JP2618090B2 - Photosensitive and thermosensitive recording materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial application field" The present invention relates to a photosensitive / thermosensitive recording material which can be used for color or black and white proof, slide, overhead projector, second original drawing, copier, fax and the like. About.

"Prior Art" Hereinafter, a conventional technique will be described by taking a color proof as an example for convenience, but the same thing can be said in other fields only for a different purpose of use.

One of the typical methods of color proof is an overlay method. In this method, a multi-color image is reproduced by superimposing a film having a single color image, 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
Inc., color art (Fuji Photo Film), etc. are known, but all require four photosensitive films corresponding to each color, and waste is generated.

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. I have. 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 multiple sheets, transfer sheets,
There are some drawbacks, such as generation of waste such as toner, difficulty in handling in a bright room, and the need for a developing system using a developing solution.

The following method has been proposed as a method 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.

Specific recording materials include, for example, JP-A-52-89915
There is known a recording material disclosed in Japanese Patent Application Laid-Open Publication No. H10-260, 1988. 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 without coloring of the non-image portion, for example, as disclosed in JP-A-61-123838, a photopolymerizable composition comprising a vinyl monomer having an acidic group and a photopolymerization initiator 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 of obtaining a negative image by the same method, 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 which overcomes the coloring of the non-image area and the low image density, Japanese Patent Application No.
There is a recording material described in 224930. 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 different photosensitive wavelengths and different coloring hues may be used. As more preferred examples of multicolor recording materials, Japanese Patent Application No. 1-224930, Japanese Patent Application No. 2-19710
Recording materials described in (1). For example,
A first photosensitive layer having a plurality of photosensitive layers that are sensitive to light of different wavelengths and emit colors in different hues, and that is sensitive to light of a central wavelength λ1 as a layer configuration from the exposure light source side to the support side of the recording material. A photosensitive layer, an intermediate layer that absorbs light having a center wavelength λ1,
A second photosensitive layer which is sensitive to light having a central wavelength λ2 and emits light of a different color from the first photosensitive layer; ‥‥, an intermediate layer which absorbs light having a central wavelength λi-1; 1, second,
, And i-th color developing different color from the i-1st photosensitive layer
At least two or more photosensitive layers are laminated on the support in the order of the third photosensitive layer, and the center wavelength λ1 <λ2...
-Multicolor recording media characterized by <λi can be mentioned. Here, i is an integer of 2 or more.

These photosensitive and heat-sensitive recording materials use microcapsules of finite size, so the pixel size is defined by the size of the microcapsules, so the resolution is poor, and the image quality is reduced due to light scattering. There was a problem. This problem is particularly important in applications requiring high resolution, for example, proof applications and slide applications, and improvements have been required.

[Problems to be Solved by the Invention] An object of the present invention is to provide a completely dry-processed black-and-white or color photosensitive / thermosensitive photosensitive recording material that does not generate unnecessary waste and does not require the use of a developer or the like. Another object of the present invention is to provide a photosensitive / thermosensitive recording material having a high resolution, a small light scattering and a clear image quality.

[Means for Solving the Problems] An object of the present invention is to form a latent image on a photocurable composition outside a microcapsule by exposure, and heat the electron-accepting compound in the photosensitive material in accordance with the latent image. A photosensitive / thermosensitive recording material for forming an image by moving an electron-donating colorless dye in a microcapsule to form an image, wherein the average particle size of the microcapsule is 2 μm or less. Recording material.

Specific examples of the recording material according to the present invention include:
For example, a photopolymerizable composition containing a compound having a photopolymerization initiator and a compound having an electron-accepting portion and a polymerizable vinyl monomer portion in the same molecule outside the microcapsules described in Japanese Patent Application No. 1-224930. Recording material provided with a layer containing a material and microcapsules containing an electron-donating colorless dye. When the recording material is exposed, the exposed portion of the photopolymerizable composition outside the microcapsules is polymerized to form a latent image, and then, when heated, the electron-accepting compound is formed in the photosensitive material according to the latent image. It diffuses to form a colorless electron-donating dye in the microcapsules, thereby forming a positive color 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.

Specific examples of this method include, for example,
No. 710, a microcapsule containing a photopolymerizable composition containing an electron-accepting compound, a polymerizable vinyl monomer and a photopolymerization initiator, and an electron-donating colorless dye outside the microcapsules described in the specification And a recording material provided with a layer containing When this recording material is exposed, 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 sensitive to the latent image. By diffusing in the material, the color of the electron-donating colorless dye in the microcapsules is developed, and a negative image with good contrast can be formed.

As described above, a latent image is formed on the photocurable composition outside the microcapsules by exposure, which is the recording material of the present invention, using various methods, and the electron-accepting compound is heated according to the latent image by heating. Thus, a light-sensitive and heat-sensitive recording material that forms an image by moving in a light-sensitive material to form a colorless electron-donating dye in a microcapsule can be prepared.

In these recording materials, microcapsules having an average particle size of 2 μm or less are used to isolate the components.

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 may be a monochromatic so-called B / W recording material or a multicolor recording material. 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. That is, a microcapsule containing an electron-donating colorless dye that develops cyan and a layer containing a photocurable composition sensitive to wavelength λ1 are provided on a support, and an electron-donating colorless that develops magenta thereon. A layer containing a dye-containing microcapsule and a photocurable composition that is sensitive to wavelength λ2 is provided, and a microcapsule containing an electron-donating colorless dye that develops yellow and photocuring that is sensitive to wavelength λ3. A configuration in which a layer containing a sexually active substance is provided, a configuration in which an intermediate layer is provided between layers, a configuration in which an ultraviolet absorber is contained in the intermediate layer, and the like can be used.

In the case of a multicolor recording material, it is particularly preferable that the intermediate layer contains an ultraviolet absorber. As the constitution, for example, a layer containing a microcapsule containing an electron-donating colorless dye that develops cyan and a photocurable composition sensitive to a wavelength λ1 is provided on a support, and a layer containing a wavelength λ1 An intermediate layer containing an ultraviolet absorber that absorbs shorter-wave light is provided, and a microcapsule containing an electron-donating colorless dye that develops magenta and a photocurable composition that is sensitive to wavelength λ2 are provided thereon. Layer, on which an intermediate layer containing an ultraviolet absorber absorbing light having a wavelength shorter than wavelength λ2 is provided. On top of this, a microcapsule containing an electron-donating colorless dye that develops yellow and a light sensitive to wavelength λ3 are provided. There is a configuration in which a layer containing a photocurable composite material is provided, and a protective layer is further provided thereon.

The electron-accepting and polymerizable vinyl monomer mainly used in the positive recording material used in the present invention may be any compound containing an electron-accepting group and a vinyl group in the molecule. Such compounds include, for example, JP-A-63-17368
No. 2 methacryloxyethyl ester of a benzoic acid having a hydroxy group described in No. 2 and acryloxyethyl ester which can be synthesized by a similar synthesis method and No. 59-83693,
Nos. 60-141587 and 62-99190, esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene, and hydroxystyrene described in European Patent No. 29323, JP-A-62-167077, and JP-A-62-167077. Various compounds can be used which can be synthesized with reference to a zinc halide N-vinylimidazole complex described in JP-A-62-16708 and a developer monomer described in JP-A-63-317558.

Specific examples include, for example, styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, zinc β-methacryloxyethoxysalicylate, zinc β-acryloxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β-methacryloxyethylorselinate, β -Acryloxyethylorselinate, β-methacryloxyethoxyphenol, β-acryloxyethoxyphenol, β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate, hydroxystyrenesulfonic acid-N-ethylamide , Β-
Methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p-hydroxybenzoate, methacryloxymethylphenol, acryloxymethylphenol, methacrylamidepropanesulfonic 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-distyrenesulfonamide phenol, methacryloxy Tokishifutaru acid, acryloxy ethoxy phthalic acid, methacrylic acid, acrylic acid,
Methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid, 3-β-hydroxyethoxyphenol, β-methacryloxyethyl-
p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate, β′-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid, β-acryloxyethyloxycarbonylhydroxybenzoic acid, N , N '
-Di-β-methacryloxyethylaminosalicylic acid, N,
N′-di-β-acryloxyethylaminosalicylic acid, N,
N′-di-β-methacryloxyethylaminosulfonylsalicylic acid, N, N′-di-β-acryloxyethylaminosulfonylsalicylic acid and the like, and metal salts thereof such as zinc salt can be preferably used.

As the photopolymerization initiator suitably used in 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-dimethylamino Acetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers such as 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-diphenyl Imidazole 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, compounds described in 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 ( Trichloromethyl) -S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6-bis (trichloromethyl) -S
Compounds such as triazine, 2- (P-methoxystyryl) -4,6-bis (trichloromethyl) -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,
Compounds such as 3 ', 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 0223587: for example the tetramethylammonium salt of triphenylbutyrate borate, the tetrabutylammonium salt of triphenylbutyrate borate And tri (P-methoxyphenyl) butyrate borate such as tetramethylammonium salt; and other well-known photopolymerization initiators such as diaryliodonium salts and iron allene complexes.

Further, a combination of two or more compounds is known as a photopolymerization initiator system, and these combinations can also be used in the recording material of the present invention. Examples of the combination of two or more compounds include a combination of a 2,4,5-triarylimidazole dimer and a mercaptobenzoxazole, and the like, 4,4′- described in U.S. Pat.
Combinations of bis (dimethylamino) benzophenone and benzophenone or benzoin methyl ether, benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6 as described in U.S. Pat. No. 4,239,850.
-(4'-methoxyphenyl-triazole combinations, dialkylaminobenzoic acid esters and dimethylthioxanthone described in JP-A-57-23602, and 4,4 in JP-A-59-78339. Examples of three combinations of '-bis (dimethylamino) benzophenone, benzophenone, and a polymethyl halide compound include, more preferably, a combination of 4,4'-bis (diethylamino) benzophenone and benzophenone, and 2,4-diethylthioxanthone. And ethyl 4-dimethylaminobenzoate, and 4,4′-bis (diethylamino) benzophenone
Combinations of 2,4,5-triarylimidazole dimers are included.

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 from 0.01 to 20% by weight, and more preferably from 0.2 to 15% by weight, and most preferably from 5 to 10% by weight, based on the total weight of the photopolymerizable composition.
% 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 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 the photosensitive wavelength. As the spectral sensitizing dye, various compounds known in the art can be used. Examples of spectral sensitizing dyes include the above patents on photopolymerization initiators and Research Disclosure, Vol. 200, 1980
December, Item 20036 and pages 160-163 of "Sensitizers" (Katsumi Tokumaru and Shin Okawara / ed. Kodansha 1987) can be referred to.

Examples of specific spectral sensitizing dyes include, for example,
Japanese Patent Application No. 58-15503 discloses a 3-ketocoumarin compound.
No. 58-40302 discloses a thiopyrylium salt in Japanese Patent Publication No. 59-283.
No. 28, No. 60-53300, naphthothiazole merocyanine compound, JP-B-61-9621, JP-B-62-3842, JP-A-59-8
Nos. 9303 and 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 hemioxanol 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 may further contain a reducing agent such as an oxygen scavenger and a chain transfer agent of an active hydrogen donor as an auxiliary agent for accelerating the polymerization. Other compounds that promote polymerization can be added to the mixture. 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.

Further, it is preferable to use an electron-accepting compound 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 a phenol derivative, a salicylic acid derivative, a metal salt of an aromatic carboxylic acid, acidic clay, bentonite, a novolak resin, a metal-treated novolak resin, and a metal complex. Examples of these are JP-B-40-9309 and JP-B45-1403
No. 9, JP-A-52-140483, JP-A-48-51510, JP-A-57
-210886, JP-A-58-87089, JP-A-59-11286, JP-A-60-176795, JP-A-61-95988, and the like.

To illustrate some of these, examples of phenolic compounds include 2,2′-bis (4-hydroxyphenyl) propane, 4-t-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, and 1,1 ′. -Screw (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-butylidenediphenol, 4-tert
-Octylphenol, 4-p-methylphenylphenol, 4,4'-methylcyclohexylidenephenol, 4,
4'-isopentylidenephenol, benzyl p-hydroxybenzoate and the like. The salicylic acid derivative is 4-
Pentadecylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (ter-octyl) salicylic acid, 5-octadecylsalicylic acid, 5-α- (p-α-
Methylbenzylphenyl) ethylsalicylic acid, 3-α-
Methylbenzyl-5-ter-octylsalicylic acid, 5-tetradecylsalicylic acid, 4-hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid,
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, it is preferable to use 5 to 1000% by weight of the electron donating colorless dye.

In the photocurable composition of the negative recording material used in the present invention, a monomer having at least one vinyl group in a 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 preferred compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol. Dimethacrylate and the like.

About the molecular weight of the polyfunctional monomer, about 100 to about 5000
And more preferably about 300 to about 2000.

In addition to these compounds, photocrosslinkable compositions such as polyvinyl cinnamate, polyvinyl cinnamylidene acetate,
A photocurable composition having an α-phenylmaleimide group 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. Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, t-butylcatechol,
Pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride,
Examples include phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine and the like.

The preferable addition amount of the thermal polymerization inhibitor is 0.001 to 5% by weight, more preferably 0.01 to 1% by weight based on the total weight of the photocurable composition. If it is less than 0.001% by weight, the thermal stability is poor, and if it exceeds 5% by weight, the sensitivity decreases.

The photocurable composition of the recording material of the present invention may be used by being encapsulated 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 dyes relating to the recording material of the present invention are conventionally known triphenyl methanephthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leuco auramine compounds, rhodamine lactam compounds. , Triphenylmethane compounds,
Various compounds such as triazene compounds, spiropyran compounds and fluorene compounds can be used. Specific examples of phthalides are U.S. Reissue Patent No. 23,024, U.S. Patent Nos. 3,491,111, 3,491,112, and 3,491,116.
No. 3,509,174, specific examples of fluorans are U.S. Pat.Nos. 3,624,107, 3,627,787,
No. 641,011, No. 3,462,828, No. 3,681,390, No.
Nos. 3,920,510 and 3,959,571, specific examples of spirodipyrans are U.S. Pat.No. 3,971,808, and pyridine and pyrazine compounds are described in U.S. Pat.
Nos. 3,853,869 and 4,246,318, and specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989. If some of these compounds are disclosed, triarylmethane-based compounds include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide and 3,3-bis (p-
Dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,3 dimethylindole-3-
Yl) phthalide, 3- (p-dimethylaminophenyl)-
3- (2-methylindol-3-yl) phthalide, and the like, and diphenylmethane-based compounds include 4,4′-bis-dimethylaminobenzhydrin benzyl ether, N
-Halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like, and as the xanthene compounds, rhodamine-B-anilinolactam, rhodamine- (P-nitrino) lactam, 2- ( Dibenzylamino) fluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3
-Methyl-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluor Oran, 2-anilino-3-chloro-6-diethylaminofluoran, 2
-Anilino-3-methyl-6-N-ethyl-N-isobutylaminofluoran, 2-anilino-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-
Methyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-3-methyl-6-piperidinoaminofluoran, 2- (o-chloroanilino) -6-diethylaminofluoran, 2- (3,4-dichloroanilino ) -6
-Diethylaminofluoran, etc., and as the thiazine-based compound, benzoylleuconmethylene blue, p
-Nitrobenzyl leucomethylene blue and the like, and as spiro compounds, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran 3,3′-dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl -Naphtho- (3-methoxy-
Benzo) -spiropyran, 3-propyl-spiro-dibenzopyran and the like.

In particular, when used for a full-color recording material, cyan, magenta, U.S. Pat.No. 4,800,148 and the like as electron-donating colorless dyes for yellow, U.S. Pat. JP-A-63-53542 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 example, U.S. Pat.No. 2,800,457, a method using a coacervation of a hydrophilic wall-forming material as found in U.S. Pat.No. 2,8000,458, U.S. Pat.
No. 38-19574, JP 42-446, Interfacial polymerization method as found in JP 42-771, U.S. Pat.
U.S. Pat.
Method using isocyanate polyol wall material found in 3796669, method using isocyanate wall material found in U.S. Pat.No. 3,914,511, U.S. Pat.
U.S. Pat. No. 4,087,376, U.S. Pat. No. 4,980,802, Urea-formaldehyde, Urea-formaldehyde-Resorcinol-based method using wall-forming material, U.S. Pat.No. 4,025,455 Melamine-formaldehyde resin, Using wall-forming material such as hydroxypropylcellulose Method, Japanese Patent Publication 36-9
No. 168, JP-A-51-9079, in situ method by polymerization of monomers, British Patent Nos. 952807 and 965
Electrolytic dispersion cooling method found in No. 074, U.S. Pat.
And the spray drying method shown 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 for the method of forming the microcapsule wall of the recording material of the present invention, particularly when a microencapsulation method by polymerization of a reactant from the inside of an oil droplet is used, the effect is large.
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 the capsule wall material, a polyvalent isocyanate and, if necessary, a second substance (e.g., polyol,
(Polyamine) is mixed with an oily liquid to be encapsulated, emulsified and dispersed in water, and then heated to cause a polymer-forming reaction at the oil droplet interface to form microcapsule walls. 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 polyvalent isocyanate to be used and the polyol and polyamine to be reacted therewith are described in U.S. Pat. Nos. 3,281,383, 3,773,695, 3,793,268, and JP-B-48-1983.
No. 40347, No. 49-24159, JP-A-48-80191, No. 48-8408
No. 6 and they can be used.

Examples of the polyvalent isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, and 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-1,2-diisocyanate , Butylene-1,2-diisocyanate, diisocyanate such as cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate, 4,4 ′, 4 ''-triphenylmethane triisocyanate, toluene-2,4 Triisocyanates such as 6,6-triisocyanate, tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, 4-tolylene diisocyanate and trimethylolprop Adducts, adducts of xylylene diisocyanate and trimethylolpropane, there are isocyanate prepolymers such as tolylene diisocyanate and hexane triol adducts.

Examples of the polyol include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, and hydroxypolyalkylene ethers. The following polyols described in JP-A-60-49991 are also used. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,
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 A condensation product of an aromatic polyhydric alcohol such as resorcinol dihydroxyethyl ether and an alkylene oxide,
p-xylylene glycol, m-xylylene glycol, α, α′-dihydroxy-p-diisopropylbenzene, 4,4′-dihydroxy-diphenylmethane, 2- (p,
p'-dihydroxydiphenylmethyl) benzyl alcohol, an adduct of ethylene oxide with bisphenol A,
Bisphenol A may include adducts of propylene oxide. The polyol is preferably used in a ratio of 0.02 to 2 mol of the hydroxyl group to 1 mol of the isocyanate group.

As polyamines, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxy Trimethylenediamine, 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 microcapsules, a water-soluble polymer can be used, but the water-soluble polymer may be any of a water-soluble anionic polymer, a nonionic polymer, and an amphoteric polymer. As the anionic polymer, either a natural polymer or a synthetic polymer can be used, and examples thereof include polymers having a -COO-, SO2- group or the like. 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.

As the nonionic polymer, polyvinyl alcohol,
Examples include hydroxyethyl cellulose and methyl cellulose.

 Examples of the amphoteric compound include gelatin.

These water-soluble polymers are used as a 0.01 to 10% by weight aqueous solution. The average particle size of the microcapsules is adjusted to 2 μm or less.

The average particle size of the capsule used for the recording material of the present invention is 2
μm or less, and particularly preferably 0.5 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 a microcapsule 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 based on 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,
Paraffin, naphthenic oil, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene and 1-phenyl-1-xylylethane, 1-
Diarylethanes such as phenyl-1-p-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 ester (octyl benzoate), alkyl amide (eg, diethyl lauryl amide), fatty acid ester (eg, dibutoxyethyl succinate, dioctyl acetate), trimesic acid ester (eg, tributyl trimesate), ethyl acetate , Lower alkyl acetates such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve Seteto, there is cyclohexanone and the like.

At the time of microencapsulation, a volatile solvent may be used in combination with another solvent as an auxiliary solvent for dissolving the electron-donating colorless dye. 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 to 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, carboxynitrophenyl starch and the like. There are starch particles and the like, and those having a particle size of 1 to 20 μm are preferable. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. As silica particles, for example, FUJI-DEVISON CHE
SICHLOID AL-1, 65, 72, 79, 74, 40 manufactured by MICHAL LTD.
4, 620, 308, 978, 161, 162, 244, 255, 266, 150 and the like are preferable. The addition amount of the matting agent is preferably 2-500 mg / m2, and particularly preferably 5-100 mg / m2.

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 photosensitive / thermosensitive 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 a photographic light-sensitive material is useful, for example, an aldehyde compound such as formaldehyde and glutaraldehyde, and US Pat. No. 3,635,718.
No. 3,357,718 and others, compounds having a reactive ethylenically unsaturated bond described in U.S. Pat.
Aziridine compounds described in 3017280 and others, epoxy compounds described in U.S. Patent No. 3091537 and others, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane, dioxane such as dichlorodioxane or U.S. Pat. No. 3,687,707, vinyl sulfones described in U.S. Pat.No. 3,384,72, vinyl sulfone precursors described in U.S. Pat.No. 3,640,720, ketovinyls described in U.S. Pat. Chromium alum, zirconium sulfate, boric acid, etc. can be used. Among these curing agents, particularly preferred compounds are 1,3,5-triacroyl-hexahydro-s-triazine, 1,2-bisvinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, and bis ( α-vinylsulfonylacetamido) ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenimino-s-triazine, boric acid and the like. Addition amount is based on the binder
0.5-5% by weight is preferred.

In addition, colloidal silica may be added to the protective layer to reduce the adhesiveness. As colloidal silica, for example, Nissan Chemical's Snowtex 20, Snowtex 30, Snowtex C, Snowtex O,
Snowtex N and the like are preferred. 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 the multicolor recording material of the recording material used in the present invention, for example, a multi-layer containing a microcapsule containing an electron-donating colorless dye that develops a different hue and a photo-curable composition sensitive to light of a different wavelength in each layer. An intermediate layer containing an ultraviolet absorber may be provided between the photosensitive and heat-sensitive layers using the structure of the recording material.

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.

Benzotriazole compounds as ultraviolet absorbers,
Known compounds in the industry, such as a cinnamic acid ester compound, an aminoarylidenemalone 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 organic solvent having a boiling point of, for example,
After dissolving in a single solution of a so-called auxiliary solvent at a temperature of not lower than 160 ° C. and not higher than 160 ° C. or a mixed solution of both, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution or aqueous polyvinyl alcohol solution in the presence of a surfactant. Examples of high boiling organic solvents are described in U.S. Pat. No. 2,322,027 and the like. 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. Further, the dispersion may be accompanied by a phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, Nudel washing, ultrafiltration or the like before use for coating.

Specific examples of the latex dispersing process, the effect and the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230,
9-74538, 51-59943, 54-32552 and Resea
rch Disclosure, Vol. 148, August 1976, Item 14850. Suitable latexes include, for example, acrylates or methacrylates (eg, ethyl acrylate, n-butyl acrylate, n
-Butyl methacrylate, 2-acetoacetoxyethyl methacrylate, etc.) and acid monomers (eg, acrylic acid,
A copolymer latex of 2-acrylamide-2-methylpropanesulfonic acid or the like) is preferred.

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 an adjacent layer, for example, a polymer or latex copolymerized with an ultraviolet absorber. Such ultraviolet absorbers include, for example, European Patent No. 127,819 and JP-A-59-68731,
Nos. 9-26733, 59-23344, UK Patent 2,118,315, JP-A-58-111942, U.S. Patent 4,307,184, 4,202,836
Nos. 4,202,834, 4,207253, 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. As the reactive polymer,
Compounds that dissolve in water at 25 ° C. in an amount of 5% by weight or more are preferred. Specific examples thereof include proteins such as gelatin, gelatin derivatives, albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sodium alginate, and starches (denatured). Sugar derivatives such as starch), gum arabic, polyvinyl alcohol, styrene
Examples thereof include a maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, a saponified vinyl acetate-polyacrylic acid copolymer, and a synthetic polymer such as polystyrene sulfonate. Among these, gelatin and polyvinyl alcohol are preferred.

In the recording material of the present invention, as a binder for each layer of the recording material such as a protective layer, a photosensitive / thermosensitive layer, and an intermediate layer, the water-soluble polymer and polystyrene, polyvinyl formal,
Polyvinyl butyral, acrylic resin: for example, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and copolymers thereof, phenol resin, styrene-butadiene resin, ethyl cellulose, epoxy resin, urethane resin,
Or a polymer latex of these. Among these, gelatin and polyvinyl alcohol are preferred.

Coating aid for each layer of the photosensitive and heat-sensitive recording material of the present invention,
Various surfactants may be used for various purposes such as antistatic, improving slipperiness, emulsifying and dispersing, and preventing adhesion.

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 -Acyl-N-alkyltaurines,
Anionic surfactants such as sulfosuccinates and sulfoalkylpolyoxyethylenalkylphenyl ethers; amphoteric surfactants such as alkylbetaines and alkylsulfobetaines; and aliphatic or aromatic quaternary ammonium salts. A cationic surfactant can be used if necessary.

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 improvers for preventing irradiation and halation are Research Disclosure, Vol.176, December 1978, Item 1764
3, and Vol. 187, November 1979, Item 18716.

The coating material 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 as necessary, coated on a desired support, and dried to obtain the recording material of the present invention. Is obtained. In that case, as the solvent used,
Water, alcohol: for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec
-Butanol, methyl cellosolve, 1-methoxy-2-
Propanol; halogen-based solvent: for example, methylene chloride, ethylene chloride; ketone: for example, acetone, cyclohexanone, methyl ethyl ketone; ester: for example, methyl acetate, ethyl acetate, methyl acetate;
Mixtures of more than one species are mentioned by way of example. Of these, water is particularly preferred.

To coat the coating solution for each layer on the support, a blade coater, rod coater, knife coater, roll doctor coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain coater, extrusion coater, etc. Can be used. Research application method
Disclosure, Vol.200, December 1980, Item 20036 Item XV can be referred to. An appropriate thickness of the recording layer is 0.1 μ to 50 μ.

The recording material of the present invention can be used for various uses. For example, the recording material of the present invention can be used for applications such as copiers, faxes, printers, labels, color proofs, overhead projectors, and second original drawings. Suitable supports for these include paper, coated paper, laminated paper, synthetic paper and other supports and transparent films such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, aluminum, zinc, and the like. Examples thereof include a plate made of metal such as copper, and a substrate obtained by subjecting the surface of the above-described support to various treatments such as surface treatment, undercoating, and metal vapor deposition. Research Disclosur as support
e, Vol. 200, December 1980, Item 20036. In addition, 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 rear surface, if necessary.

The recording material of the present invention can record at high sensitivity with light in a wide range from ultraviolet light to visible light. As the light source, 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, a fluorescent lamp and the like can be used.

As the image recording method, various exposure methods such as contact exposure of an original such as a lith film, enlargement exposure of a slide or a liquid crystal image, and reflection exposure using reflected light of the original 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 above 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, preferably 1 ° C.
00 ° C to 160 ° C. Heating time is 1 second to 5 minutes,
Preferably it is 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.

"Examples" Hereinafter, the present invention will be described in more detail based on examples,
The present invention is not limited to these.

<Adjustment of coating liquid> 1. [Adjustment of electron-donating colorless dye (1) capsule] 12.4 g of electron-donating colorless dye (1) was dissolved in 10.4 g of ethyl acetate, and Takenate D-110N (Takeda Pharmaceutical Co., Ltd.) Made)
27 g and 3 g of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. This solution was added to a mixed solution of 4.6 g of polyvinyl alcohol and 74 g of water, and emulsified and dispersed at 20 ° C.
An emulsion was obtained. 100 g of water was added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring. After 2 hours, a capsule liquid containing the electron-donating colorless dye (1) in the core was obtained. The average particle size of the obtained capsule was 0.5 μm.

2. [Preparation of emulsion of photocurable composition] 2-a. Preparation of emulsion of photocurable composition (1) 0.1 g of photopolymerization initiator (1) and spectral sensitizing dye (1) 0.05g
8 g of a polymerizable electron-accepting compound (1) was added to a solution of 0.2 g of N-phenylglycine ethyl ester in 3 g of ethyl acetate as an auxiliary for accelerating the polymerization. This solution was added to 7.5
10000 by a homogenizer (manufactured by Nippon Seiki Co., Ltd.) added to a mixed solution of 9.6 g of a 2% aqueous solution of PVA, 9.6 g of a 2% aqueous surfactant (1) and 0.8 g of a 2% aqueous solution of a surfactant (2).
The mixture was emulsified for 5 minutes by rotation to obtain an emulsion of the photocurable composition (1).

2-b. Preparation of emulsion of photocurable composite (4) Photopolymerization initiator (1) 0.2 g, spectral sensitizing dye (1) 0.2 g and N-phenyl as an auxiliary for accelerating polymerization To a solution of 0.2 g of glycine ethyl ester in 4 g of ethyl acetate were added 10 g of (1-methyl-2-phenoxy) ethyl resorcinate, an electron-accepting compound, and 8 g of trimethylolpropane triacrylate monomer. This solution was added to a mixed solution of 19.2 g of a 15% PVA aqueous solution, 4.8 g of water, 0.8 g of a 2% surfactant (1) aqueous solution and 0.8 g of a 2% surfactant (2) aqueous solution, and a homogenizer (Nippon Seiki) (Manufactured by Co., Ltd.) at 10,000 rpm for 5 minutes to obtain an emulsion of the photocurable composition (4).

3. [Preparation of coating solution for positive-type photosensitive / thermosensitive layer] Electron-donating colorless dye (1) 4 g of capsule, 12 g of emulsion of photocurable composition (1) and 12 g of 15% PVA aqueous solution are mixed and mixed. A coating solution for the mold photosensitive / thermosensitive layer (1) was prepared.

4. [Preparation of coating solution for negative-type photosensitive / thermosensitive layer] A mixture of 1 g of an electron-donating colorless dye (1) capsule and 10 g of an emulsion of a photo-curable composite (4) is mixed with a negative-type photosensitive / thermosensitive layer ( 4) A coating solution was prepared.

5. [Preparation of Coating Solution for Protective Layer] 4.5 g of 10% gelatin aqueous solution, 1.5 g of distilled water, 0.5 g of 2% surfactant (3) aqueous solution and 1% of 2,4-dichloro-6-hydroxy-s- 1.5 g of an aqueous solution of sodium triazine and SYLOD 72 (manufactured by FUJI-DEVISON CHEMICHAL LTD.) Were mixed in an amount of 50 mg / m2 with Snowtex N1 g to prepare a coating solution for the protective layer (3). .

The structural formulas of the compounds used for preparing each of the above solutions are shown below.

Surfactant _{(2) C 12 H 25 SO} 3 Na < photosensitive and thermosensitive recording create materials and Evaluation> Example 1 The positive photosensitive heat-sensitive recording material photosensitive and heat-sensitive layer coating solution (1) to 100μ polyethylene terephthalate film dry weight of the coating layer using a coating bar. the coating is a 8 g / m ² on one at 30 ° C.
Dried for 0 minutes. A coating solution for the protective layer (1) is applied thereon using a coating bar so that the dry weight of the applied layer becomes ² g / m ² , and dried at 30 ° C. for 10 minutes to form a positive photosensitive / thermosensitive recording material. I got

A 1000W high-pressure mercury lamp (manufactured by Oak Co., Ltd.) passed through a lith film obtained by developing an image for cyan on the obtained photosensitive and heat-sensitive recording material and an optical filter (SC-41 filter: manufactured by Fuji Photo Film Co., Ltd.) that blocks light of 410 nm or less. (Jet Light). Then, when heated on a hot plate at 110 ° C. for 5 seconds, a clear cyan image was obtained. The resolution of the image was high and clear without turbidity.

Example 2 Negative-type photosensitive / thermosensitive recording material The photosensitive / thermosensitive layer coating solution (4) was applied on a 100 μm polyethylene terephthalate film using a coating bar so that the dry weight of the coating layer was 8 g / m ^2. 1 at 30 ° C
Dried for 0 minutes. Next, the coating liquid for the protective layer (1) was applied thereon by using a coating bar, and the dry weight of the applied layer was 5 g / m ^2.
And dried at 30 ° C. for 10 minutes to obtain a negative photosensitive / thermosensitive recording material.

The obtained photosensitive / thermosensitive recording material was exposed to ultraviolet light from a 1000 W high-pressure mercury lamp (Oak Jetlight) through a lith film in which a black-and-white image was developed.

Next, when heated on a hot plate at 110 ° C. for 5 seconds, a clear cyan negative image was obtained. A cyan image was obtained.
The resolution of the image was high and clear without turbidity.

Examples 3 and 4, Comparative Examples 1 and 2 Liquids containing microcapsules having various particle diameters were obtained according to the method described in 1. [Preparation of colorless electron-donating dye capsule]. That is, the emulsification conditions when adjusting the microcapsules were changed to obtain microcapsules having the average particle diameter shown in Table 1, and the liquid was used to prepare a photosensitive / thermosensitive recording material according to the method of Example 1. Exposure in the same way
Development was performed and evaluated.

 Table 1 shows the results.

[Effect of the Invention] Since the recording material of the present invention uses microcapsules having a fine particle diameter, pixels are small and a high-resolution image is provided. Further, since the particle diameter of the microcapsules is small, light scattering in the layer is small and a clear image is provided.

Continuation of the front page (56) References JP-A-57-124343 (JP, A) JP-A-59-91438 (JP, A) JP-A-58-88740 (JP, A) JP-A-63-294548 (JP, A) , A) JP-A-4-211252 (JP, A) JP-A-3-87827 (JP, A)

Claims (5)

(57) [Claims] 1. A latent image is formed on a photocurable composition outside a microcapsule by exposure, and an electron-accepting compound moves in a photosensitive material in accordance with the latent image by heating to provide an electron in the microcapsule. 1. A photosensitive / thermosensitive recording material which forms an image by coloring an insoluble colorless dye, wherein the microcapsules have an average particle size of 2 μm or less. 2. The photocurable composition according to claim 1, wherein the photocurable composition contains a compound having an electron-accepting portion and a polymerizable vinyl monomer portion in the same molecule and a photopolymerization initiator. A photosensitive / thermosensitive recording material, characterized in that: 3. In claim 1) or 2),
The photosensitive / thermosensitive recording material is a multicolor recording material. 4. A first photosensitive layer according to claim 3, wherein said photosensitive / thermosensitive recording material is exposed to light having a center wavelength λ1 from an exposure light source side to a support side of said recording material. an intermediate layer that absorbs light of λ1, a second photosensitive layer that is sensitive to light of center wavelength λ2 and develops a color different from that of the first photosensitive layer, an intermediate layer that absorbs light of center wavelength λi-1, and a center wavelength λi Layer structure in which at least two or more photosensitive layers are laminated on a support in the order of an i-th photosensitive layer that is sensitive to light and develops a color different from the first, second, and i-1st photosensitive layers. Having, and
A photosensitive / thermosensitive recording material characterized by having a center wavelength λ1 <λ2 <... <λi. Here, i is an integer of 2 or more. 5. The photosensitive recording material according to claim 4, wherein the center wavelengths λ1, λ2, and λ3 of the photosensitive recording material are 320 nm or more, and λ1 and λ
2. A photosensitive / thermosensitive recording material, wherein 2 is less than 400 nm and λ3 is 400 nm or more.