosensitive / thermosensitive layer of the recording material of the present invention and the coating solution for each of the above-mentioned layers may be dissolved in a solvent, if necessary, coated on a desired support, and dried. Is obtained. Examples of the solvent used in this case include water and alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, methyl cellosolve, 1-
Methoxy-2-propanol; Halogen solvent: for example, methylene chloride, ethylene chloride; Ketone:
For example, acetone, cyclohexanone, methyl ethyl ketone; esters: for example, methyl cellosolve acetate, ethyl acetate, methyl acetate; single substances such as toluene and xylene, and mixtures of two or more thereof. Of these, water is particularly preferred.

To coat the coating solution for each layer on the support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a curtain coater, an extender A lution coater or the like can be used. As a coating method, Research Disclosure, V
ol. 200, December 1980, Item 2003
You can refer to Section 6 XV. As the thickness of the recording layer,
0.1 μm to 50 μm is suitable.

The recording material of the present invention can be used for various purposes. Like copiers, faxes, printers, labels,
The recording material of the present invention can be used for a color proof, a second original drawing and the like.

The support suitable for the recording material of the present invention can be selected from known support base materials. For example, there is a polyester film such as polyethylene terephthalate or polybutylene terephthalate, and the thickness thereof is 50 to 2
00 μm is preferred. Whitening of these substrate materials is either filled with pigments or coated with pigments. As the pigment to be filled, silica, titanium dioxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate,
Examples thereof include lithopone alumina white, zinc oxide, antimony trioxide, titanium phosphate and the like. These can be used alone or as a mixture. The particle size of these pigments is
0.1-8 μm is preferable. The filling amount is preferably 1 to 30%. In order to disperse these pigments in the resin, it is possible to use a metal soap such as zinc stearate or aluminum stearate, or another surfactant as a dispersant. The above pigments can be used even when whitening is performed by applying a pigment. As the binder, any of water-soluble, water-dispersible and non-aqueous binders can be used, and can be appropriately selected and used from "Latest Binder Technology Handbook" edited by General Technology Center. Gelatin as a water-soluble binder,
PVA, casein, etc. can be used. In these cases, it is desirable to use a curing agent together. Examples of the water-dispersible binder include butadiene copolymer latex, vinyl acetate resin emulsion, acrylic emulsion, and polyolefin emulsion. As a non-aqueous binder,
Polyester type, vinyl acetate type, thermoplastic elastomer type, polyurethane type, melamine type, urea type, alkyd type, acrylic type, phenol type and the like can be used. Also,
If necessary, these supports may be provided with an antihalation layer on the front surface and a slip layer, an anti-stick layer, an anti-curl 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, a wide range of light sources such as various lasers such as a mercury lamp, an ultra high pressure mercury lamp, an electrodeless mercury lamp, a xenon lamp, a tungsten lamp, a metal halide lamp, an argon laser, a helium neon laser, a semiconductor laser, an LED, and a fluorescent lamp can be used.

The image recording method includes contact exposure of an original such as a lith film, enlargement exposure of a slide or liquid crystal image,
Various exposure methods such as reflection exposure using reflected light of a document can be used. When performing multi-color recording, single-exposure or multiple-time image recording may be performed using light having different wavelengths. Light having different wavelengths can be obtained by changing the light source or the optical filter.

The recording material of the present invention is subjected to a heat development treatment simultaneously with or after the imagewise exposure. Various conventionally known methods can be used as a heating method in the heat development processing. The heating temperature is generally 80 ° C to 200 ° C.
° C, preferably 100 ° C to 160 ° C. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute. It is preferable that the entire surface of the recording material of the present invention is exposed after the heat development process, and that the uncured portion is also photocured. Since the entire surface exposure suppresses the coloring reaction of the background and the decoloring reaction of the coloring portion, the storability of the image is improved. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0048]

EXAMPLES <Preparation of coating liquid> [Preparation of Electron-donating Colorless Dye Capsule] 1-a. Preparation of Electron Donating Colorless Dye (1) Capsule 8.9 g of electron donating colorless dye (1) was added to ethyl acetate.
The resultant was dissolved in 9 g, 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. This solution was added to a mixture of 42 g of 8% phthalated gelatin and 1.4 g of a 10% sodium dodecylbenzenesulfonate solution, and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 72 g of a 2.9% aqueous solution of triethylenepentamine were added to the obtained emulsion, and the mixture was heated to 60 ° C. while stirring.
After a lapse of time, a capsule liquid containing the electron-donating colorless dye (1) in the core and having an average particle size of 0.5 μm was obtained.

1-b. Preparation of Electron-donating Colorless Dye (2) Capsule 1-a. 1-a. Except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (2). A capsule containing an electron-donating colorless dye (2) having an average particle size of 0.5 μm was obtained in the same manner as described above.

1-c. Preparation of Electron Donating Colorless Dye (3) Capsule 1-a. 1-a. Except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (3). A capsule containing an electron-donating colorless dye (3) having an average particle size of 0.5 μm was obtained in the same manner as described above. The chemical structural formulas of the electron-donating colorless dyes (1), (2) and (3) are shown below.

[0051]

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2. [Preparation of Emulsion of Photocurable Composition] 2-a. Preparation of emulsion of photocurable composition (1) 0.13 g of photopolymerization initiator (1) and spectral sensitizing dye (1)
5 g of a polymerizable electron-accepting compound (1) was added to a mixed solution of 3 g of isopropyl acetate and 0.1 g of an auxiliary for promoting polymerization (1). This solution was combined with 13 g of a 13% aqueous solution of gelatin and 0.8% of a 2% aqueous solution of surfactant (1).
g and a 2% aqueous solution of surfactant (2) 0.8 g were added to a mixed solution and emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 10,000 rpm for 5 minutes to prepare a photocurable composition (1).
Emulsion was obtained.

2-b. Preparation of Emulsion of Photocurable Composition (2) 2-a. 2-a. Except that 0.13 g of the photopolymerization initiator (1) and 0.1 g of the spectral sensitizing dye (1) were changed to 0.2 g of the photopolymerization initiator (2). An emulsion of the photocurable composition (2) was obtained by the same method as described above.

2-c. Preparation of Emulsion of Photocurable Composition (3) 2-a. 2-a. Except that 0.13 g of the photopolymerization initiator (1) and 0.1 g of the spectral sensitizing dye (1) were changed to 0.2 g of the photopolymerization initiator (3). An emulsion of the photocurable composition (3) was obtained by the same method as described above.

2-d. Preparation of Emulsion of Photocurable Composition (4) 0.2 g of photopolymerization initiator (1) and spectral sensitizing dye (1) of 0.
As an aid for accelerating the polymerization, 2 g of N-phenylglycine ethyl ester (0.2 g) in ethyl acetate (4 g) was added to an electron accepting compound, resorcinic acid (1-methyl-2).
10 g of (phenoxy) ethyl and 8 g of trimethylolpropane triacrylate monomer were added. This solution was mixed with 19.2 g of a 15% aqueous gelatin solution, 4.8 g of water and 2
% Surfactant (1) aqueous solution 0.8 g and 2% surfactant (2) aqueous solution 0.8 g were added to a mixed solution and homogenized (manufactured by Nippon Seiki Co., Ltd.) at 10,000 rpm for 5 times.
It was emulsified for minutes to obtain an emulsion of the photocurable composition (4). The chemical structural formulas of the photopolymerization initiators (1), (2) and (3) are shown below.

[0056]

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The polymerizable electron-accepting compound (1) is shown below.
The chemical structural formula of is shown.

[0058]

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The chemical structural formula of the auxiliary agent (1) for promoting the polymerization is shown below.

[0060]

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3. [Preparation of Dispersion of Ultraviolet Absorber] 3-a. Preparation of emulsion of ultraviolet absorber (1) 7.5 g of ultraviolet absorber (1) and ultraviolet absorber (2)
A solution of 4 g in 17.5 g of ethyl acetate was added to 15%
It was added to a mixed solution of 62 g of an aqueous gelatin solution and 1 g of a 62% aqueous solution of dodecylbenzenesulfonic acid, and emulsified at 10,000 rpm for 5 minutes with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion of the ultraviolet absorbent (1). .

3-b. Preparation of emulsion of ultraviolet absorber (3) A solution of 5 g of ultraviolet absorber (3) in 19 g of ethyl acetate was added to a mixed solution of 65 g of 15% aqueous gelatin solution and 1 g of 62% aqueous dodecylbenzenesulfonic acid solution. 1000 with a homogenizer (manufactured by Nippon Seiki Co., Ltd.)
The emulsion was emulsified for 5 minutes at 0 rotation to obtain an emulsion of the ultraviolet absorber (3). Below, the ultraviolet absorbers (1), (2) and (3)
The chemical structural formula of is shown.

[0063]

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4. [Preparation of coating solution for photosensitive / thermosensitive layer] 4-a. Preparation of coating liquid for photosensitive / thermosensitive layer (1) Photosensitive / thermosensitive layer was prepared by mixing 4 g of electron-donating colorless dye (1) capsules, 12 g of photocurable composition (1) emulsion and 12 g of 15% PVA aqueous solution. A coating liquid for (1) was prepared.

4-b. Preparation of coating liquid for photosensitive / thermosensitive layer (2) Photosensitive / thermosensitive layer was prepared by mixing 4 g of the electron-donating colorless dye (2) capsules, 12 g of emulsion of photocurable composition (2) and 12 g of 15% PVA aqueous solution. A coating liquid for (2) was prepared.

4-c. Preparation of coating liquid for photosensitive / thermosensitive layer (3) Photosensitive / thermosensitive layer was prepared by mixing 4 g of the electron-donating colorless dye (3) capsules, 12 g of emulsion of photocurable composition (3) and 12 g of 15% PVA aqueous solution. A coating liquid for (3) was prepared.

4-d. Preparation of coating liquid for photosensitive / thermosensitive layer (4) A mixture of 1 g of the electron-donating colorless dye (1) capsules and 10 g of an emulsified liquid of the photocurable composition (4) was mixed to form a photosensitive / thermosensitive layer (4).
A coating solution was prepared.

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

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

6. [Preparation of Coating Solution for Protective Layer] 6-a. Preparation of Coating Solution for Protective Layer (1) 4.5 g of 10% gelatin aqueous solution, 4.5 g of distilled water and 2%
Surfactant (3) aqueous solution 0.5 g, 2% surfactant (4) aqueous solution 0.3 g and 2% hardener (1) aqueous solution 0.5
g and Syloid 72 (FUJI-DEVISON CH
EMICALLTD. A coating solution for the protective layer (1) was prepared by mixing an amount such that the coating amount was 50 mg / m ² and 1 g of Snowtex N. The chemical structural formulas of the surfactants (1), (2), (3) and (4) are shown below.

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Embedded image

Examples 1 to 3, Comparative Example 1: Positive-Type Photosensitive and Thermosensitive Recording Material A photosensitive and thermosensitive recording material was prepared in the following manner by using the following A to D as a support. 1. Support A A wood pulp consisting of 20 parts of LBSP and 80 parts of LBKP was beaten to a Canadian freeness of 300 cm ³ with a disc cliff einer, and sodium stearate was added to 1.
0 parts, 0.5 parts of anionic polyacrylamide, 1.5 parts of aluminum sulfate, and 0.5 part of polyamide polyamine epichlorohydrin were added at an absolute dry weight ratio to wood pulp, and the basis weight was 80 g / m2 by a fourdrinier paper machine. Paper ² was made. Density is 1.0 by machine calender
g / cm ³ . After corona-discharging these atoms, low-density polyethylene (MI = 7 g / 10 min, density 0.923
g / cm ³ ) containing 10% by weight of titanium oxide, and a polyethylene resin layer was formed by extrusion coating so as to have a thickness of 20 μm. Next, after the other surface (back surface) of the substrate was subjected to corona discharge treatment, a high-density polyethylene (MI = 8 g / 10 min, density 0.950 g / cm) was formed thereon.
³ ) was extruded and coated to form a total polyethylene resin having a thickness of 20 μm to prepare a double-sided polyethylene laminated paper. 2. Support B Lumirror E-6 manufactured by Toray Industries, Inc.
0 (100 μm) (polyester film filled with white pigment) 3. Support C Lumirror E-2 manufactured by Toray Industries, Inc.
0 (38 μm) (polyester film filled with white pigment) 4. Support D ICI Co., Ltd. Melinex 99
0 (184 μm) (polyester film filled with white pigment (barium sulfate)) 5. Support E Yupo FPG manufactured by Oji Paper Co., Ltd.
(110 μm) (polyester film filled with white pigment)

The coating liquid (1) for the light- and heat-sensitive layer was coated on these supports using a coating bar so that the dry weight of the coating layer would be 8 g / m ² , and dried at 30 ° C. for 10 minutes. The intermediate layer (1) has a dry weight of 2 g / m on this layer.
² and then the coating solution (2) for the light- and heat-sensitive layer is coated and dried to a dry weight of 8 g / m ² , and then the intermediate layer (2) is dried and dried. Coating and drying to ² g / m ² , coating and drying the photosensitive / heat-sensitive layer coating solution (3) to 8 g / m ² , and further coating solution for the protective layer (1). Using a coating bar so that the dry weight of the coating layer is 2 g / m ^2, and
Samples of Examples and Comparative Examples were obtained by drying at 10 ° C. for 10 minutes.

A 2,000 W high-frequency lighting type was passed through a lith film developed with a cyan image on the obtained light- and heat-sensitive recording material and an optical filter (SC-41 filter: manufactured by Fuji Photo Film Co., Ltd.) for blocking light of 410 nm or less. Ultra high pressure mercury lamp
P627GA) and exposed to ultraviolet light. Next, a magenta image-developed lith film and 365 nm to 400 nm
exposed through a mercury lamp through an interference filter that transmits only nm light, and then exposed through a mercury lamp through a lith film that has developed a yellow image and an interference filter that transmits only 340 nm to 365 nm light. Got the statue.
Then, it heated for 5 second with a 120 degreeC hot plate. At this time, 10 minutes after the exposure, heat development was performed to evaluate the resolution, density unevenness and fog OD (cyan density of RD918 type, reflection density measuring instrument manufactured by MACBETH) of the obtained image. Table 1 shows the results.

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[Table 1]

Examples 4 to 6 and Comparative Examples 2 and 3: Negative type photosensitive / thermosensitive recording material The coating liquid (4) for photosensitive / thermosensitive layer was applied onto the support shown in Table 2 using a coating bar. Dry weight of the layer is 8g / m
^It was applied so as to be ^2, and dried at 30 ° C. for 10 minutes. Next, the coating liquid for protective layer (1) was applied thereon by using a coating bar so that the dry weight of the coating layer would be 5 g / m ² , and dried at 30 ° C. for 10 minutes to obtain Examples and Comparative Examples. I got a sample of. The resulting light- and heat-sensitive recording material was exposed to ultraviolet light from a 1000 W high-pressure mercury lamp (Jetlight manufactured by Oak Co.) through a lith film which was developed with a black and white image. After exposure, evaluation was performed according to the method of Example 1. Table 2 shows the results.

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[Table 2]

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Since the recording material of the present invention uses a support in which polyester is filled with a white pigment as the support, deterioration of resolution and uneven image density due to unevenness of the support do not occur. Therefore, a clear image can be obtained by using the recording material of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuro Fuchizawa 200, Onakazato, Fujinomiya-shi, Shizuoka Fuji Shashin Film Co., Ltd. (56) References JP-A-61-24495 (JP, A) JP-A-59 -30537 (JP, A) JP 63-294548 (JP, A) JP 63-239444 (JP, A) JP 61-180244 (JP, A) JP 49-6207 (JP, B1) )

Claims (4)

(57) [Claims] 1. A latent image is formed on the photocurable composition is outside the microcapsules upon exposure, develop the electron-donating colorless dye in Ma microcapsules electron-accepting compound by heating in accordance with the latent image A light- and heat-sensitive recording material, characterized in that a light- and heat-sensitive layer for forming an image is provided on at least one side of a support in which polyester is filled with a white pigment. 2. A microcapsule containing an electron-donating colorless dye, a photopolymerization containing a compound having an electron-accepting portion and a polymerizable vinyl monomer portion in the same molecule outside the microcapsule, and a photopolymerization initiator. A photosensitive / thermosensitive recording material, characterized in that a layer containing a functional composition is provided on at least one side of a support in which a white pigment is filled in polyester. 3. A process according to claim in 1 or claim 2, photosensitive and heat-sensitive recording material, wherein the photosensitive-thermosensitive recording material is a multi-color recording material. 4. The first photosensitive layer according to claim 3, wherein the photosensitive / thermosensitive recording material is exposed to light having a central wavelength λ1 from the exposure light source side toward the support side of the recording material, the central wavelength λ1. Intermediate layer that absorbs the light of the central wavelength λ2, a second photosensitive layer that is exposed to the light of the central wavelength λ2 and develops a color different from the first photosensitive layer, an intermediate layer that absorbs the light of the central wavelength λi-1, and the central wavelength λi A layer structure in which at least two or more photosensitive layers are laminated on a support in the order of the i-th photosensitive layer which is exposed to light and develops a color different from the first, second and i-1th photosensitive layers. A photosensitive / thermosensitive recording material having a central wavelength λ1 <λ2 <... <λi. Here, i is an integer of 2 or more.