JPH0387827A - Photosensitive and thermosensitive recording material - Google Patents

Abstract

PURPOSE:To form the above material as a monosheet type and to obtain distinct multicolor images only by the exposing and heating by providing two layers of specific photosensitive and thermosensitive layers consisting of a photosetting compsn. contg. colorless dyes and providing an intermediate layer contg. a UV absorbent therebetween. CONSTITUTION:Two layers of the photosensitive and thermosensitive layers contg. the photosetting compsn. which contain an electron acceptive and polymerizable vinyl monomer and a photopolymn. initiator and microcapsules contg. the electron donative colorless dyes are provided and the intermediate layer contg. the UV absorbent is provided therebetween. The photosetting compsn. is cured by image exposing and is thereafter uniformly heated to bring the electron acceptive monomer and the electron donative colorless dyes of the microcapsules into contact with each other to develop colors. The cured part is delayed in diffusion and the contact with the colorless dyes is hindered so that no colors are developed in the cured part. The overlap regions of photosensitive wavelength regions are eliminated by the intermediate layer. The distinct multicolor images are thus obtd.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention is a novel photosensitive method using photothermography that can be used for applications such as copiers, fascis, printer labels, color proofs, and overhead projectors - second original drawings.・Insert into heat-sensitive recording material.

More specifically, we will develop a new mono-sheet type recording material that does not use unnecessary consumables.

``Prior art'' The method of obtaining an image by exposing the image to light and then developing it by heating is called photothermography (light- and heat-sensitive image forming method), and the feature is that the image can be easily obtained using only dry processing. have.

These methods include, for example, Japanese Patent Application Laid-Open No. 52-8991.
As disclosed in Japanese Patent No. 5, a method is known in which a photopolymerizable composition and a heat-sensitive coloring material are used to form a visible image by heat development. This is because when the two components of a two-component thermosensitive coloring material are placed separately inside and outside or on both sides of a microcapsule containing a photopolymerizable composition, when the material is exposed to light and heated, the parts that have been cured by the exposure Since the heat-sensitive material does not move, it does not develop color, but in unexposed areas it moves, reacts, and develops color to form an 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.

Further, as another method, for example, JP-A-61-12383
As disclosed in Japanese Patent No. 8, 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 form a visible image by causing the dye precursor to react with the diffused monomer having an unpolymerized acid group. . These recording materials can be of a transfer type using two sheets, but a mono-sheet type that does not use unnecessary sheets is particularly desirable.

If this method is used, a multicolor recording material can be obtained in a monosheet by laminating at least two photosensitive/thermosensitive layers having different photosensitive wavelengths and coloring hues.

However, it has been difficult to separate the sensitive wavelength ranges of each photosensitive/thermosensitive layer. 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 US Pat.
, 576.891), attempts have been made to add ultraviolet absorbers to photosensitive compositions.

However, although this method shows improvement, there is still a large overlap in the sensitive wavelength range.

We have conducted extensive research into ways to reduce the overlap of the photosensitive wavelength ranges, and have finally arrived at the present invention. In the present invention, we succeeded in eliminating this overlap region by providing an intermediate layer containing an ultraviolet absorber between the photosensitive and thermosensitive layers to limit the light reaching the lower layer.

Object of the present invention The first object of the present invention is to provide a multicolor photosensitive/thermosensitive recording material using a method of converting (developing) a polymer image obtained by photocuring into a visible image by heat treatment. It is.

The second object is to provide a multicolor photosensitive/thermosensitive recording material that allows images to be obtained by simple operations of image exposure and heat treatment.

The third objective is to provide a mono-sheet type multicolor recording material that does not use unnecessary consumables.

The fourth object is to provide a 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.

``Means for Solving the Problems'' The purpose of the present invention is to provide a photocurable composition containing an electron-accepting and polymerizable vinyl monomer and a photopolymerization initiator on a support; and ■ an electron-donating colorless composition. By a photosensitive/thermosensitive recording material having at least two photosensitive/thermosensitive layers containing microcapsules containing a dye, and an intermediate layer containing an ultraviolet absorber between the photosensitive/thermosensitive layers. achieved.

The image according to the present invention is produced by exposing and curing a photocurable composition containing an electron-accepting and polymerizable vinyl monomer and a photopolymerization initiator, and then uniformly heating it to generate electrons in uncured areas. It is obtained by a method of bringing a receptive monomer into contact with an electron-donating colorless dye in microcapsules to develop color.

In the cured part, the diffusion of the electron-accepting monomer is slowed down, preventing contact with the electron-donating colorless dye, and no color develops.

In the present invention, a photosensitive resin containing the above-mentioned photocurable composition is used.
Since it has at least two heat-sensitive layers, and each layer has a different color hue and a different sensitive wavelength range, it is possible to independently form images of different colors in each layer.

Conventionally known photopolymerization initiators or photopolymerization initiators/
When a combination of spectral sensitizers is used, the sensitivity wavelength ranges of each layer overlap, but in the present invention, the sensitivity wavelength range of each layer overlaps.
They succeeded in eliminating this overlap region by providing an intermediate layer containing a UV absorber between the heat-sensitive 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, forming minute droplets and introducing them into the intermediate layer. There is a way. In this method, the organic solvent or surfactant may act on the adjacent photosensitive/thermosensitive layer, resulting in adverse effects such as a decrease in 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, a UV absorber is dissolved in a water-insoluble volatile organic solvent, and the solution is emulsified and dispersed in an aqueous dispersion medium containing a surfactant, formed into minute droplets, and then mixed with a polymer latex. do it. Even in this method, adverse effects of the surfactants used may occur.

Another method is to introduce a polymer latex containing an ultraviolet absorber monomer as a polymerization component into the intermediate layer. This method is the most preferred because it uses the least amount of surfactant and the adverse effects of the surfactant are least likely to occur.

The photosensitive/thermosensitive layer of the present invention can be created in various configurations depending on the purpose.

One preferred configuration supports a layer consisting of minute droplets of a photocurable composition containing an electron-accepting and polymerizable vinyl monomer and a photopolymerization initiator and microcapsules containing an electron-donating colorless dye. This is a configuration installed on the body. In this case, the droplet may be the core material of the microcapsule.

There may also be a binder in this layer.

Another preferred configuration supports a layer in which microcapsules containing an electron-donating colorless dye are present in a continuous phase of a photocurable composition containing an electron-accepting and polymerizable vinyl monomer and a photoinitiator. This is a configuration installed on the body. This continuous phase may be a mixture of photocurable composition and binder.

Another preferred configuration is that the photocurable composition containing an electron-accepting and polymerizable vinyl monomer and a photopolymerization initiator and the microcapsules containing an electron-donating colorless dye form a continuous phase mainly composed of a binder. The layer present therein is provided on a support.

The multicolor recording material of the present invention includes, for example, a multilayer recording material in which each layer contains microcapsules containing an electron-donating colorless dye that develops colors in different hues and a photocurable composition that is sensitive to light of different wavelengths. The following configuration can be used.

For example, a layer containing microcapsules containing an electron-donating colorless dye that develops a cyan color and a photocurable ductile material that is sensitive to a wavelength of 1 is provided on a support, and a layer containing a photocurable ductile material that is sensitive to a wavelength of 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 illuminant that is sensitive to wavelengths in the range 2 is provided on top of the intermediate layer. An intermediate layer that absorbs 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 ductile material that is sensitive to wavelength λ3 is provided on top of the intermediate layer. It is possible to use a structure in which a protective layer is provided and a protective layer is further provided thereon.

The electron-accepting and polymerizable vinyl monomer used in the present invention may be any compound containing an electron-accepting group and an ethylenically unsaturated bond in the molecule. Examples of such compounds include methacryloxyethyl ester of benzoic acid having a hydroxyl group as described in JP-A No. 63-173682, acryloxyethyl ester synthesized by a similar synthesis method, and JP-A No. 59-83693. , same 6
The ester of benzoic acid having a hydroxyl group and hydroxymethylstyrene described in Nos. 0-141587 and 62-99190, the hydroxystyrene described in European Patent No. 29323, and JP-A-62-1670
No. 77, N-vinylimidazole complexes of zinc halide described in No. 62-16708 and No. 63-31.
Various compounds that can be synthesized with reference to the developer monomer described in No. 7558 can be used.

Specific examples include styrene sulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, zinc β-methacryloxyethoxysalicylate, zinc β-acryloxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β-methacryloxyethyl orseinate, β - Acryloxyethyl orselinate, 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, methacrylamide propane sulfone,
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 distyrene sulfone Acid amide phenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid, acrylic acid, methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid, 3-β-hydroxyethoxyphenol, β-methacryloxyethyl- p-
Hydroxybenzoate, β-acryloxyethyl-p
-Hydroxybenzoate, β'-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid, β-acryloxyethyloxycarbonylhydroxybenzoic acid, N, N'
-di-β-methacryloxyethylaminosalicylic acid, N
, N'-di-β-acryloxyethylaminosalicylic acid, N,N'-di-β-methacryoxyethylaminosulfonylsalicylic acid, N,N'-di-β-acryloxyethylaminosulfonylsalicylic acid, etc., and these metals. Salts such as zinc salts can be preferably used.

As the photopolymerization initiator suitably used in the present invention, one type or a combination of two or more types of compounds may be selected from among the compounds capable of initiating photopolymerization of the compound containing an ethylenically unsaturated bond. can.

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, benzoinphenyl ether; and 2,4.5-)
Realyl imidazole dimer: for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(0-chlorophenyl)-4,5-di(m-methoxyphenyl) imidazole dimer, 2-(0-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(0-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 57-1
No. 819, Japanese Patent Publication No. 57-6096, U.S. Patent No. 361
Compounds described in each specification of No. 5455, JP-A-58-
S-) riazine derivatives having a trihalogen-substituted methyl group described in No. 29803: For example, 2,4.6-)lis(
trichloromethyl)-S-triazine, 2-methoxy-
4゜6-bis(trichloromethyl)-5-) riazine,
2-amino-4,6-bis(trichloromethyl)-S-
) riazine, 2-(P-methoxystyryl)-4,6-
compounds such as bis(trichloromethyl)-3-) riazine; and organic peroxides such as those described in JP-A-59-189340, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3.5-
1-limethylcyclohexanone peroxide, benzoyl peroxide, ditertiary butyl diperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tertiary-butyl peroxybenzoate, α, α'- Compounds such as bis(tert-butylperoxyisopropyl)benzene, dicumyl peroxide, 3,3'4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone. and azinium salt compounds as described for example in US Pat. No. 4,743,530; and organoboron compounds as described in, for example, EP 0223587: for example the tetramethylammonium salt of triphenylbutylborate, the tetrabutylammonium salt of triphenylbutylborate. , tetramethylammonium salt of tri(P-methoxyphenyl)butylborate, etc.;
Other photopolymerization initiators well known in the art, such as diaryliodonium salts and iron arene complexes, can be usefully used.

Furthermore, combinations of two or more types of compounds are known as photopolymerization initiator systems, and such combinations can also be used in the present invention. Examples of combinations of two or more compounds include a combination of 2,4゜5I-triarylimidazole dimer and mercaptobenzoxazole, and 4,4゜ described in U.S. Pat. No. 3,427,161.
"-Bis(dimethylamino)benzophenone and benzophenone or benzoin methyl ether combination, benzoyl- as described in U.S. Pat. No. 4,239,850
A combination of N-methylnaphthothiazoline and 2,4-bis(trichloromethyl)-6-(4'-methoxyphenyl)-triazole, and a dialkylaminobenzoic acid ester and dimethyl described in JP-A-57-23602. Interlacing of thioxanthone, Mani JP-A-69-7SAA9
The combination of 4,49-bis(dimethylamino)benzophenone, benzophenone, and polyhalogenated methyl compound described in the above specification can be mentioned. More preferred examples include a combination of 4,4'-bis(diethylamino)benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and 4-dimethylaminobenzoic acid ether, and a combination of 4,4'-bis(diethylamino)benzophenone and 2.4-dimethylaminobenzoic acid. .5-Triarylimidazole dimer combination.

Among these photopolymerization initiators, particularly preferred compounds include benzoin ethers, S-) riazine derivatives having a trihalogen-substituted methyl group, organic peroxides, azinium salt compounds, and organic boron compounds.

The content of the photopolymerization initiator is preferably 0.01 to 20% by weight, and more preferably 0.2 to 15% by weight, and the most preferable content is 5% by weight, based on the total weight of the photopolymerizable composition. ~10% by weight. Sensitivity is insufficient when the amount is 0.01% by weight without grooves, and no increase in sensitivity can be expected when it exceeds 10% by weight.

In addition to an electron-accepting and polymerizable vinyl monomer and a photopolymerization initiator, the photocurable composition of the present invention may contain a spectral sensitizing dye for adjusting its photosensitive wavelength. As the dye-sensitive dye, various compounds known in the art can be used. Examples of spectral sensitizing dyes include the above-mentioned patents related to photopolymerization initiators and Re5earch Disclo.
sure, Vol. 200. December 1980, Ite
You can refer to pages 160-163 of ``Sensitizer'' (edited by Katsumi Tokumaru and Shin Okawara, Kodansha, 1987).

As a specific example of a spectral sensitizing dye, for example,
No. 8-15503 discloses a 3-ketocoumarin compound,
JP-A-58-40302 discloses thiopyrylium salts, JP-A-59-28328 and JP-A-60-53300 disclose naphthothiazole merocyanine compounds, JP-A-61
No.-9621, No. 62-3842, JP-A-59-89
No. 303 and No. 60-500 each disclose merocyanine compounds. These spectral sensitizers can extend the spectral sensitivity of the photopolymerization initiator to the visible range. In the above example, a triheromethyl-8-triazine compound is used as a photopolymerization initiator, but as a 0-spectral sensitizing dye that may be combined with other photopolymerization initiators,
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, acridine dyes, aniline dyes and azo dyes, cyanine, hemicyanine and styryl dyes as non-keto polymethine dyes.

In addition, the photopolymerizable composition of the present invention may further contain a reducing agent, such as an oxygen scavenger, as an auxiliary agent for promoting polymerization.
En scavengers) and active hydrogen donor chain transfer agents, as well as other compounds that promote polymerization in a chain transfer manner can also be used in combination. Oxygen scavengers that have been found to be useful are phosphines, phosphonates, phosphites, 1B salts and other compounds that are readily oxidized by oxygen. For example, N-phenylglycine,
Trimethylbarbyl, N,N-dimethyl-2,6
- diitubrovir aniline, N, N, N, -2,4,8
-pentamethylaniline, etc. Furthermore, thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, and the like shown below are also useful as polymerization accelerators.

Moreover, a non-polymerizable electron-accepting compound can be used in combination in the photopolymerizable composition of the present invention, if necessary. This combination improves the color density.

Examples of the electron-accepting compound include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins, and metal complexes. Examples of these are Ashiko Sho 40-9309, JP 45-14039, JP 52-140483, JP 48-51510, JP 57-210886, and JP 58-8708.
No. 9, JP-A-59-11286, JP-A-60-176
No. 795, JP-A No. 61-95988, etc. To give some examples of these, phenolic compounds include 2,2'-bis(4-hydroxyphenyl)propane, 4-t-butylphenol, 4-phenylphenol, 4-hydroxycyphenoxyto, l, 1 '-Bis(3-chloro-4-hydroxyphenyl)cyclohexane, 1.1'-bis(4-hydroxyphenyl)
Cyclohexane, 1.1'-bis(3-chloro-4-hydroxyphenyl)-2-ethylbutane, 4°4'-5
ec-isooctylidene diphenol, 4.4'-5e
c-butylidene diphenol, 4-tert-octylphenol, 4-p-methylphenylphenol, 4゜4'-methylcyclohexylidenephenol, 4.4'
Examples include isopentylidenephenol and benzyl p-hydroxybenzoate. Salicylic acid derivatives include 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, 4-pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid, etc., and zinc and aluminum thereof , calcium, copper, and lead salts. When these electron-accepting compounds are used together, 5 to 10 electron-donating colorless dyes are used.
It is preferable to use 01j1%.

The photocurable composition of the present invention may contain a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule. For example, acrylic acid and its salts, acrylic esters, acrylamide, etc. ; Methacrylic acid and its salts, methacrylic esters, methacrylamide; 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 having a plurality of ethylenically unsaturated double bonds in the molecule are particularly preferred, such as acrylic esters and methacrylic esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol; Examples include acrylate- or methacrylate-terminated epoxy resins, acrylate- or methacrylate-terminated polyesters, and the like. 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. methacrylate, etc.

The molecular weight of the polyfunctional monomer is about 100 to about 50
00 is preferred, more preferably about 300 to about 200
It is 0.

In addition to these compounds, photocrosslinkable compositions such as polyvinyl cinnamate, polycinnamylidene vinyl acetate, α
- A photosensitive resin etc. having a phenylmaleimide group can be added.

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.

Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol,
2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,
Examples include 6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-)luidine, and the like.

The amount of the thermal polymerization inhibitor added is preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight, based on the total weight of the photopolymerizable composition. 0°001% by weight ungrooved thermal stability is poor, and if it exceeds 5% by weight, sensitivity decreases.

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-mentioned patents.

Electron-donating colorless dyes according to the present invention include conventionally known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenyl Various compounds such as methane compounds, 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, U.S. Patent Specification No. 3.491゜112,
3,491,116 and 3.509,17
No. 4, specific examples of fluorans are given in U.S. Patent Specifications Nos. 3 and 6.
No. 24,107, No. 3゜627.787, No. 3,
No. 641,011, No. 3,462,828, No. 3
, 681,390, 3,920,510, 3,959.571, specific examples of spiropyrans are U.S. Pat. No. 3,971,808, and pyridine and pyrazine compounds are U.S. Patent No. 3.775,4
No. 24, No. 3,853,869, No. 4,246,
No. 318, specific examples of fluorene compounds are disclosed in Japanese Patent Application No. 1983-
It is described in No. 240989, etc. If some of these are disclosed, triarylmethane compounds include 3,
3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1°3 dimethyl indol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(
2-methylindol-3-yl) phthalide, etc., and diphenylmethane compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N
-Herophenylleukoolamine, N-2,4,5-
)lichlorophenylleucoolamine, etc., and xanthine compounds include rhodamine-B-anilinolactam, rhodamine=(p-nitrino)lactam, 2-(
dibenzylamino)fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-
3-Methyl-6-sibutylaminofluorane, 2-7nilino-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-sibutylaminofluorane, 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. Thiazine compounds include benzoylleuconmethylene blue, p-nitrobenzylleucomethylene blue, etc. Spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl -spiro-dinaphthopyran 3,3
'-Cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-
Examples include methoxy-benzo)-spiropyran and 3-propyl-spiro-dibenzobilane.

In particular, when used in full-color recording materials, electron-donating colorless dyes for cyan, magenta, and yellow include U.S. Pat. No. 4,800,149, and yellow-coloring dyes include U.S. Pat. For the cyan coloring type, reference may be made to JP-A No. 63-53542.

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, coacervation of a hydrophilic wall-forming material as seen in U.S. Pat. Nos. 2,800,457 and 2,800,458 U.S. Patent No. 3,287,154, British Patent No. 990,443, Japanese Patent Publication No. 38-19574, No. 42
-446, interfacial polymerization method as seen in US Pat. No. 42-771, US Pat. No. 3,418,250, US Pat.
No. 3, U.S. Pat.
No. 796,669; a method using isocyanate wall materials as found in U.S. Pat. No. 3,914,511;
No. 001140, No. 4087376, No. 408980
A method using wall-forming materials such as urea-formaldehyde-based and urea-formaldehyde-resorcinol-based materials as seen in No. 2, a method using wall-forming materials such as melamine-formaldehyde resin and hydroxypropyl cellulose as seen in U.S. Pat. -9168,
In situ method by polymerization of monomers as seen in JP-A-51-9079, British Patent No. 9528
No. 07, electrolytic dispersion cooling method found in No. 965074,
US Patent No. 3111407, UK Patent No. 930422
There is a spray drying method as seen in the issue.

Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

The microcapsule wall of the present invention is particularly effective when using a microencapsulation method by polymerizing a glue actant 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 emulsified in water. By dispersing and then increasing the temperature, a polymer formation reaction occurs at the oil-temperature 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, regarding the polyvalent isocyanate to be used and the polyol and polyamine to be reacted with it, US Pat.
No. 268, Special Publication No. 48-40347, No. 49-241
No. 59, JP-A-48-80191, JP-A No. 4B-8408
No. 6, and they can also be used.

Examples of polyvalent isocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate,
2.6-) lylene diisocyanate, 2.4-) lylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3 .3'-dimethyldiphenylmethane-
4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1°2-diisocyanate, butylene-1,2-diisocyanate, dichlorohedralide Diisocyanates such as xylene-1,2-diisocyanate and cyclohexylene-1,4-diisocyanate; triisocyanates such as 4.4',4'-triphenylmethane triisocyanate and toluene-2,4,6-) diisocyanate; , 4'-dimethyldiphenylmethane-2,2',5.5'-tetraisocyanate, an adduct of hexamethylene diisocyanate and trimethylolpropane, 2.4-) an adduct of lylene diisocyanate and trimethylolpropane, There are isocyanate prepolymers such as adducts of xylylene diisocyanate and trimethylolpropane and adducts of tolylene diisocyanate and hexanetriol.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers.

The following polyols described in JP-A-60-49991 can also be used. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol, 1,7-hebutanediol, 1,8-octanediol, propylene glycol, 2 , 3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2.
2-dimethyl-1,3-propanediol, 2,4-bentanediol, 2,5-hexanediol, 3-methyl-1,5-bentanediol, 1,4-cyclohexane dimetatool, dihydroxycyclohexane, diethylene glycol, 1,2.6-trihydroxyhexane, 2-phenylpropylene glycol, 1,1.1-)
Aromatic polyhydric alcohols such as limethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4-di(2-hydroxyethoxy)benzene, resorcinol dihydroxyethyl ether, etc. Condensation products with alkylene oxide, p-xylylene glycol, m-xylylene glycol, α, α'-dihydroxy-p-diisopropylbenzene, 4,4'-dihydroxy-diphenylmethane, 2-(p, p'-dihydroxy Diphenylmethyl)benzyl alcohol, an adduct of ethylene oxide to bisphenol A, an adduct of propylene oxide to bisphenol A, etc. The polyol is preferably used in a ratio of 0.02 to 2 moles of hydroxyl groups per mole of isocyanate groups.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylbiperazine, 2,5-dimethylbiperazine, and 2-hydroxytriamine. Examples include methylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenehentamine, 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 water-soluble anionic polymers, nonionic polymers, or amphoteric polymers.
Both natural and synthetic anionic polymers can be used, such as -C00-1S O2-
Examples include those having a group or 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 20μm
Adjusted below.

The size of the capsule used in the present invention is 80 μm or less, preferably 20 μm or less from the viewpoint of storage stability and handling. If the capsule is too small, the surface area for a given solid content becomes large and a large amount of wall material is required. becomes. 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 the solvent used in the capsule is preferably 1 to 500 parts by weight per 100 parts by weight of the electron-donating colorless dye.

Natural oil or synthetic oil can be used in combination as 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 -Diarylethanes such as phenyl-1-p-ethyl phenylethane, 1,1'-ditolylethane, and the like. Phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphoric acid 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), aliphatic esters (e.g. dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters (e.g. tributyl trimesate), ethyl acetate, acetic acid Examples include lower alkyl acetates such as butyl, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone.

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 silica, magnesium oxide,
These include inorganic compounds such as barium sulfate, strontium fC acid, and silver halide; polymer particles such as polymethyl methacrylate, polyacrylonitrile, and polystyrene; and starch particles such as carboxy starch, corn starch, and carboxy nitrophenyl starch. 1-20
Preferably, the thickness is μm. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. Examples of silica particles include FuJiDEVISON
Thyroid AL manufactured by CHEMIC) IAL LTD.
-1,65,72,79,74,404,620,30
8,978,161,162,244,255,266
, 150, etc. are preferable. The amount of matting agent added is 2-
500 mg/m2 is preferred, particularly preferably 5-100 mg/m2.

In 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 an IF 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, "gelatin hardening agent" used in the production of photographic light-sensitive materials is useful,
For example, aldehyde-based compounds such as formaldehyde and glutaraldehyde, compounds containing reactive halogens as described in U.S. Pat. No. 3,635,718 and others, and reactive ethylenically unsaturated bonds as described in U.S. Pat. aziridine compounds described in U.S. Pat. No. 3,017,280 and others, epoxy compounds described in U.S. Pat. No. 3,091,537 and others, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane,
Dioxanes such as dichlorodioxane or vinyl sulfones described in US Pat. No. 3,642,486 and US Pat. No. 3,687,707, US Pat. No. 3,84187
Vinyl sulfone precursors described in No. 2,
Ketovinyls as 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-)
Liacroyl-hexahydro-5-) riazine and 1.2
-Bisvinylsulfonylmethane, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(αvinylsulfonylacetamido)ethane, 2,4-dichloro-
6-hydroxy-8-triazine sodium salt, 2,
4.6-) Liethylenimino S-) Compounds such as riazine and boric acid. The amount added is 0.0% based on the binder.
5-5% by weight is preferred.

In addition, colloidal silica may be added to the protective layer to reduce its tackiness. Examples of colloidal silica include Snowtex 20, Snowtex 3o, Snowtex C, and Snowtex O manufactured by Gosan Kagaku.
, Snowtex N, etc. are preferable. The amount added is preferably 5-80% by weight based on the binder.

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, the structure is 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. and an intermediate layer containing an ultraviolet absorber is provided between the photosensitive and heat-sensitive layers.

The intermediate layer mainly consists of a binder and an ultraviolet absorber, and can contain additives such as a curing agent and polymer latex, if necessary.

As the ultraviolet absorber, compounds known in the industry such as benzotriazole compounds, cinnamic acid ester compounds, aminoallylidene mannitrile 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, especially an intermediate layer. In the oil-in-water dispersion method, the boiling point is, for example, 175°C.
or higher boiling point organic solvents and for example boiling points of 30°C or higher 1
After dissolving in either one of the so-called auxiliary solvents alone or in a mixture of both at 60° C. or lower, it is finely dispersed in an aqueous medium such as water, an aqueous gelatin solution, or an aqueous polyvinyl alcohol solution in the presence of a surfactant. 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.

Further, the dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, Nudel water washing, ultrafiltration, etc. before use for coating.

The process and effects of the latex dispersion method and specific examples of latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application No.
, No. 541,230, JP-A-49-74538, No. 5
No. 1-59943, No. 54-32552 and Re
5earch Disclosure, Vol. 148
．． It is described in August 1976, 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.). -2-methylpropanesulfonic acid, etc.) copolymer latex is preferred.

The ultraviolet absorber most preferably used in the present invention includes an ultraviolet absorber having a structure that does not easily diffuse into adjacent layers, such as a polymer or latex copolymerized with an ultraviolet absorber. Examples of such ultraviolet absorbers include European special patent No. 127,819, Japanese Patent Application Laid-Open No. 59-68731,
No. 59-26733, No. 59-23344, British Patent No. 2゜118.315, Japanese Patent Application Publication No. 58-111942, U.S. Patent No. 4,307,184, No. 4,202゜83
No. 6, No. 4,202,834, No. 4,207253, No. 4,178,303, JP-A-47-560, etc. may be referred to.

These UV absorbers are added to the intermediate layer, but are maintained as necessary! It may be added to fffi, photosensitive/thermosensitive layers, antihalation layers, etc.

In the present invention, the dispersion of the photocurable illuminant and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer. Compounds that dissolve 5% by weight or more in water at a temperature of
(including modified starch), gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol,
Examples include synthetic polymers such as polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymers, and polystyrene sulfonate. Among these, gelatin and polyvinyl alcohol are preferred.

In the present invention! tN, rE% The binders for each layer of this recording material, such as the photo/thermal layer and the intermediate layer, include the above-mentioned water-soluble polymers, polystyrene, polyvinyl formal, polyvinyl butyral, and acrylic resins such as polymethyl acrylate, polybutyl acrylate, and polymethyl methacrylate. , polybutyl methacrylate and their copolymers, phenol resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, urethane resins, and other solvent-soluble polymers or latexes of these polymers can be used. Among these, gelatin and polyvinyl alcohol are preferred.

Various surfactants may be used in each layer of the photosensitive/thermosensitive recording material produced using the present invention for various purposes such as coating aids, antistatic properties, improved slipperiness, emulsification and dispersion, and prevention of adhesion.

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, and alkyl sulfates. Anionic surfactants such as esters, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylenelkyl phenyl ethers,
Amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, and cationic surfactants such as aliphatic or aromatic quaternary ammonium salts can be used as required.

Various additives, including the additives described above, can be added to the recording material of the present invention as necessary. For example, representative 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 Re5earch Disclosure. , Vol. 1
76, December 1978, Item 17643, and Vo I, 187, November 1979, It
em 18716.

Photosensitive/sensitive aF of the present invention! The recording material of the present invention can be obtained by dissolving the coating liquid for use and the coating liquid for each of the above-mentioned shoes 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, 5ec-butanol, methyl cellosolve, l-methoxy-2-propanol; halogen-based Solvents: e.g. methylene chloride, ethylene chloride; Ketones: e.g. acetone, cyclohexanone, methyl ethyl ketone; Esters: e.g. methyl cellosolve acetate, ethyl acetate, methyl acetate; toluene, xylene, etc. alone and mixtures of two or more thereof. Examples include: Among these, water is particularly preferred.

To apply the coating solution for each application onto the support, use a blade coater, rod coater, knife coater, roll doctor coater, comma coater, reverse roll coater, etc.
, transfer roll coater, gravure coater,
A kiss roll coater, curtain coater, extrusion coater, etc. can be used. The application method is Re5earch Disclosure, Vol.
, 200. December 1980, l tem20036
You can refer to the XV section. The thickness of the recording layer is
A value of 0.1μ to 50μ is appropriate.

The recording material of the present invention can be used for various purposes.

For example, the recording material of the present invention can be used for applications such as copiers, faxes, printers, labels, color proofs, overhead projectors - second original drawings, and the like. Suitable supports include paper, coachite paper, laminated paper, synthetic paper, transparent films such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, aluminum,
Examples include plates of metal such as zinc and 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 treatment. As a support, Re5search
Disclosure, Vol. 200. December 1980, tel++20036 The support described in Section X■ can also be referred to. Further, these supports can be provided with layers depending on the purpose, such as an antihalation layer on the front surface and a slip layer, anti-stack layer, anti-curling layer, adhesive layer, etc. on the back surface, if necessary.

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 lamp, xenon lamp, tungsten lamp, metal halide lamp, argon laser, helium neon laser.
1. A wide range of light R can be used, including various lasers such as semiconductor lasers, LEDs, and fluorescent lights.

As an image recording method, various exposure methods can be used, such as close exposure of an original such as 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. The heating temperature is generally 80°C to 200°C, preferably 100"C to 160°C. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute.

The recording material of the present invention is preferably exposed to light over the entire surface after heat development treatment to photocure even the uncured portions.

Full-surface exposure suppresses the color development reaction in the background area and the decolorization reaction in the color development area, thereby improving the storage stability of the image.

"Effects of the Invention" The recording material of the present invention is of a mono-sheet type that does not require unnecessary materials, and can easily produce clear multicolor images just by 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.

"Synthesis Example" A specific synthesis example of the ultraviolet absorber latex that can be used in the present invention will be described below.

Electron-accepting compound (1): Hydroxyethyl acrylate monophthalate Photoinitiator (2): 2,2-dimethoxy-1,2-diphenylethane-1'
-ON Spectral sensitizing color 51: (1) Nitudiethylamino-4-methylcoumarin polymerizable ultraviolet absorber (l): Surfactant (2): C42H25SO3Na <Synthesis example 1> [Synthesis of ultraviolet absorber latex (1) ] Distilled water 20
0ml and 0.5g of surfactant were placed in a flask and stirred at 80°C in a nitrogen stream. 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 adding the entire amount, 0% potassium persulfate was added to T.
．． 1 by adding 5g and 0.25g of sodium bisulfite.
Stir for hours. The pH of the obtained solution was adjusted with IN caustic soda solution.
6 and filtered through filter paper to obtain the desired latex.

Synthesis Example 2> [Synthesis of UV absorber latex (2)] Synthesis Example 1
Same method as in Synthesis Example 1 except that 16 g of polymerizable ultraviolet absorber (1), 33 g of butyl acrylate, and Ig acrylic acid were replaced with 5 g of polymerizable ultraviolet absorber (2), 44 g of butyl acrylate, and 1 g of acrylic acid. This was carried out to obtain ultraviolet absorber latex (2).

<Synthesis Example 3> [Synthesis of latex (1) for dispersing ultraviolet absorbent latex] 400 ml of distilled water and surfactant 18 were placed in a flask and stirred at 80°C in a nitrogen stream. To this were added 1 g of potassium persulfate and 0.5 g of sodium bisulfite. 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, and after the entire amount was added, Ig of potassium persulfate and 0.5 g of sodium bisulfite were further added and stirred for 1 hour. The obtained solution was diluted with IN caustic soda solution p)16
The target latex was obtained by neutralizing it and filtering it with a filter paper.

"Example" Examples of the present invention are shown below, but the present invention is not limited thereto.

<Preparation of coating solution for Examples> 1. Preparation of electron-donating colorless dye capsules 1-a, Electron-donating colorless dye (1) Capsule adjustment Add 12.4 g of electron-donating colorless dye (1) to acetic acid. Dissolved in 10.43 ethyl, 12.4 g of dicyclohexyl phthalate and 27 g of Takenate D-11ON (Takeda Pharmaceutical Co., Ltd. *)
3 g of Tomi') Onate MR200 (manufactured by Nippon Polyurethane Industries, Ltd.) was added. This solution was added to a mixture of 4.6 g of polyvinyl alcohol and 74 g of water, and
The mixture was emulsified and dispersed at ℃ to obtain an emulsion having an average particle size of 2.5 μm.

Add 100g of water to the obtained emulsion, and add 60g of water while stirring.
After 2 hours, a capsule liquid containing the electron-donating colorless dye (1) in the core was obtained.

1-b, Preparation of electron-donating colorless dye (2) capsules Electron-donating colorless dye was prepared by the same method as in a, except that electron-donating colorless dye (1) in a was changed to electron-donating colorless dye (2). Dye (2) capsules were obtained.

1-c, Electron-donating colorless dye (3) Preparation of capsules Electron-donating colorless dye was prepared by the same method as in a, except that the electron-donating colorless dye (1) in a was changed to the electron-donating colorless dye (3). Dye (3) capsules were obtained.

2. [Preparation of emulsion of photocurable composition] 2-a. Adjustment of emulsion of photocurable composition (1) Photopolymerization initiator (1)
To a solution of 0.05 g of spectral sensitizing dye (1) and 3 g of ethyl acetate containing 0.28 g of N-phenylglycine ethyl ester as an auxiliary agent for promoting polymerization, 8 g of electron-accepting compound (1) was added. . This solution was mixed with 7.5% P
9.6 g of VA aqueous solution and 0.0 g of 2% surfactant (1) aqueous solution.
88 and 0.8 g of a 2% surfactant (2) aqueous solution and emulsified for 5 minutes at 10,000 rpm using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to form a photocurable assembled material (1
) was obtained.

2-b, Preparation of emulsion of photocurable ductility # (2) a. 0.05 g of photopolymerization initiator (1) and spectral sensitizing dye (,
1) 0.05g photopolymerization initiator (2) 0.8g
An emulsion of a photocurable assembled product (2) was obtained by the same method as in a, except that the following was changed.

2-c, Preparation of emulsion of photocurable ductile material (3) a. 0.05 g of photopolymerization initiator (1) and spectral sensitizing dye (1)
A photocurable ductile material (3) was prepared using the same method as a, except that 0.05 g of the photopolymerization initiator (3) was changed to 0.2 g.
) was obtained.

2-d, Preparation of emulsion of photocurable ductile material (4) a. 0.05 g of photopolymerization initiator (1) and spectral sensitizing dye (1)
Photocurable ductility was determined by the same method as a, except that 0.05g of photopolymerization initiator (1), 0.05g of spectral sensitizing dye (1), and 0-2g of ultraviolet absorber (1) were used. An emulsion of product (4) was obtained.

2-e, Preparation of emulsion of photocurable ductile material (5) a. 0.05 g of photopolymerization initiator (1) and spectral sensitizing dye (1)
A photocurable silk emulsion of ¥1 IJ (5) was obtained by the same method as in a, except that 0.05 g was changed to 0.8 g of photopolymerization initiator (2) and 0.2 g of ultraviolet absorber (2). Ta.

3. Preparation of dispersion of ultraviolet absorber 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 prepared. , 9.6 g of 7.5% PVA aqueous solution, 0.8 g of 2% surfactant (1) aqueous solution, and 2
% surfactant (2) in a mixed solution with 0.8 g of aqueous solution and homogenizer (manufactured by Nippon Seiki Co., Ltd.) to 100%
Emulsification was carried out at 00 rpm for 5 minutes to obtain an emulsion of ultraviolet absorber (1).

3-b, Preparation of emulsion of ultraviolet absorber (2) A solution of 0.26 g of ultraviolet absorber light (2) dissolved in 3 g of ethyl acetate and 5 g of dibutyl phthalate was mixed with 7.5% PVA.
9.6g of aqueous solution and 0.8g of 2% surfactant (1) aqueous solution
and 0.8 g of a 2% surfactant (2) aqueous solution and homogenized with a homogenizer (manufactured by Nippon Seiki Co., Ltd.).
Emulsification was carried out at 0,000 rpm for 5 minutes to obtain an emulsion of ultraviolet absorber (2).

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 765% PVA aqueous solution and 2%
0.8 g of surfactant (1) aqueous solution 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 and stirred with 9.25 g of latex (1) for latex dispersion of ultraviolet absorber and 25.5 g of 5% PVA aqueous solution to obtain a latex dispersion of ultraviolet absorber (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 0.88 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 and stirred with 9.253 g of latex (1) for latex dispersion of ultraviolet absorbent and 25.5 g of a 5% PVA aqueous solution to obtain a latex dispersion of ultraviolet absorbent (2).

46 [Preparation of coating solution for photosensitive/thermal use] 4-a, Photosensitive/
Adjustment of coating solution for heat-sensitive layer (1) Electron-donating colorless dye (1)
A photosensitive/thermosensitive layer (1
) was prepared.

4-b, Preparation of coating solution for photosensitive/thermal N (2) 4 g of electron donating colorless dye (2) capsules, 12 g of emulsion of photocurable ductile material (2) and 12 g of 15% PVA aqueous solution were mixed and photosensitive.・Adjusted the coating liquid for thermosensitive N (2).

4-c, R1 electron-donating colorless dye (3) of coating liquid for photosensitive/thermal N (3) Capsule 48 and photocurable ductile material (3)
A coating solution for photosensitive/thermal N (3) was prepared by mixing 12 g of the emulsion and 12 g of a 15% PVA aqueous solution.

4-d, Preparation of coating solution for photosensitive/thermal layer (4) 4 g of electron-donating colorless dye (1) capsules, 12 g of emulsion of photocurable ductile material (4) and 12 g of 15% PVA aqueous solution were mixed and photosensitive. - A coating solution for the heat-sensitive layer (4) was prepared.

4-e, 4 g of yA electron-donating colorless dye (2) capsules of coating liquid for photosensitive/thermal N (5) and photocurable ductile material (5)
Emulsion 128 and 12 g of 15% PVA aqueous solution were mixed to prepare a coating solution for photosensitive/thermal N(5).

5. [Preparation of coating liquid for intermediate layer] 5-a. Preparation of coating liquid for intermediate N (1) 4 g of 15% PVA aqueous solution, 3 g of distilled water, 0.5 g of 2% surfactant (3) aqueous solution, and ultraviolet absorption Emulsion of agent (1) 3
g to prepare a coating liquid for intermediate N(1).

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, 065 g of 2% surfactant (3) aqueous solution, and ultraviolet absorber (2)
8 to prepare a coating liquid for intermediate N (2).

5-C1 Preparation of coating solution for intermediate layer (3) Mix 4 g of 15% PVA aqueous solution, 3 g of distilled water, 0.5 g of 2% surfactant (3) aqueous solution, and 4 g of latex dispersion of ultraviolet absorber (1). A coating solution for the intermediate layer (3) was prepared.

5-d, Preparation of coating liquid for intermediate N (4) 4 g of 15% PVA aqueous solution, 3 g of distilled water, 0.5 g of 2% surfactant (3) aqueous solution, and latex dispersion liquid 48 of ultraviolet absorber (2). These were mixed to prepare a coating solution for intermediate layer (4).

5-e, Preparation of coating solution for intermediate layer (5) 15% PVA aqueous solution 4g, distilled water 3g, 2% surfactant (3) aqueous solution 0.58 and ultraviolet absorber latex (1)
A coating liquid for the intermediate layer (5) was prepared by mixing 3 g of the above-mentioned mixture with 3 g.

5-f, 15% PVA of coating liquid for intermediate PI (6)
A coating liquid for intermediate N (2) was prepared by mixing 4 g of an aqueous solution, 3 g of distilled water, 0.5 g of a 2% surfactant (3) aqueous solution, and 4 g of ultraviolet absorber latex (6).

5-g, intermediate! (7) Preparation of coating solution 4 g of 15% PVA aqueous solution, 3 g of distilled water, and 2% surfactant (3) Aqueous solution 0
．． A coating liquid for the intermediate layer (7) was prepared by mixing 5 g of the above.

6. [Adjustment corose of coating solution for protective layer. Preparation of coating solution for protection N (1) 4.5 g of 10% gelatin aqueous solution, 1.5 g of distilled water and 2%
Surfactant (3) 0.5 g of aqueous solution and 1.5 g of 1% 2,4-dichloro-6-hydroxy-5-)riazine sodium salt aqueous solution and Siloy)-72 (FU, jl-DE
(manufactured by VISON CHEMICHAL LTD) and Snowtex N in an amount that makes the coating amount 50mg/m2.
A coating solution for Ho1JJtl (3) was prepared by mixing with Ig.

<Comparative Example, 1> Coating liquid (1) for photosensitive/thermosensitive layer was applied onto a 100μ polyethylene terephthalate film using a coating bar until the dry weight of the coating layer was 8 g/l+? It was applied evenly and dried at 30°C for 10 minutes. On top of this layer is a middle layer (
7) was coated and dried to a dry weight of 58/m'l, then coating liquid (2) for photosensitive/thermosensitive layer was coated and dried to a dry weight of 83/m'l, and then In the middle layer (
7) was coated and dried at a dry weight force S of 5 g/i, the photosensitive/thermosensitive layer coating liquid (3) was coated and dried at a dry weight of 8 g/i, and a protective layer ( 1) Use a coating bar to apply the coating solution until the dry weight of the coating layer is 5.
It was coated to give a ratio of g/a and dried at 30° C. for 10 minutes to obtain a sample of Comparative Example 1.

A 1000W high-pressure mercury lamp (oak) was applied to the resulting photosensitive/thermosensitive recording material 'N through a lith film on which a cyan image was developed and an optical filter (SC-41 filter: manufactured by Fuji Photo Film Co., Ltd.) that blocks light of 410 nm or less. The images were exposed to ultraviolet light from a commercial jet light. Next, we used a 360nm lithium film with a developed image for magenta.
Optical filter that transmits only nearby light (BPB-36)
Filter: Fuji Photo Film Co., Ltd.) exposed to light from a high-pressure mercury lamp, and then developed with a yellow image and an optical filter (BPB-30 filter) that transmits only light around 300 nm. Co., Ltd.) and exposed to light from a high-pressure mercury lamp to obtain a retained 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 that was mainly yellow.

<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 88/d.
℃]0 minutes. On top of this, Intermediate N (7) was applied and dried to a dry weight of 5 g/ln'', and then
The dry weight of the photosensitive/thermosensitive layer coating liquid (5) is 88/T11.
Next, the intermediate layer (7) was coated and dried to a dry weight of 5 g/ln, and the photosensitive/thermosensitive layer coating liquid (3) was coated and dried to a dry weight of 83/ffl. The coating solution for the protective layer (1) was applied on top of it using a coating bar so that the dry weight of the coating layer was 58/phase', and the coating was dried at 30°C for 10 minutes. Comparative Example 2 sample was obtained.

The obtained photosensitive/thermal recording material was used in Comparative Example 1. When exposed and heat-developed in the same manner as above, an unclear full-color image with low color density was obtained.

<Example, 1> Comparative Example: Samples were prepared in which intermediate layer (1) and intermediate layer N (2) were applied as the intermediate layer of sample 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 8g/〆.
It was dried for 10 minutes at ℃. On this layer, intermediate N (1) was applied and dried to a dry weight of 5 g/m', and then photosensitive/thermosensitive layer coating liquid (2) was applied to a dry weight of 8 g/Ti''. Next, apply and dry the intermediate layer (2) to a dry weight of 5 g/n, and then apply the photosensitive/thermosensitive layer coating liquid (3) to a dry weight of 8 g/lr. After drying, the protective N(1) coating solution was applied using a coating bar so that the dry weight of the coating layer was 5 g/-, and dried at 30°C for 10 minutes to obtain the coating solution of Example 1. Got the sample.

The obtained photosensitive/thermal recording material was used in Comparative Example 1. When exposed and heat-developed in the same manner as above, a clear full-color image was obtained. The density of cyan, magenta, and yellow in the unexposed area is different! , 1.1.2.0.9.

<Example 2> Intermediate layer (1), which is the intermediate layer used in Example 1, and intermediate N
Instead of (2), samples were prepared in which intermediate N (3) and intermediate layer (4) were applied.

The obtained photosensitive/thermal recording material was used in Comparative Example 1. When exposed and heat-developed in the same manner as above, a clear full-color image was obtained. The densities of cyan, magenta, and yellow in the unexposed area were 1.2.1.2.1.0, respectively.

<Example 3> A sample was created in which intermediate layer (5) and intermediate layer (6) were applied instead of intermediate layer (1) and intermediate layer (2) used in Example 1. .

The obtained photosensitive/thermal recording material was used in Comparative Example 1. When exposed and heat-developed in the same manner as above, a clear full-color image was obtained. The densities of cyan, magenta, and yellow in the unexposed area were 1.4.1.4.1.1, respectively.

As is clear from this example, when the photosensitive/thermosensitive recording material of the present invention provided with an intermediate layer containing an ultraviolet absorber is used, the photosensitive wavelengths of each photosensitive/thermosensitive layer can be sufficiently separated, and a clear multilayer image can be obtained. You can get color images. In particular, when a latex made by copolymerizing an ultraviolet absorber with a monomer is used, a clear multicolor image with high color density can be obtained.

Claims (4)

[Claims] (1) Containing, on a support, [1] a photocurable composition containing an electron-accepting and polymerizable vinyl monomer and a photopolymerization initiator, and [2] microcapsules containing an electron-donating colorless dye. It has at least two photosensitive and heat-sensitive layers, and has photosensitive and heat-sensitive layers.
A photosensitive/heat-sensitive recording material characterized in that an intermediate layer containing an ultraviolet absorber is provided between heat-sensitive layers. (2) The photosensitive/thermosensitive recording material according to claim (1), wherein the ultraviolet absorber is dispersed in the form of fine particles. (3) The photosensitive/thermosensitive recording material according to claim (2), wherein the ultraviolet absorber is dispersed in latex. (4) The photosensitive/thermosensitive recording material according to claim (2), wherein the ultraviolet absorber is a latex copolymerized with an ultraviolet absorbent monomer.