JPH04211252A - Photosensitive and thermosensitive recording material - Google Patents

Abstract

PURPOSE:To provide a monosheet type photosensitive and heatsensitive type recording material with which a multicolor negative type image free of the superposition in the single color region or the photosensitive wave length region by the simple operation of image light exposure and heat treatment. CONSTITUTION:A photosensitive and heatsensitive layer which contains the light-hardened type composition consisting of the micro-capsules containing the electron donner type colorless dye, polymerizable compound containing the ethylene type unsaturated bonds, photopolymerization starting agent, and an electron receiving type color development agent is formed on a supporting body.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a novel photosensitive/thermosensitive recording material using photothermography that can be used for copiers, faxes, printers, labels, color proofs, overhead projectors, second original drawings, etc. . More specifically, the present invention relates to a novel mono-sheet type recording material that does not use unnecessary consumables.

0002

[Prior Art] Photothermography is a method of developing an image by uniformly heating it after exposing it to light.
This method is called a photosensitive and thermal image forming method) and has the characteristic that images can be easily obtained using only dry processing. As one of these methods, a method is known in which a visible image is formed by heat development using a photopolymerizable composition and a heat-sensitive coloring material, as disclosed in, for example, Japanese Patent Application Laid-Open No. 52-89915. When the two components of a two-component heat-sensitive coloring material are placed separately inside and outside microcapsules containing a photopolymerizable composition and exposed to light and heated, the heat-sensitive coloring material becomes does not move, so it does not develop color, but
In unexposed areas, the particles move, react, and develop color to form a positive image. However, this method cannot sufficiently suppress the color development of the photocured area during heat development, and only unclear images with large so-called background fog can be obtained.

[0003] As another method, for example, JP-A-61
As disclosed in Japanese Patent No. 123838, there is known a recording material comprising a photopolymerizable composition comprising a vinyl monomer having an acidic group and a photopolymerization initiator, and a dye precursor capable of producing a dye with an acid. After imagewise exposure, this recording material is uniformly heated in close proximity to the dye precursor to cause the dye precursor to react with the unpolymerized monomer having an acid group that has been diffused, thereby producing a positive visible image. It is something that forms. However, all of these methods utilize photopolymerizability to slow down the thermal diffusivity of the cured portion, suppressing contact between color-forming components and attempting to obtain a positive visible image. Therefore, there is no known method of obtaining a negative colored visible image using photopolymerization and heat development.

[0004] In addition, in such photosensitive/thermosensitive recording materials, a transfer type using two sheets is also possible, but
By laminating at least two photosensitive/thermosensitive layers having different photosensitive wavelengths and coloring hues, a particularly desirable multicolor recording material in the form of a monosheet can be obtained since unnecessary sheets are not used. However, it is not easy to separate the sensitive wavelength ranges of each photosensitive/thermosensitive layer. That is, when conventionally known photopolymerization initiators or photopolymerization initiator/spectral sensitizer combinations are used, the sensitive wavelength ranges of each layer overlap, making it difficult to photopolymerize each layer independently. Regarding this point, for example, Japanese Patent Application Laid-Open No. 61-24495 (or U.S. Patent No. 4
Attempts have been made to add ultraviolet absorbers into photosensitive compositions, such as those found in US Pat. However, although this method shows improvement, there is still a large overlap in the sensitive wavelength ranges.

[0005]

As a result of intensive research, the present inventors have succeeded in obtaining a so-called negative image in which the photocured portion develops color using a simple process of image exposure/thermal development. We succeeded in eliminating this overlapping region by providing an intermediate layer containing an ultraviolet absorber between the photosensitive and thermosensitive layers to limit the light reaching the underlying layer. The first object of the present invention is to provide a photosensitive/thermosensitive recording material using a method in which a polymer image obtained by photocuring is converted (developed) into a negative visible image by heat treatment. That is, it is an object of the present invention to provide a photosensitive/thermosensitive recording material that can obtain a monochromatic or multicolor negative image by simple operations of image exposure and heat treatment. The second object is to provide a monochromatic or multicolor photosensitive/thermosensitive recording material in which the photosensitive wavelength ranges of the respective photosensitive/thermosensitive layers have little overlap and each color image can be recorded independently. The third objective is to provide a mono-sheet type monochrome or multicolor recording material that does not use unnecessary consumables.

[0006]

[Means for Solving the Problems] The object of the present invention is to prepare, on a support, (1) microcapsules containing an electron-donating colorless dye, (2) a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator and A photosensitive/thermosensitive recording material comprising a photosensitive/thermosensitive layer containing a photocurable composition comprising an electron-accepting color developer, and a photosensitive/thermosensitive recording material having at least two such photosensitive/thermosensitive layers. This has been achieved by a photosensitive/thermosensitive recording material characterized in that an intermediate layer containing an ultraviolet absorber is provided between the photosensitive/thermosensitive layers.

The image according to the present invention is obtained by curing a photocurable composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an electron-accepting color developer, and then curing the composition. It is obtained by a method in which the electron-accepting color developer selectively moves in the cured area by uniform heating and comes into contact with the electron-donating colorless dye in the coexisting microcapsules to develop color. In the hardened part, polymerization reduces the interaction between the polymerizable compound having an ethylenically unsaturated bond and the electron-accepting developer, so that the developer spreads faster and becomes electron-donating and colorless in the capsule. It develops color when it comes into contact with dyes. On the other hand, in the uncured part, the electron-accepting color developer is trapped in a polymerizable compound having an ethylenically unsaturated bond, and even when heated, it cannot come into contact with the electron-donating colorless dye in the capsule, making it visible. No image is formed.

Therefore, the photosensitive/thermosensitive layer of the present invention can be prepared in various configurations depending on the purpose. Preferable 1
One composition consists of minute droplets of a photocurable composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an electron-accepting color developer, and a microdroplet containing an electron-donating colorless dye. It has a structure in which a layer consisting of capsules is provided on a support. In this case, the minute droplets may be in the form of an emulsion or may be the core material of a microcapsule. A binder may be present in this layer. Another preferred configuration includes an electron-donating colorless dye in the continuous phase of the photocurable composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an electron-accepting color developer. It has a structure in which a layer containing microcapsules is provided on a support. This continuous phase may be a mixture of photocurable composition and binder.

The recording material of the present invention can be a monochromatic so-called B/W recording material or a multicolor recording material by using the above-mentioned photosensitive/thermosensitive layer. In the case of a recording material, for example, it is possible to use a multilayer recording material structure in which each layer contains microcapsules containing electron-donating colorless dyes that develop colors in different hues and photocurable compositions that are sensitive to light of different wavelengths. can. Specifically, a layer containing microcapsules containing an electron-donating colorless dye that develops a cyan color and a photocurable composition that is sensitive to wavelength λ1 is provided on a support, and a layer containing an electron-donating dye that develops a magenta color is placed on the support. Microcapsules containing colorless dye and wavelength λ2
A layer containing a photocurable composition sensitive to wavelength λ3 was provided, and a layer containing microcapsules containing an electron-donating colorless dye that develops a yellow color and a photocurable composition sensitive to wavelength λ3 was provided thereon. A structure in which an intermediate layer is provided between each layer, a structure in which an ultraviolet absorber is contained in this intermediate layer, etc. can be used. When using an intermediate layer, for example, a layer containing microcapsules containing an electron-donating colorless dye that develops a cyan color and a photocurable composition that is sensitive to a wavelength λ1 is provided on a support, and a layer containing a photocurable composition that is sensitive to a wavelength λ1 is provided on the support. λ
1, an intermediate layer that absorbs shorter wavelength light is provided, and a layer containing microcapsules containing an electron-donating colorless dye that develops a magenta color and a photocurable composition that is sensitive to wavelength λ2 is provided thereon; An intermediate layer absorbing light with a wavelength shorter than wavelength λ2 is provided on top, and a layer containing microcapsules containing an electron-donating colorless dye that develops a yellow color and a photocurable composition sensitive to wavelength λ3 is provided on top of the intermediate layer. Specific examples include a structure in which a protective layer is provided on the protective layer.

When conventionally known photopolymerization initiators or combinations of photopolymerization initiators/spectral sensitizers are used, the photosensitive wavelength ranges of each layer overlap, but in the present invention, the photosensitive/thermosensitive This overlap region can be eliminated by providing an intermediate layer containing a UV absorber between the layers to limit the light reaching the underlying layer. Various conventionally known methods can be used to introduce this ultraviolet absorber into the intermediate layer. One is the so-called emulsion dispersion method, in which an ultraviolet absorber is dissolved in a water-insoluble organic solvent, and the solution is emulsified and dispersed in an aqueous dispersion medium containing a surfactant to form minute droplets and introduced into the intermediate layer. There is a way to be called. In this method, the organic solvent or surfactant may act on the adjacent photosensitive/thermosensitive layer, causing some adverse effects such as lowering the color density. Another method is to introduce a polymer latex carrying an ultraviolet absorber into the intermediate layer. Polymer latexes carrying ultraviolet absorbers can be obtained using methods known in the art. For example, an ultraviolet absorber is dissolved in a water-insoluble volatile organic solvent, and the solution is emulsified and dispersed in an aqueous dispersion medium containing a surfactant, formed into minute droplets, and then mixed with a polymer latex. Bye. Even in this method, adverse effects may occur depending on the amount and type of surfactant used. Yet another method is to introduce a polymer latex containing a UV absorber monomer as a polymerization component into the intermediate layer. In this case, the amount of surfactant used is the smallest and adverse effects of the surfactant are less likely to occur, so it is most preferable.

The polymerizable compound having an ethylenically unsaturated bond that can be used in the photocurable composition of the present invention is a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule. . 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, etc. can be used. Among these, polymerizable compounds containing a heteroatom having at least one lone pair of electrons in the molecule are preferred. The term "heteroatom having a lone pair of electrons" as used herein refers to atoms such as oxygen, nitrogen, sulfur, phosphorus, and halogen. Specifically, ester bonds, amide bonds, carbonyl bonds,
Included are those having a thiocarbonyl bond, ether bond, thioether bond, and groups such as amine, alcohol, thioalcohol, phosphine, and halogen. Among these, polymerizable polymers with ethylenically unsaturated bonds that have at least one ester bond, amide bond, amine, carbonyl bond, and/or ether bond in the molecule that have strong interaction with electron-accepting color developers Preferably, the compound is
Particularly preferred are compounds having highly polymerizable ester bonds and amide bonds. In addition, in order to make the polymerization efficiency (curing speed) advantageous, it is necessary to have multiple ethylenic unsaturated molecules in the molecule.
Polymerizable compounds having a double bond are preferred, such as acrylic esters and methacrylic esters of polyhydric alcohols such as trimethylolpropanayapentaerythritol; acrylate- or methacrylate-terminated epoxy resins; and acrylate- or metharylate-terminated polyesters. . Specific examples of particularly preferred compounds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol Examples include dimethacrylate. The molecular weight of these polymerizable compounds can be about 100 to about 5,000, but it is more preferable to use a compound that is difficult to thermally diffuse into the electron-donating colorless dye-containing microcapsules.
00 or higher are particularly useful.

As the photopolymerization initiator suitably used in the present invention, one or a combination of two or more compounds from among the compounds capable of initiating photopolymerization of the above-mentioned ethylenically unsaturated bond-containing compound can be used. You can choose. 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, 2-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-53-133428, JP-B-Sho 57-1819,
Compounds described in the specifications of Japanese Patent Publication No. 57-6096 and U.S. Patent No. 3,615,455, Japanese Patent Publication No. 58-29803
S-triazine derivatives having a trihalogen-substituted methyl group as described in No. 2, for example, 2,4,6-tris(trichloromethyl)-S-triazine, 2-methoxy-4,6-bis(trichloromethyl)-S-triazine , 2-amino-4,6-bis(trichloromethyl)-S-triazine, 2-(P-methoxystyryl)-4,6-bis(trichloromethyl)-S-triazine, and the like. and organic peroxides such as those described in JP-A-59-189340, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditertiary butyl diperoxy isophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxybenzoate, α,α'-bis(tert-butylperoxyisopropyl)benzene, dicumyl peroxide, 3,3' , 4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone and the like. and azinium salt compounds as described, for example, in US Pat. No. 4,743,530; and, for example, in European Patent No. 0
Organoboron compounds described in No. 223587: for example, tetramethylammonium salt of triphenylbutylborate, tetrabutylammonium salt of triphenylbutylborate, tetramethylammonium salt of tri(P-methoxyphenyl)butylborate, etc.; and other diaryliodoniums. Photopolymerization initiators well known in the art such as salts and iron allene complexes can be usefully used.

[0013] Furthermore, as a photopolymerization initiator system, combinations of two or more types of compounds are known, and such combinations can also be used in the present invention. Examples of combinations of two or more compounds include the combination of 2,4,5-triarylimidazole dimer and mercaptobenzoxazole, and the 4,4'- combinations of bis(dimethylamino)benzophenone and benzophenone or benzoin methyl ether; benzoyl-N-methylnaphthothiazoline and 2,4-bis(trichloromethyl)-6-(4'-) as described in U.S. Pat. No. 4,239,850; methoxyphenyl)-triazole combination, and JP-A-57-2360
The combination of dialkylaminobenzoic acid ester and dimethylthioxanthone described in the specification of No. 2, and JP-A-59-
The combination of 4,4'-bis(dimethylamino)benzophenone, benzophenone, and polyhalogenated methyl compound described in No. 78339 can be mentioned. More preferred examples include a combination of 4,4'-bis(diethylamino)benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, and a combination of 4,4'-bis(diethylamino)benzophenone and 2,4 , 5-triarylimidazole dimer. Among these photopolymerization initiators, particularly preferred compounds include benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group,
Mention may be made of organic peroxides, azinium salt compounds and organic boron compounds. The content of photoinitiator is
Based on the total weight of the photopolymerizable composition, preferably from 0.01 to
20% by weight, and more preferably 0.2-15% by weight
The most preferable content is 1 to 10% by weight. If it is less than 0.01% by weight, the sensitivity will be insufficient, and if it exceeds 10% by weight, no increase in sensitivity can be expected.

The photocurable composition of the present invention may contain, in addition to a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator, a spectral sensitizing dye for adjusting its sensitivity wavelength. . Various compounds known in the art can be used as the spectral sensitizing dye. Examples of spectral sensitizing dyes include the above-mentioned patents related to photopolymerization initiators, Research
h Disclosure, Vol. 200, 1980
December 2003, Item 20036, "Sensitizer" (Katsumi Tokumaru/Shin Okawara/ed. Kodansha 1987) No. 1
You can refer to pages 60-163. As a specific example of a spectral sensitizing dye, for example, JP-A-58-15503
3-ketocoumarin compound is disclosed in Japanese Patent Application Laid-Open No. 58-4
No. 0302 discloses thiopyrylium salts in Japanese Patent Publication No. 59-
No. 28328 and No. 60-53300 disclose naphthothiazole merocyanine compounds, and Japanese Patent Publication No. 61-9621,
No. 62-3842, JP-A No. 59-89303, No. 6
No. 0-60104 each discloses a merocyanine compound. These spectral sensitizers can extend the spectral sensitivity of the photopolymerization initiator to the visible range. In the above example, trihalomethyl-S was used as the photoinitiator.
- Although a triazine compound is mentioned, it may be combined with other photoinitiators. Spectral sensitizing dyes include keto dyes such as coumarin (including ketocoumarin or sulfonocoumarin) dyes, merostyryl dyes, oxonol dyes, and hemioxonol dyes, non-keto dyes such as non-keto polymethine dyes, anthracene dyes, rhodamine dyes, Included are acridine dyes, aniline dyes and azo dyes, cyanine, hemicyanine and styryl dyes as non-keto polymethine dyes.

The photopolymerizable composition of the present invention may further contain reducing agents such as oxygen scavengers and chain transfer agents for active hydrogen donors, as well as auxiliary agents for promoting polymerization. Other compounds that promote polymerization can also be used in combination. 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. Furthermore, thiols, thioketones, trihalomethyl compounds, lofin dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, and the like shown below are also useful as polymerization accelerators.

Furthermore, in addition to these compounds, a thermal polymerization inhibitor can be added to the photopolymerizable composition as required. Thermal polymerization inhibitors are added to prevent thermal polymerization and polymerization over time of photopolymerizable compositions, thereby improving the chemical stability of photopolymerizable compositions during preparation and storage. can be increased. As an example of a 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- Examples include butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine, and the like. The preferable addition amount of the thermal polymerization inhibitor is 0.00000000000000000000000000000000000000000000000000,000,000,000,000,000,000,000 which is based on the total weight of the photopolymerizable composition.
001 to 5% by weight, more preferably 0.01 to 5% by weight
It is 1% by weight. If it is less than 0.001% by weight, thermal stability will be poor, and if it exceeds 5% by weight, sensitivity will be reduced.

The photocurable composition of the present invention may be used by being encapsulated in microcapsules, if necessary. For example, it can be encapsulated in microcapsules with reference to European Patent No. 0223587 and the above patents.

[0018] As the electron-accepting color developer according to the present invention,
Phenol derivatives, sulfur-containing phenol derivatives, organic carboxylic acid derivatives (e.g. salicylic acid, stearic acid, resorcinic acid, etc.) and their metal salts, sulfonic acid derivatives, urea or thiourea derivatives, etc., acid clay, bentonite, novolac. Resin, metal processing novolak resin,
Examples include metal complexes. These examples are described in Paper and Pulp Technology Times (1985) pages 49-54 and 65-70, as well as in Japanese Patent Publications No. 40-9309 and No. 45-1403.
9, Japanese Patent Publication No. 52-140483, 48-51510,
57-210886, 58-87089, 59-11286, 60-176795, 61-9598
8 etc. To give some examples of these, phenolic compounds include 2,2'-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-isooctylidene diphenol, 4
, 4'-sec-butylidene diphenol, 4-ter
Al includes t-octylphenol, 4-p-methylphenylphenol, 4,4'-methylcyclohexyritenephenol, 4,4'-isopentylidenephenol, benzyl p-hydroxybenzoate, and the like. Examples of salicylic acid derivatives include 4-pentadecylsalicylic acid, 3,5-di(α
-methylbenzyl)salicylic acid, 3,5-di(tert)
-octyl)salicylic acid, 5-octadecylsalicylic acid, 5-α-(p-α-methylbenzylphenyl)ethylsalicylic acid, 3-α-methylbenzyl-5-tert-
Octylsalicylic acid, 5-tetradecylsalicylic acid, 4
-Hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid, 4-pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid, etc., and their zinc, aluminum, calcium, copper, and lead salts There is. These electron-accepting compounds can be used alone or in combination of two or more. The amount of the electron-accepting compound used is preferably in the range of 10 to 4,000% by weight, particularly preferably 100 to 2,000% by weight of the electron-donating colorless dye.

Electron-donating colorless dyes according to the present invention include conventionally known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucoolamine compounds, and rhodamine lactam compounds. compound, triphenylmethane compound,
Various compounds such as triazene compounds, spiropyran compounds, and fluorene compounds can be used. Specific examples of phthalides include U.S. Reissue Patent Specification No. 23,024, U.S. Patent Specification No. 3,491,111, and U.S. Patent Specification No. 3,491.
, No. 112, No. 3,491,116 and No. 3,
No. 509,174, specific examples of fluorans are U.S. Pat. No. 3,624,107 and U.S. Pat.
No. 3,641,011, No. 3,462,82
No. 8, No. 3,681,390, No. 3,920,5
No. 10, No. 3,959,571; specific examples of spirodipyrans are described in U.S. Pat. Specific examples of fluorene compounds are described in Japanese Patent Application No. 3,853,869, No. 4,246,318, and Japanese Patent Application No. 61-240989. To disclose some of these, triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophthalide),
- dimethylaminophenyl) phthalide, 3-(p-
dimethylaminophenyl)-3-(1,3-dimethylindol-3-yl) phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl) phthalide, etc. , diphenylmethane compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoauramine, N-2,4,5-trichlorophenylleucoauramine, and xanthene compounds. Rhodamine-B-anilinolactam, rhodamine-(p-nitrino)lactam, 2-(
dibenzylamino) fluoran, 2-anilino-3-
Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N
- Isoamylaminofluorane, 2-anilino-3-
Methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chloro-6-
Diethylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-methyl- N-
Tetrahydrofurfurylaminofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 2-(o-chloroanilino)-6-diethylaminofluorane, 2-(3,4-dichloroanilino)-
6-diethylaminofluorane, etc., and thiazine compounds include benzoylleucomethylene blue, p
-Nitrobenzylleucomethylene blue, etc., and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran 3,
3'-dichloro-spiro-dinaphthopyran, 3-
Benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)-spiropyran, 3-
Examples include propyl-spiro-dibenzopyran. In particular, when used in full-color recording materials, electron-donating colorless dyes for cyan, magenta, and yellow are disclosed in US Pat.
, 800,149, etc., for the yellow coloring type, U.S. Pat.

When the electron-donating colorless dye of the present invention is microencapsulated, it can be prepared by a method known in the art. For example, US Patent No. 2800457, US Patent No. 28000
458, U.S. Pat. No. 3,287,154.
No., British Patent No. 990443, Special Publication No. 38-1957
No. 4, US Pat. No. 42-446, and US Pat. No. 42-771, interfacial polymerization methods, US Pat.
660304, a method by polymer precipitation,
Methods using isocyanate polyol wall materials found in U.S. Pat. No. 3,796,669, U.S. Pat. No. 39,145
A method using isocyanate wall materials as found in No. 11,
Methods using urea-formaldehyde-based and urea-formaldehyde-resorcinol-based wall-forming materials as seen in U.S. Pat. No. 4,001,140, U.S. Pat. No. 4,087,376, and U.S. Pat. Method of using wall-forming materials, Japanese Patent Publication No. 36-
9168, the in situ method by polymerization of monomers as seen in JP-A-51-9079, the electrolytic dispersion cooling method as seen in British Patent Nos. 952807 and 965074, US Patent No. 3111407, British Patent There is a spray drying method as seen in No. 930422. Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

[0021] The microcapsule wall of the present invention is particularly effective when using a microencapsulation method by polymerizing a reactant from inside an oil droplet. That is, it is possible to obtain capsules, which are desirable as a recording material and have a uniform particle size and excellent storage stability, within a short time. For example, when polyurethane is used as the capsule wall material, a polyvalent isocyanate and, if necessary, a second substance that reacts with it to form the capsule wall (e.g., polyol, polyamine) are mixed into the oily liquid to be encapsulated, and then the polyisocyanate is mixed into the oily liquid to be encapsulated. By emulsifying and dispersing the oil and then increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming microcapsule walls. At this time, a co-solvent with a low boiling point and strong dissolving power can be used in the oily liquid. In this case, the polyvalent isocyanate used and the polyol and polyamine to be reacted with it are disclosed in US Pat. No. 3,281,383.
No. 3773695, No. 3793268, Japanese Patent Publication No. 48-40347, No. 49-24159, Japanese Unexamined Patent Publication No. 49-24
No. 8-80191 and No. 48-84086, and these 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, diphenyl methane-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, cyclohexylene-1,2-diisocyanate, cyclohexylene-1 , 4-diisocyanate, 4,4',4''-triphenylmethane triisocyanate, toluene-2,4,6
- triisocyanates, such as triisocyanates, 4
,4'-dimethyldiphenylmethane-2,2',5,5
Tetraisocyanates such as '-tetra isocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, tolylene diisocyanate. and isocyanate prepolymers such as hexanetriol adducts.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers. Tokukai 1986
The following polyols described in No.-49991 can also be 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- Condensation products of aromatic polyhydric alcohols such as di(2-hydroxyethoxy)benzene, resorcinol dihydroxyethyl ether, and alkylene oxides, p-xylylene glycol, m-xylylene glycol, α,α'-dihydroxy-p -diisopropylbenzene, 4,4'-dihydroxy-diphenylmethane, 2-(p,p'-dihydroxydiphenylmethyl)benzyl alcohol, adducts of ethylene oxide to bisphenol A, adducts of propylene oxide to bisphenol A, etc. Can be mentioned. The ratio of hydroxyl groups to 1 mole of isocyanate groups in polyols is 0.02 to 1.
Preferably, 2 mol is used.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylene
Examples include triamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds. Polyvalent isocyanates can also react with water to form polymeric materials.

When making microcapsules, water-soluble polymers can be used, and the water-soluble polymers may be any of water-soluble anionic polymers, nonionic polymers, and amphoteric polymers. Both natural and synthetic anionic polymers can be used, such as -COO-
, -SO2- groups, and the like. Specific anionic natural polymers include gum arabic, alginic acid, pectin, etc., and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfonic acid, etc. In addition, synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, and vinylbenzenesulfonic acid-based polymers and copolymers. , carboxy-modified polyvinyl alcohol, etc.

Examples of nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose. Examples of amphoteric compounds include gelatin. These water-soluble polymers are used as a 0.01 to 10% by weight aqueous solution. The particle size of microcapsules is 20
Adjusted to below μm. The size of the capsules used in the present invention is 80 μm or less, and preferably 20 μm or less from the viewpoint of storage stability and handling properties. Also, if the capsule is too small, the surface area for a given solids content will be large and a large amount of wall material will be required. For this reason, the thickness is preferably 0.1 μm or more.

The electron-donating colorless dye according to the present invention may be present in the microcapsules in a solution state or in a solid state. When a solvent is used in combination, the amount of solvent used in the capsule is 100% of the electron-donating colorless dye.
A ratio of 1 to 500 parts by weight is preferred.

Natural oils or synthetic oils can be used in combination with the solvent used in the present invention. 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-xylylethanes, 1- phenyl-1-p-ethyl phenylethane,
Diarylethanes such as 1,1'-ditolylethane. Phthalic acid alkyl ester (dibutyl phthalate,
dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (
(e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters (e.g. tributyl trimesate). ), lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, and the like. Further, during microencapsulation, a volatile solvent may be used in combination as an auxiliary solvent for dissolving the electron-donating colorless dye. Examples of this type of solvent include ethyl acetate, butyl acetate, methylene chloride, and the like.

In the present invention, it is preferable to add a matting agent to the protective layer. Examples of matting agents include inorganic compounds such as silica, magnesium oxide, barium sulfate, strontium sulfate, and silver halide; polymer particles such as polymethyl methacrylate, polyacrylonitrile, and polystyrene; and carboxy starch, corn starch, and carboxynitrophenyl starch. Examples include starch particles, preferably those having a particle size of 1 to 20 μm. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. Examples of silica particles include FUJI-D
EVISON CHEMICHAL LTD. Cyroid AL-1, 65, 72, 79, 74, 404, 6
20, 308, 978, 161, 162, 244, 25
5, 266, 150, etc. are preferred. The amount of the matting agent added is preferably 2-500 mg/m2, particularly preferably 5-100 mg/m2.

In the present invention, it is preferable to use a curing agent in each layer of the recording material of the present invention, such as the photosensitive/thermosensitive layer, intermediate layer, and protective layer. In particular, it is preferable to use a curing agent in the protective layer in order to reduce the adhesiveness of the protective layer. As a hardening agent, for example, a "gelatin hardening agent" used in the production of photographic light-sensitive materials is useful, such as aldehyde-based compounds such as formaldehyde and glutaraldehyde, and US Pat. No. 3,635.
Compounds having reactive halogens as described in No. 718 and others, compounds having reactive ethylenically unsaturated bonds as described in U.S. Pat. No. 3,635,718 and others;
Aziridine compounds described in U.S. Patent No. 3017280 and others, epoxy compounds described in U.S. Patent No. 3091537 and others, halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, or U.S. Patent No. 3642486 and U.S. Patent No. 368770
Vinyl sulfones described in U.S. Pat. No. 7, U.S. Pat.
The vinyl sulfone precursors described in US Pat. No. 8,418,72, the ketovinyls described in US Pat. No. 3,640,720, or inorganic hardeners such as chromium alum, zirconium sulfate, boric acid, etc. can be used. Among these curing agents, particularly preferred compounds are 1,
3,5-triacryloyl-hexahydro-s-triazine, 1,2-bisvinylsulfonylmethane, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(αvinylsulfonylacetamido)ethane, 2,4-
These are compounds such as dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenimino-s-triazine, and boric acid. The amount added is preferably 0.5-5% by weight based on the binder. In addition, colloidal silica may be added to the protective layer to reduce its tackiness. Examples of colloidal silica include Snowtex 20 and Snowtex 30 manufactured by Nissan Chemical.
Snowtex C, Snowtex O, Snowtex N, etc. are preferred. The amount added is 5 to the binder.
-80% by weight is preferred. Further, a fluorescent whitening agent or a blue dye as a bluing agent may be added to the protective layer to increase the whiteness of the recording material of the present invention.

In the case of the multicolor recording material of the present invention, for example, a multilayer recording material in which each layer contains microcapsules containing electron-donating colorless dyes that develop colors in different hues and photocurable compositions that are sensitive to light of different wavelengths. Using the material structure, an intermediate layer containing an ultraviolet absorber is provided between the photosensitive and thermosensitive layers. The middle layer mainly consists of a binder and a UV absorber.
Additives such as a curing agent and polymer latex can be contained as necessary. As the ultraviolet absorber, compounds known in the industry such as benzotriazole compounds, cinnamic acid ester compounds, aminoarylidenemalonitrile compounds, and benzophenone compounds can be used.

The ultraviolet absorber used in the present invention can be emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method and then added to a desired layer, particularly an intermediate layer. In the oil-in-water dispersion method, after dissolving either a high-boiling point organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a boiling point of 30°C or higher and 160°C or lower, either alone or in a mixture of the two, surface active Finely dispersed in an aqueous medium such as water or an aqueous gelatin solution or an aqueous polyvinyl alcohol solution in the presence of an agent. Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Further, as specific examples of the high boiling point organic solvent and the auxiliary solvent, the same solvents as those used in the encapsulation described above can be preferably used. In addition, dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be distilled or
It may be used for application after being removed or reduced by nude washing or ultrafiltration. The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. No. 4,199,363, OLS
) No. 2,541,274 and No. 2,541,23
No. 0, JP-A-49-74538, JP-A No. 51-59943
No. 54-32552 and Research
Disclosure, Vol. 148, 1976 8
Month, Item 14850, etc. Suitable latexes include, for example, acrylic or methacrylic esters (e.g. ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, etc.) and acid monomers (e.g. acrylic acid, 2-acrylamide, etc.). −
A copolymer latex of 2-methylpropanesulfonic acid, etc.) is preferred.

[0033] As the ultraviolet absorber most preferably used in the present invention, there is an ultraviolet absorber having a structure that makes it difficult to diffuse into adjacent layers, such as a polymer or latex copolymerized with an ultraviolet absorber. Examples of such ultraviolet absorbers include European Patent No. 127,819 and Japanese Unexamined Patent Publication No. 59-6
No. 8731, No. 59-26733, No. 59-2334
No. 4, British Patent No. 2,118,315, Japanese Unexamined Patent Publication No. 58-1
No. 11942, U.S. Pat. No. 4,307,184, U.S. Patent No. 4,
No. 202,836, No. 4,202,834, No. 4,2
No. 07253, No. 4,178,303, JP-A-47-
You can refer to No. 560 etc. These ultraviolet absorbers are added to the intermediate layer, but may also be added to the protective layer, photosensitive/thermal layer, antihalation layer, etc., if necessary.

In the present invention, the dispersion of the photocurable composition and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer. is preferably a compound that dissolves at least 5% by weight in water at 25°C, and specifically includes gelatin, gelatin derivatives, proteins such as albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sodium alginate,
Saponification of sugar derivatives such as starches (including modified starches), gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, vinyl acetate-polyacrylic acid copolymer synthetic polymers such as polystyrene sulfonate and polystyrene sulfonate. Among these, gelatin and polyvinyl alcohol are preferred.

In the present invention, binders for each layer of the recording material, such as the protective layer, photosensitive/thermosensitive layer, and intermediate layer, include the above-mentioned water-soluble polymers, polystyrene, polyvinyl formal,
Polyvinyl butyral, acrylic resin: For example, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and their copolymers, phenolic resin, styrene-butadiene resin, ethyl cellulose, epoxy resin, urethane resin, etc. with high solvent solubility Molecules or polymer latexes thereof can be used. Among these, gelatin and polyvinyl alcohol are preferred.

Various surfactants are used in each layer of the photosensitive/thermosensitive recording material produced using the present invention for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification dispersion, and preventing adhesion. Good too. Examples of surfactants include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfate esters, N -Anionic surfactants such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylenyl phenyl ethers, amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines, fatty or A cationic surfactant such as aromatic quaternary ammonium salts can be used if necessary.

Various additives, including the additives mentioned above, can be added to the recording material of the present invention as necessary. For example, typical examples of dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents, and slipperiness improvers are listed in Research Disclosure,
Vol. 176, December 1978, Item 176
43, and the same Vol. 187, November 1979,
Described in Item 18716. The recording material of the present invention can be obtained by dissolving the coating liquid for the photosensitive/thermosensitive layer of the present invention and the coating liquid for each layer described above in a solvent as necessary, coating it on a desired support, and drying it. . Solvents used in that case include water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, methyl cellosolve, 1-methoxy-2-propanol; halogen solvents such as Examples include methylene chloride, ethylene chloride; ketones: for example, acetone, cyclohexanone, methyl ethyl ketone; esters: for example, methyl cellosolve acetate, ethyl acetate, methyl acetate; toluene, xylene, etc. alone and mixtures of two or more thereof. Among these, water is particularly preferred.

To apply the coating solution for each layer onto the support, a blade coater, rod coater, knife coater, roll doctor coater, comma coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain can be used. A coater, extrusion coater, etc. can be used. The application method is Research Disclos.
ure, Vol. 200, December 1980, Item
You can refer to Section 20036 XV. The 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 purposes. For example, copiers, faxes, printers, labels, etc.
Color proof, overhead projector, 2nd
The recording material of the present invention can be used for purposes such as original drawings. Suitable supports include paper, coated paper, laminated paper, synthetic paper, transparent films such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, aluminum, zinc, Examples include plates of metal such as copper, and those obtained by subjecting the surface of the above-mentioned support to various treatments such as surface treatment, undercoating, and metal vapor deposition. As a support, Resea
rch Disclosure, Vol. 200,19
The support described in December 1980, Item 20036, Section XVII can also be referred to. In addition, these supports have an antihalation layer on the front surface, a slip layer on the back surface, and
Layers such as an anti-stack layer, an anti-curl layer, and an adhesive layer can be provided depending on the purpose.

The recording material of the present invention can record with high sensitivity using light in a wide range from ultraviolet light to visible light. Light sources include mercury lamps, xenon lamps, tungsten lamps,
Various lasers such as metal halide lamps, argon lasers, helium neon lasers, semiconductor lasers, LE
D. A wide range of light sources such as fluorescent lights can be used. As an image recording method, various exposure methods can be used, such as close exposure of an original such as a lithographic film, enlarged exposure of a slide or liquid crystal image, and reflection exposure using reflected light from the original. When performing multicolor recording, image recording may be performed multiple times using light of different wavelengths. Light of different wavelengths can be obtained by changing the light source or changing the optical filter.

The recording material of the present invention is subjected to heat development treatment simultaneously with or after the imagewise exposure. As a heating method in this heat development treatment, various conventionally known methods can be used. Heating temperature is generally 80℃ to 200℃
℃, preferably 100℃ to 160℃. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute. EXAMPLES The present invention will be explained in more detail by Examples below, but the present invention is not limited thereto.

[0042]

[Example] [Synthesis of ultraviolet absorber latex] Synthesis example 1
: Synthetic distilled water of ultraviolet absorber latex (1) 200%
ml and 0.5 g of surfactant (sodium dodecylbenzene sulfonate) in a flask and heated for 80 minutes in a nitrogen stream.
Stir at ℃. To this were added 0.5 g of potassium persulfate and 0.25 g of sodium bisulfite. Furthermore, a mixture of 16 g of polymerizable ultraviolet absorber (1), 33 g of butyl acrylate, and 1 g of acrylic acid was added little by little, and after the total addition, 0.5 g of potassium persulfate and 0.25 g of sodium hydrogen sulfite were added. The mixture was stirred for 1 hour. The resulting liquid was adjusted to pH 6 with 1N caustic soda solution and filtered using filter paper to obtain the desired latex.

Synthesis Example 2: Ultraviolet absorber latex (2
) Synthesis Example 1 except that 16 g of polymerizable ultraviolet absorber (1), 33 g of butyl acrylate, and 1 g of acrylic acid in Synthesis Example 1 were replaced with 5 g of polymerizable ultraviolet absorber (2), 44 g of butyl acrylate, and 1 g of acrylic acid. Ultraviolet absorber latex (2) was obtained in the same manner as above.

Synthesis Example 3: Synthesis of latex (1) for dispersing ultraviolet absorbent latex 400 ml of distilled water and 1 g of surfactant (sodium dodecylbenzenesulfonate) were placed in a flask and stirred at 80°C in a nitrogen stream. did. In this, 1g of potassium persulfate
and 0.5 g of sodium bisulfite were added. Furthermore, a mixture of 79 g of butyl methacrylate, 20 g of butyl acrylate, and 1 g of acrylic acid was added little by little into the mixture, and after the entire amount was added, 1 g of potassium persulfate and 0.5 g of sodium bisulfite were further added and stirred for 1 hour. The resulting liquid was adjusted to pH 6 with 1N caustic soda solution and filtered through filter paper to obtain the desired latex.

[Preparation of coating solution] 1. Preparation of electron-donating colorless dye capsules 1-a.
Electron-donating colorless dye (1) Preparation of capsules Dissolve 12.4 g of electron-donating colorless dye (1) in 10.4 g of ethyl acetate, add 12.4 g of dicyclohexyl phthalate and Takenate D-110N (manufactured by Takeda Pharmaceutical Company Limited). 27 g and 3 g of Millionate MR200 (manufactured by Nippon Polyurethane Industries, 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. to obtain an emulsion having an average particle size of 1.5 μm. 100 g of water was added to the obtained emulsion and heated to 60° C. while stirring, and after 2 hours, a capsule liquid containing the electron-donating colorless dye (1) in the core was obtained.

1-b. Electron-donating colorless dye (2) Preparation of capsules 1-a. 1-a. except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (2). Electron-donating colorless dye (2) capsules were obtained in the same manner as above.

1-c. Preparation of electron-donating colorless dye (3) capsules 1-a. 1-a. except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (3). Electron-donating colorless dye (3) capsules were obtained in the same manner as above.

2. Preparation of emulsion of photocurable composition 2
-a. Preparation of emulsion of photocurable composition (1) 0.2 g of photopolymerization initiator (1), 0.2 g of spectral sensitizing dye (1), and N-phenylglycine ethyl ester as an auxiliary agent for promoting polymerization. 10 g of electron-accepting compound (1) trimethylolpropane triacrylate monomer (trifunctional acrylate, molecular weight approximately 29
6) 8g was added. This solution was added to a mixed solution of 19.2 g of 15% PVA aqueous solution, 4.8 g of water, 0.8 g of 2% surfactant (1) aqueous solution, and 0.8 g of 2% surfactant (2) aqueous solution. Emulsification was performed for 5 minutes at 10,000 revolutions using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion of photocurable composition (1).

2-b. Preparation of emulsion of photocurable composition (2) 2-a. 2-a. except that 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (2). The photocurable composition (2
) was obtained.

2-c. Preparation of emulsion of photocurable composition (3) 2-a. 2-a. except that 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (3). The photocurable composition (3
) was obtained.

2-d. Preparation of emulsion of photocurable composition (4) 2-a. 0.2g of photopolymerization initiator (1) and 0.2g of spectral sensitizing dye (1) were combined. )0.2
2-a. except that it was changed to g. An emulsion of photocurable composition (4) was obtained in the same manner as described above.

2-e. Preparation of emulsion of photocurable composition (5) 2-a. 2- except that 0.2 g of photoinitiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photoinitiator (2) and 0.2 g of ultraviolet absorber (2). a. An emulsion of photocurable composition (5) was obtained in the same manner as described above.

2-f. Preparation of emulsion of photocurable composition (6) 2-a. 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (2), and further 2-a. The acrylate monomer of monomer (
2-a. except that it was changed to 1). An emulsion of photocurable composition (6) was obtained in the same manner as described above.

2-g. Preparation of emulsion of photocurable composition (7) 2-a. 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (2), and further 2-a. The acrylate monomer of monomer (
2) except for the change to a. An emulsion of photocurable composition (7) was obtained in the same manner as described above.

2-h. Preparation of emulsion of photocurable composition (8) 2-a. 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (2), and further 2-a. The acrylate monomer of monomer (
2-a except for changing to 3). An emulsion of photocurable composition (8) was obtained in the same manner as described above.

2-i. Preparation of emulsion of photocurable composition (9) 2-a. 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (2), and further 2-a. The acrylate monomer of monomer (
4) except for the change to a. An emulsion of photocurable composition (9) was obtained in the same manner as described above.

2-j. Preparation of emulsion of photocurable composition (10) 2-a. 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (2), and further 2-a. The acrylate monomer of monomer (
2-a. except for the change to 5). An emulsion of photocurable composition (10) was obtained in the same manner as described above.

3. Preparation of ultraviolet absorber dispersion 3-
a. Preparation of emulsion of ultraviolet absorber (1) A solution of 0.26 g of ultraviolet absorber (1) dissolved in 3 g of ethyl acetate and 5 g of dibutyl phthalate was added to a 7.5% PVA aqueous solution 9.
6 g of 2% surfactant (1) aqueous solution and 0.8 g of 2% surfactant (2) aqueous solution were added to a mixed solution of 0.8 g of 2% surfactant (1) aqueous solution and heated at 10,000 rpm for 5 minutes using a homogenizer (manufactured by Nippon Seiki Co., Ltd.). The mixture was emulsified to obtain an emulsion of ultraviolet absorber (1).

3-b. Preparation of emulsion of UV absorber (2) A solution of 0.26 g of UV absorber (2) dissolved in 3 g of ethyl acetate and 5 g of dibutyl phthalate was mixed with 7.5% P.
9.6 g of VA aqueous solution and 0.0 g of 2% surfactant (1) aqueous solution.
It was added to a mixed solution of 8 g and 0.8 g of a 2% surfactant (2) aqueous solution, and emulsified at 10,000 rpm for 5 minutes using a homogenizer (manufactured by Nippon Seiki Co., Ltd.).
An emulsion was obtained.

3-c. Preparation of latex dispersion of UV absorber (1) A solution of 0.26 g of UV absorber (1) dissolved in 3 g of ethyl acetate was mixed with 9.6 g of 7.5% PVA aqueous solution and 2% surfactant (1) aqueous solution. 0.8g and 2% surfactant (2
) was added to a mixed solution with 0.8 g of an aqueous solution and emulsified for 5 minutes at 10,000 rpm using a homogenizer (manufactured by Nippon Seiki Co., Ltd.). This emulsion was mixed with 9.25 g of latex (1) for latex dispersion of ultraviolet absorber and 25 g of 5% PVA aqueous solution.
．． A latex dispersion of ultraviolet absorber (1) was obtained by mixing and stirring with 5 g of the ultraviolet absorbent (1).

3-d. Preparation of latex dispersion of UV absorber (2) A solution of 0.26 g of UV absorber (2) dissolved in 3 g of ethyl acetate was mixed with 9.6 g of 7.5% PVA aqueous solution and 2% surfactant (1) aqueous solution. It was added to a mixed solution of 0.8 g and 0.8 g of 2% surfactant (2) aqueous solution, and the mixture was heated using a homogenizer (
(Nippon Seiki Co., Ltd.) at 10,000 rpm for 5 minutes. This emulsion was mixed with 9.25 g of latex (1) for latex dispersion of ultraviolet absorber and 25.5 g of 5% PVA aqueous solution.
A latex dispersion of ultraviolet absorbent (2) was obtained.

4. Preparation of coating solution for photosensitive/thermosensitive layer 4-
a. Preparation of Coating Solution for Photosensitive/Thermosensitive Layer (1) 1 g of electron-donating colorless dye (1) capsules and 10 g of emulsion of photocurable composition (1) were mixed to prepare a coating solution for photosensitive/thermosensitive layer (1). Prepared.

4-b. Preparation of coating solution for photosensitive/thermosensitive layer (2) 1 g of electron-donating colorless dye (2) capsules and 10 g of emulsion of photocurable composition (2) are mixed to form photosensitive/thermosensitive layer (2).
A coating solution was prepared.

4-c. Preparation of coating solution for photosensitive/thermosensitive layer (3) 1 g of electron-donating colorless dye (3) capsules and 10 g of emulsion of photocurable composition (3) are mixed to form photosensitive/thermosensitive layer (3).
A coating solution was prepared.

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

4-e. Preparation of coating solution for photosensitive/thermosensitive layer (5) 1 g of electron-donating colorless dye (2) capsules and 10 g of emulsion of photocurable composition (5) are mixed to form photosensitive/thermosensitive layer (5).
A coating solution was prepared.

4-f. Preparation of coating solution for photosensitive/thermosensitive layer (6) 1 g of electron-donating colorless dye (2) capsules and 10 g of emulsion of photocurable composition (6) are mixed to form photosensitive/thermosensitive layer (6).
A coating solution was prepared.

4-g. Preparation of coating solution for photosensitive/thermosensitive layer (7) 1 g of electron-donating colorless dye (2) capsules and 10 g of emulsion of photocurable composition (7) are mixed to form photosensitive/thermosensitive layer (7).
A coating solution was prepared.

4-h. Preparation of coating solution for photosensitive/thermosensitive layer (8) 1 g of electron-donating colorless dye (2) capsules and 10 g of emulsion of photocurable composition (8) are mixed to form photosensitive/thermosensitive layer (8).
A coating solution was prepared.

4-i. Preparation of coating solution for photosensitive/thermosensitive layer (9) 1 g of electron-donating colorless dye (2) capsules and 10 g of emulsion of photocurable composition (9) are mixed to form photosensitive/thermosensitive layer (9).
A coating solution was prepared.

4-j. Preparation of Coating Solution for Photosensitive/Thermosensitive Layer (10) 1 g of electron-donating colorless dye (2) capsules and 10 g of emulsion of photocurable composition (10) were mixed to form a coating solution for photosensitive/thermosensitive layer (10).
0) was prepared.

5. Preparation of coating liquid for intermediate layer 5-a.
Preparation of coating solution for intermediate layer (1) 4 g of a 15% PVA aqueous solution, 3 g of distilled water, 0.5 g of a 2% surfactant (3) aqueous solution, and 3 g of an emulsion of ultraviolet absorber (1) were mixed to form the intermediate layer ( 1)
A coating solution was prepared.

5-b. Preparation of coating solution for intermediate layer (2) Emulsion 3 of 4 g of 15% PVA aqueous solution, 3 g of distilled water, 0.5 g of 2% surfactant (3) aqueous solution, and ultraviolet absorber (2)
g to prepare a coating solution for intermediate layer (2).

5-c. Preparation of coating liquid for intermediate layer (3) 1
4g of 5% PVA aqueous solution, 3g of distilled water, and 2% surfactant (
3) A coating solution for the intermediate layer (3) was prepared by mixing 0.5 g of the aqueous solution and 4 g of the latex dispersion of the ultraviolet absorber (1).

5-d. Preparation of coating liquid for intermediate layer (4) 1
4g of 5% PVA aqueous solution, 3g of distilled water, and 2% surfactant (
3) A coating solution for the intermediate layer (4) was prepared by mixing 0.5 g of the aqueous solution and 4 g of the latex dispersion of the ultraviolet absorber (2).

5-e. Preparation of coating liquid for intermediate layer (5) 1
4g of 5% PVA aqueous solution, 3g of distilled water, and 2% surfactant (
3) 0.5g of aqueous solution and ultraviolet absorber latex (1) 3
g to prepare a coating solution for intermediate layer (5).

5-f. Preparation of coating liquid for intermediate layer (6) 1
4g of 5% PVA aqueous solution, 3g of distilled water, and 2% surfactant (
3) 0.5g of aqueous solution and ultraviolet absorber latex (2) 4
g to prepare a coating solution for intermediate layer (6).

5-g. Preparation of coating liquid for intermediate layer (7) 1
4g of 5% PVA aqueous solution, 3g of distilled water, and 2% surfactant (
3) A coating solution for intermediate layer (7) was prepared by mixing with 0.5 g of an aqueous solution.

6. Preparation of coating liquid for protective layer 6-a.
Preparation of coating solution for protective layer (1) 10% gelatin aqueous solution 4.
5g, distilled water 1.5g and 2% surfactant (3) aqueous solution 0
．． 5g and 1% 2,4-dichloro-6-hydroxy-s
- 1.5 g of triazine sodium salt aqueous solution and Thyroid 72 (FUJI-DEVISON CHEMICHI)
AL LTD. A protective layer (
A coating solution for 1) was prepared.

[Preparation and evaluation of photosensitive/thermal recording material] Example 1 Coating solution (2) for photosensitive/thermal layer was applied onto a 100 μm polyethylene phthalate film using a coating bar until the dry weight of the coated layer was 8 g. /m2 and dried at 30°C for 10 minutes. On top of that a protective layer (1)
The sample of Example 1 was obtained by applying the coating solution using a coating bar so that the dry weight of the coating layer was 5 g/m 2 and drying at 30° C. for 10 minutes.

Example 2 Coating liquid (6) for photosensitive/thermosensitive layer was applied in the same manner as in Example 1.
The sample of Example 2 was obtained by drying.

Example 3 Coating liquid (7) for photosensitive/thermosensitive layer was applied in the same manner as in Example 1.
The sample of Example 3 was obtained by drying.

Example 4 Coating liquid (8) for photosensitive/thermosensitive layer was applied in the same manner as in Example 1.
The sample of Example 4 was obtained by drying.

Example 5 Coating liquid (9) for photosensitive/thermosensitive layer was applied in the same manner as in Example 1.
The sample of Example 4 was obtained by drying.

Example 6 The photosensitive/thermosensitive layer coating liquid (10) was applied and dried in the same manner as in Example 1 to obtain a sample of Example 4. Each of the obtained photosensitivity
Step wedge for heat-sensitive recording material (FUJI CO.
NTROL WEDGE (manufactured by Fuji Photo Film Co., Ltd.)
The sample was exposed to ultraviolet light from a 1000W high-pressure mercury lamp (Jet Light, manufactured by Oak Co.). Thereafter, when heated for 5 seconds on a hot plate at 120° C., clear magenta negative images were obtained for each sample. However, compared to Examples 3 and 4, Examples 1 and 2 provided images with higher contrast, and the sensitivity was about 4 times higher. Furthermore, in Examples 5 and 6, slight background fogging occurred on the background, and the contrast of the images was somewhat inferior to Examples 1 to 4. As is clear from the above results, in order to obtain a clear negative image, the monomer used must have at least one ester bond and/or amide bond in the molecule, and a polyfunctional monomer with a molecular weight of 200 or more. It turns out that one is more preferable.

Comparative Example 1 Coating solution (1) for photosensitive/thermosensitive layer was applied onto a 100μ polyethylene terephthalate film using a coating bar so that the dry weight of the coating layer was 8 g/m2.
It was dried at 0°C for 10 minutes. An intermediate layer (7) was applied and dried on top of this layer to a dry weight of 5 g/m2, and then
Coating liquid (2) for photosensitive/thermosensitive layer was applied and dried to a dry weight of 8 g/m2, and then intermediate layer (7) was coated and dried to a dry weight of 5 g/m2. Coating liquid (3) for the heat-sensitive layer was applied and dried so that the dry weight was 8 g/m2, and then the coating liquid for the protective layer (1) was applied on top of it using a coating bar so that the dry weight of the coated layer was 5 g/m2. The sample of Comparative Example 1 was obtained by coating the sample in such a manner as to give the following properties and drying it at 30° C. for 10 minutes. The obtained photosensitive/thermosensitive recording material is coated with a lithium film in which a yellow image is developed and an optical filter (SC-41 filter) that blocks light below 410 nm.
The film was exposed to ultraviolet light from a 1000 W high-pressure mercury lamp (Jet Light, manufactured by Oak Co., Ltd.) through a 1000 W high-pressure mercury lamp (Jet Light manufactured by Oak Co., Ltd.). Next, the image for magenta was exposed to light from a high-pressure mercury lamp through a developed lithium film and an optical filter (BPB-36 filter, manufactured by Fuji Photo Film Co., Ltd.) that only transmits light around 360 nm. A lithographic film with a developed image and an optical filter that only transmits light around 300 nm (BPB-30 filter:
Fuji Photo Film Co., Ltd.) and exposed to light from a high-pressure mercury lamp to obtain an image. Thereafter, when it was heated for 5 seconds on a hot plate at 110° C., a full color image was not obtained, but an image mainly consisting of a yellow image.

Comparative Example 2 Coating liquid (4) for photosensitive/thermosensitive layer was applied onto a 100μ polyethylene terephthalate film using a coating bar so that the dry weight of the coating layer was 8 g/m2.
It was dried at 0°C for 10 minutes. An intermediate layer (7) was applied and dried on top of this layer to a dry weight of 5 g/m2, and then
Coating liquid (5) for photosensitive/thermosensitive layer was applied and dried to a dry weight of 8 g/m2, and then intermediate layer (7) was coated and dried to a dry weight of 5 g/m2. Coating liquid (3) for the heat-sensitive layer was applied and dried so that the dry weight was 8 g/m2, and then the coating liquid for the protective layer (1) was applied on top of it using a coating bar so that the dry weight of the coated layer was 5 g/m2. The sample of Comparative Example 2 was obtained by coating the sample in such a manner as to give the following properties and drying it at 30° C. for 10 minutes. Comparative Example 1 The obtained photosensitive/thermal recording material
When exposed and heat-developed in the same manner as above, an unclear full-color image with low color density was obtained.

Example 7 A sample of Example 7 was prepared by applying intermediate layer (1) and intermediate layer (2) instead of the intermediate layer of the sample of Comparative Example 1. That is, the photosensitive/thermosensitive layer coating solution (1) was applied onto a 100μ polyethylene terephthalate film using a coating bar so that the dry weight of the coating layer was 8 g/m 2 , and dried at 30° C. for 10 minutes. On top of this layer, the intermediate layer (1) was applied and dried to a dry weight of 5 g/m2, and then the photosensitive/thermosensitive layer coating liquid (2) was applied to a dry weight of 8 g.
/m2, then apply and dry the intermediate layer (2) to a dry weight of 5g/m2, and then expose to light.
Apply and dry the heat-sensitive layer coating solution (3) to a dry weight of 8 g/m2, and then apply the protective layer (1) coating solution on top using a coating bar until the dry weight of the coating layer is 5 g/m2.
2 and dried at 30° C. for 10 minutes to obtain a sample of Example 7. When the obtained photosensitive/thermal recording material was exposed and heat-developed in the same manner as in Comparative Example 1,
Clear, full-color images were obtained. cyan in the exposed area,
The density of magenta and yellow is 1.1, 1.2, and 0.
It was 9.

Example 8 Intermediate layer (1), which is the intermediate layer used in Example 7, and intermediate layer (
Instead of 2), samples were prepared in which intermediate layer (3) and intermediate layer (4) were applied. When the obtained photosensitive/thermal recording material was exposed and heat-developed in the same manner as in Comparative Example 1, a clear full-color image was obtained. The densities of cyan, magenta, and yellow in the exposed area are 1.3, 1.3, and 1.1, respectively.
Met.

Example 9 Intermediate layer (1), which is the intermediate layer used in Example 7, and intermediate layer (
Instead of 2), samples were prepared in which intermediate layer (5) and intermediate layer (6) were applied. When the obtained photosensitive/thermal recording material was exposed and heat-developed in the same manner as in Comparative Example 1, a clear full-color image was obtained. The densities of cyan, magenta, and yellow in the exposed area are 1.6, 1.6, and 1.4, respectively.
Met.

As is clear from these Examples and Comparative Examples, when the photosensitive/thermosensitive recording material of the present invention provided with an intermediate layer containing an ultraviolet absorber is used, sufficient sensitivity wavelength of each photosensitive/thermosensitive layer can be obtained. Separation is possible and a clear multicolor negative image can be obtained. In particular, when a latex copolymerized with monomers is used as an ultraviolet absorber, a clear multicolor negative image with high color density can be obtained. The chemical structural formulas of the compounds used in the present invention are shown below.

[0092]

[Chemical formula 1]

[0093]

[Case 2]

[0094]

[Chemical formula 3]

[0095]

[C4]

[0096]

[C5]

[0097]

[C6]

[0098]

Effects of the Invention The recording material of the present invention is a mono-sheet type that does not use unnecessary materials, and it is possible to easily obtain clear multicolor images by only image exposure and heating operations. Due to the effect of the intermediate layer containing the ultraviolet absorber of the present invention, each color image can be recorded clearly, and a clear multicolor image can be obtained.

Claims (8)

[Claims] Claim 1: On a support, a photoreceptor comprising: (1) microcapsules containing an electron-donating colorless dye, and (2) a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an electron-accepting color developer. A photosensitive composition containing a curable composition.
A photosensitive/thermosensitive recording material characterized by being provided with a heat-sensitive layer. 2. The photosensitive/thermosensitive recording according to claim 1, wherein the polymerizable compound having an ethylenically unsaturated bond contains a heteroatom having at least one lone pair of electrons in the molecule. material. 3. In claim 1, the polymerizable compound having an ethylenically unsaturated bond has at least one ester bond, amide bond, amine, carbonyl bond and/or ether bond in the molecule. Characteristic photosensitive/thermosensitive recording materials. 4. The photosensitive/thermosensitive compound according to claim 1, wherein the polymerizable compound having an ethylenically unsaturated bond has a molecular weight of 200 or more and has a plurality of ethylenic double bonds. Recording materials. 5. The photosensitive/thermosensitive material according to claim 1, comprising at least two photosensitive/thermosensitive layers, and an intermediate layer containing an ultraviolet absorber provided between the photosensitive/thermosensitive layers. Recording materials. 6. The photosensitive/thermosensitive recording material according to claim 5, wherein the ultraviolet absorber is dispersed in the form of fine particles. 7. The photosensitive/thermosensitive recording material according to claim 5, wherein the ultraviolet absorber is dispersed in latex. 8. The photosensitive/thermosensitive recording material according to claim 5, wherein the ultraviolet absorber is a latex copolymerized with an ultraviolet absorbent monomer.