JPH04249256A - Production of microcapsule and photosensitive and heat sensitive recording material - Google Patents

Abstract

PURPOSE:To produce stable microcapsules not causing aggregation or the occurrence of trouble such as unevenness or crawling and enabling simultaneous coating in layers with modified gelatin as protective colloid and to provide a perfectly dry photosensitive and heat sensitive recording material using the microcapsules, not requiring the use of a developing soln., etc., and capable of forming a mono- or poly-chromatic image. CONSTITUTION:When microcapsules are produced, modified gelatin obtd. by chemically modifying amino groups of gelatin is used as hydrophilic protective colloid for emulsification and dispersion for forming microcapsules. When the resulting microcapsules are used for a photosensitive and heat sensitive recording material in which a latent image is formed by exposure in a photosetting compsn. and a component taking part in color development or color vanishment by heating is transferred in accordance with the latent image to form an image, the component taking part in color development or color vanishment is incorporated into the microcapsules.

Description

Description: [0001] The present invention relates to a photosensitive/thermosensitive recording material that can be used for color or black and white proofs, second original drawings, copiers, facsimile machines, and the like. [Prior Art] For the sake of convenience, the prior art will be explained using color proofing as an example, but the only difference is that the purpose of use is different.
Almost the same thing can be said about other fields. There are various methods of color proofing, but each has its own drawbacks. One of the typical methods of color proofing is the overlay method. This method reproduces a multicolor image by overlapping films with images of each color, and it is unavoidable to view the image through the film, resulting in poor image quality. Another method for obtaining a multicolor image on a single sheet is the surprint method. In this method, images of each color are sequentially superimposed on a single support to obtain a multicolor image. For example, Cromarin (Dupont), Match Print (3M), Color Art (Fuji Photo Film), etc. are known, but all of them require four sheets of photosensitive film for each color, resulting in waste. do. Furthermore, a color paper method is known as a method for forming a color image on a single photosensitive sheet. In this method, a film original is placed in close contact with color paper, exposed using a filter for each color, and then wet developed to obtain a color image.
Fine Checker (Fuji Photo Film) and Consensus (Konica) are well known. In this method, since the photosensitive range of color paper is the visible range, a dark room or an exposure device equipped with a dark room is required for handling, and maintenance and management of the developer is required. These methods require multiple sheets, generate waste such as transfer sheets and toner,
It has several drawbacks, such as being difficult to handle in a bright room and requiring a developing system that uses a developer, and improvements are being sought. The following method has been proposed as a method that does not have these drawbacks. That is, a photosensitive material is characterized in that a latent image is formed on a photocurable composition by exposure to light, and components involved in color development or decolorization are diffused within the photosensitive material according to the latent image by heating to form a color image.・Using a heat-sensitive recording material, expose the photosensitive recording material through an image original, cause photocuring in the exposed area to form a latent image, and then heat the recording material to cure the uncured portions. A completely dry system that does not generate waste can be realized by using a color image creation method characterized by diffusing parts involved in color development or decolorization to form a visible image. Specifically, there are several types of recording materials used in this method, and although this method is unique as a method for recording black and white images, it is a method that is particularly useful when used as a color recording material. As a specific recording material, for example, the recording material disclosed in Japanese Patent Application Laid-Open No. 52-89915 is known. This is a method in which the two components of a two-component thermosensitive color recording material, for example, an electron-accepting compound and an electron-donating colorless dye, are separated inside and outside or on both sides of a microcapsule containing a photocurable composition. This is the recording material arranged. However, in the case of this recording material, even if the photocurable composition inside the microcapsules is sufficiently cured, color development in the cured areas cannot be sufficiently suppressed, so non-image areas tend to be slightly colored, resulting in poor contrast. There is. A more preferable recording material without coloring in the non-image area is:
For example, as disclosed in JP-A-61-123838, a layer containing a photopolymerizable composition consisting of a vinyl monomer having an acidic group and a photopolymerization initiator, an isolation layer, and an electron-donating colorless dye are used. Recording materials having laminated layers are known. In the case of this recording material, the thermal diffusivity of the acidic groups in the non-image area, that is, the area cured by the photopolymerization part, is almost eliminated, so the coloring in the non-image area is eliminated, but the coloring density is somewhat low. A similar method for obtaining negative images is as follows:
For example, there is a method disclosed in Japanese Patent Laid-Open No. 119552/1983. This method uses a recording material in which a photopolymerizable composition consisting of a monomer or prepolymer that bleaches a dye and a photopolymerization initiator and a dye that is bleached by the monomer or prepolymer are present in isolation. This recording material also has the same drawbacks as the recording materials described above. The most preferable recording material that overcomes the coloration of non-image areas and low image density is disclosed in Japanese Patent Application No. 1-22499 filed by the present applicant.
There is a recording material described in No. 0. In this recording material, one of the two components of a two-component thermosensitive color recording material is encapsulated in microcapsules, and the other component is used as a curable compound of a photocurable composition, or the other component is used as a photocurable composition. It is also a recording material placed outside the microcapsule. As a recording material for negative images using a similar concept, there is a recording material described in Japanese Patent Application No. 2-19710 filed by the present applicant. A photopolymerizable composition containing an electron-accepting compound, a polymerizable vinyl monomer, and a photopolymerization initiator is placed outside the microcapsules, and a layer containing microcapsules containing an electron-donating colorless dye is coated. This is the recording material that was created. [0004] To carry out color recording using these photosensitive recording materials, basically, it is sufficient to use a recording material having a plurality of photosensitive layers having different photosensitive wavelengths and coloring hues. As an example of a more preferable multicolor recording material, Japanese Patent Application No. 1-224930
Examples include recording materials described in Japanese Patent Application No. 19710/1993. For example, it has a plurality of photosensitive layers that are sensitive to light of different wavelengths and develop colors of different hues, and has a layer structure from the exposure light source side to the support side of the recording material.
A first photosensitive layer that is sensitive to light with a center wavelength λ1, an intermediate layer that absorbs light with a center wavelength λ1, and a second photosensitive layer that is sensitive to light with a center wavelength λ2 and develops a color different from that of the first photosensitive layer. ,...
..., an intermediate layer that absorbs light with a center wavelength λi-1, a first layer, a second layer, ..., and an i-1 layer that are exposed to light with a center wavelength λi.
At least two or more photosensitive layers are laminated on a support in the order of the i-th photosensitive layer that develops a color different from the i-th photosensitive layer, and the center wavelength is λ1<λ2<...<λi. A multicolor recording medium characterized by the following characteristics can be mentioned. Here, i is an integer of 2 or more. [0005] These recording materials can be applied to various uses, but the sensitive material layer is generally used in a multilayer structure, including an overcoat layer, an undercoat layer, an intermediate layer, etc., whether monochrome or multicolor. many. In this case, it is necessary to perform multilayer coating on the support, but a method in which each layer is coated sequentially is disadvantageous from the viewpoint of manufacturing cost and yield. Conventionally, in silver salt photographic systems, all of the overlapping layers are formulated to be gelatin-based, and the low-temperature setting properties of gelatin are utilized to perform multilayer simultaneous coating. Therefore, if this technique is utilized, it should be possible to perform multilayer coating simultaneously on the above-mentioned photosensitive/thermosensitive recording materials. However, when attempting to emulsify and disperse components involved in color development or decolorization using gelatin-based protective colloids, reactants (as encapsulation wall materials)
For example, isocyanate) and gelatin react quickly, and the reaction starts already at the early stage of emulsification, causing aggregation. Therefore, it has been desired to realize stable microencapsulation using a gelatin-based protective colloid. [0006] An object of the present invention is to create stable microcapsules that can be coated simultaneously in multiple layers without agglomeration and without problems such as unevenness and repelling, using a gelatin-based protective colloid. The object of the present invention is to provide a manufacturing method and a photosensitive/thermosensitive recording material using the microcapsules, which can form completely dry monochromatic or multicolor images without using a developer or the like. Means for Solving the Problems As a result of intensive research, the inventors of the present invention found that the above purpose was achieved by chemically converting the amino groups of gelatin into hydrophilic protective colloids for emulsification and dispersion for forming microcapsules. A method for producing microcapsules characterized by using modified gelatin modified with A photosensitive/thermosensitive recording material that moves within the material to form an image, characterized in that one of the components involved in color development or decolorization upon heating is encapsulated in microcapsules produced by this method.・We have discovered that this can be achieved using a heat-sensitive recording material, and have come to form the present invention. As a specific example of the recording material according to the present invention, for example, an electron-accepting part and a polymerizable vinyl monomer part are provided outside the microcapsule described in Japanese Patent Application No. 1-224930. Examples include a recording material coated with a layer containing a photopolymerizable composition containing a compound and a photopolymerization initiator in the same molecule, and microcapsules containing an electron-donating colorless dye. When this recording material is exposed to light, the exposed parts of the photopolymerizable composition outside the microcapsules are polymerized to form a latent image, and then,
When heated, the electron-accepting compound diffuses within the sensitive material according to its image, and the electron-donating colorless dye within the microcapsules develops color, making it possible to form a positive color image with good contrast. Furthermore, negative images can be formed using similar methods relating to the recording material of the present invention. As a specific example of this method, for example, Japanese Patent Application No. 2-1971
A photopolymerizable composition containing an electron-accepting compound, a polymerizable vinyl monomer, and a photopolymerization initiator, and a microcapsule containing an electron-donating colorless dye outside the microcapsule described in the specification of No. Examples include recording materials coated with a layer containing . When this recording material is exposed to light, the exposed parts of the photopolymerizable composition outside the microcapsules polymerize to form a pattern image, and then, when heated, the electron-accepting compound in the polymerized part becomes sensitive according to the pattern image. By diffusing within the material, the electron-donating colorless dye within the microcapsules develops color, making it possible to form a negative image with good contrast. As mentioned above, using various methods,
In the recording material of the present invention, a latent image is formed in the photocurable composition by exposure, and by heating, components involved in color development or decolorization are diffused within the sensitive material according to the latent image to form a color image. It is possible to create "photosensitive/thermosensitive recording materials". The photosensitive/thermosensitive layers used in these recording materials are not limited to the above-mentioned configurations, and can have various configurations depending on the purpose. Further, the recording material used in the present invention may be a monochromatic so-called B/W recording material or a multicolor recording material. In the case of a multicolor recording material, for example, a multilayer recording material including 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 in each layer may be used. Can be used. For example, a layer containing microcapsules containing an electron-donating colorless dye that develops a cyan color and a photocurable composition 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. A layer containing microcapsules containing a colorless dye and a photocurable composition sensitive to a wavelength of λ2 is provided, and a layer containing microcapsules containing an electron-donating colorless dye that develops a yellow color and a photocurable composition sensitive to a wavelength of λ3 is provided on top of the layer. A structure in which a layer containing a photosensitive photocurable composition is provided, a structure in which an intermediate layer is provided between each layer, and a structure in which an ultraviolet absorber is further contained in this intermediate layer can be used. In the case of a multicolor recording material, a structure containing an ultraviolet absorber in the intermediate layer is particularly preferred. For example, its configuration is as follows:
A layer containing microcapsules containing an electron-donating colorless dye that develops a cyan color and a photocurable compound that is sensitive to wavelength λ1 is provided on a support, and a layer that absorbs light with a wavelength shorter than wavelength λ1 is provided on the support. An intermediate layer containing an ultraviolet absorber is provided, and a layer containing microcapsules containing an electron-donating colorless dye that develops a magenta color and a photocurable composite material that is sensitive to wavelength λ2 is provided on top of the intermediate layer. An intermediate layer containing an ultraviolet absorber that absorbs light with a wavelength shorter than wavelength λ2 is provided on the layer, and on top of that are microcapsules containing an electron-donating colorless dye that develops a yellow color and a photocurable assemblage sensitive to wavelength λ3. There is a structure in which a layer containing a substance is provided, and a protective layer is further provided on top of the layer. The electron-accepting and polymerizable vinyl monomer used mainly in the positive recording material used in the present invention may be any compound containing an electron-accepting group and a vinyl group in the molecule. 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. , No. 60-141587, No. 62-99190, the ester of benzoic acid having a hydroxyl group with hydroxymethylstyrene, hydroxystyrene described in European Patent No. 29323, and JP-A-62-167077. , 62-167
Various compounds can be used that can be synthesized with reference to the N-vinylimidazole complex of zinc halide described in No. 08 and the color developer monomer described in No. 63-317558. Specific examples include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid,
Zinc β-Methacryloxyethoxysalicylate, Zinc β-Acryloxyethoxysalicylate, Vinyloxyethyloxybenzoic acid, β-Methacryloxyethyl orselinate, 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, methacrylamidepropanesulfonic acid, acrylamidepropanesulfonic 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 sulfonamide 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-methacryloxy Ethylaminosulfonylsalicylic acid, N,N'-di-β-acryloxyethylaminosulfonylsalicylic acid, and metal salts thereof, such as zinc salts, can be preferably used. As the photopolymerization initiator suitably used in the recording material of the present invention, one type or a combination of two or more types of compounds can be selected from the above-mentioned compounds capable of initiating photopolymerization of vinyl monomers. . 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, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2 ,4,5-triarylimidazole dimer: e.g. 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-1986-13
No. 3428, Special Publication No. 57-1819, Special Publication No. 57-6
Compounds described in each specification of No. 096 and U.S. Pat. methyl)-S-
Triazine, 2-methoxy-4,6-bis(trichloromethyl)-S-triazine, 2-amino-4,6-bis(trichloromethyl)-S-triazine, 2-(P-methoxystyryl)-4,6 -bis(trichloromethyl)
Compounds such as -S-triazine. and organic peroxides 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-(tertiarybutylperoxycarbonyl)benzophenone and the like. and azinium salt compounds as described, for example, in U.S. Pat. No. 4,743,530.
and organoboron compounds as described for example in EP 0223587: for example the tetramethylammonium salt of triphenylbutylborate, the tetrabutylammonium salt of triphenylbutylborate,
Photopolymerization initiators well known in the art, such as tetramethylammonium salt of tri(P-methoxyphenyl)butylborate, and other diaryliodonium salts and iron allene complexes, can be usefully used. Combinations of two or more compounds are known as photopolymerization initiator systems, and such combinations can also be used in the recording material of the present invention. Examples of combinations of two or more compounds include 2,4,5-
Combination of triarylimidazole dimer and mercaptobenzoxazole etc., combination of 4,4'-bis(dimethylamino)benzophenone and benzophenone or benzoin methyl ether described in U.S. Pat. No. 3,427,161, U.S. Pat. No. 4,239,850 Benzoyl-N-methylnaphthothiazoline and 2 described in the specification of No.
, 4-bis(trichloromethyl)-6-(4'-methoxyphenyl)-triazole, and JP-A-57
-23602, a combination of dialkylaminobenzoic acid ester and dimethylthioxanthone, and 4,4'-bis(dimethylamino)benzophenone, benzophenone, and polyhalogenated methyl compound described in JP-A-59-78339. Three types of combinations can be mentioned. A more preferred example is a combination of 4,4'-bis(diethylamino)benzophenone and benzophenone, 2,
Examples include a combination of 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, 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 20% by weight, based on the total weight of the photopolymerizable composition.
The content is 15% by weight, and the most preferred content is 5 to 10% by weight. If it is less than 0.01% by weight, the sensitivity will be insufficient and 10
If it exceeds % by weight, no increase in sensitivity can be expected. The photocurable composition of the recording material of the present invention may contain, in addition to the polymerizable vinyl monomer and the photopolymerization initiator, a spectral sensitizing dye for adjusting the wavelength of light to which it is sensitive. Various compounds known in the art can be used as the spectral sensitizing dye. Examples of spectral sensitizing dyes are the patents related to photopolymerization initiators mentioned above and Research Di
closure, Vol. 200, December 1980, Item 20036 and 160-16 of "Sensitizer" (Katsumi Tokumaru/Shin Okawara/ed. Kodansha 1987)
You can refer to page 3 etc. Specific examples of spectral sensitizing dyes include 3-ketocoumarin compounds in JP-A No. 58-15503, thiopyrylium salts in JP-A-58-40302, and thiopyrylium salts in JP-A-59-28328.
No. 60-53300 describes naphthothiazole merocyanine compounds;
No. 842, JP-A-59-89303, JP-A No. 60-601
Each publication No. 04 discloses a merocyanine compound. These spectral sensitizers can extend the spectral sensitivity of the photopolymerization initiator to the visible range. In the above example, a trihalomethyl-S-triazine compound is used as a photopolymerization initiator, but it may be combined with other photopolymerization initiators. 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 recording material of the present invention further contains a reducing agent, such as an oxygen scavenger, as an auxiliary agent for promoting polymerization.
) and a chain transfer agent for an active hydrogen donor, as well as other compounds that promote polymerization in a chain transfer manner. Oxygen scavengers that have been found to be useful are phosphines, phosphonates, phosphites, stannous salts and other compounds that are readily oxidized by oxygen. Examples include N-phenylglycine, trimethylbarbituric acid, N,N-dimethyl-2,6-diisopropylaniline, and N,N,N-2,4,6-pentamethylaniline. Furthermore, thiols, thioketones, trihalomethyl compounds, lofin dimer compounds as shown below,
Iodonium salts, sulfonium salts, azinium salts, organic peroxides, and the like are also useful as polymerization accelerators. Further, it is preferable to use an electron-accepting compound in the photopolymerizable composition of the negative recording material used in the present invention. Further, this electron-accepting compound can be added to the photocurable composition in the positive recording material as needed, and the color density is improved by this addition. 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
No. 309, JP 45-14039, JP 52-1
No. 40483, JP-A-48-51510, JP-A-57
JP-A-210886, JP-A-58-87089, JP-A-59-11286, JP-A-60-176795, JP-A-61-95988, and the like. 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-tert-octylphenol , 4-
Examples include p-methylphenylphenol, 4,4'-methylcyclohexylidenephenol, 4,4'-isopentylidenephenol, and benzyl p-hydroxybenzoate. 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-tetra Decylsalicylic 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. When these electron-accepting compounds are used in combination, it is preferable to use them in an amount of 5 to 1000% by weight of the electron-donating colorless dye. A monomer having at least one vinyl group in the molecule can be used for the photocurable composition of the negative recording material used in the present invention. 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, monomers having a plurality of vinyl groups in the molecule are particularly preferred, such as acrylic esters and methacrylic esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol;
and acrylate- or methacrylate-terminated epoxy resins, acrylate- or methacrylate-terminated polyesters, and the like. Specific examples of particularly preferred compounds include:
Examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate. The molecular weight of the polyfunctional monomer is about 100 to about 5
000 is preferred, more preferably about 300 to about 20
It is 00. In addition to these compounds, photocurable compositions such as polyvinyl cinnamate, polycinnamylidene vinyl acetate, and α-phenylmaleimide group-containing photocurable compositions can be added as photocrosslinkable compositions. Moreover, you may use these photocrosslinkable compositions as a photocurable component. Furthermore, in addition to these compounds, a thermal polymerization inhibitor can be added to the photocurable composition as required. Thermal polymerization inhibitors are added to prevent thermal polymerization of photocurable compositions and polymerization over time, and this improves the chemical stability of photocurable 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 amount of the thermal polymerization inhibitor added is 0.00000000000000000000000000000000000000000000000,0000,0000,000,000,000,000,000 which is based on the total weight of the photocurable 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 may be encapsulated in microcapsules The photocurable composition of the recording material of the present invention may be encapsulated in microcapsules as necessary. For example, it can be encapsulated in microcapsules with reference to European Patent No. 0223587 and the above patents. The electron-donating colorless dyes used in the recording material of the present invention include conventionally known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds,
Various compounds such as indolylphthalide compounds, leukoolamine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds can be used. Specific examples of phthalides are given in U.S. Reissue Patent Specification No. 23,0.
No. 24, U.S. Pat. Specification No. 3,624,107, Specification No. 3,62
No. 7,787, No. 3,641,011, No. 3, 4
No. 62,828, No. 3,681,390, No. 3,
No. 920,510, No. 3,959,571, and specific examples of spirodipyrans are given in U.S. Patent Specification No. 3,971,8.
No. 08, pyridine-based and pyrazine-based compounds are disclosed in U.S. Patent No. 3,775,424 and U.S. Pat.
Specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989, etc. To disclose some of these, triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,
3-bis(p-dimethylaminophenyl)phthalide, 3
-(p-dimethylaminophenyl)-3-(1,3-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, etc. Examples of diphenylmethane compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoauramine, N-2,4,5-trichlorophenylleucoauramine, and xanthene. Examples of the system compounds include rhodamine-B-anilinolactam, rhodamine-(
p-nitrino)lactam, 2-(dibenzylamino)fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3- Methyl-6
-N-ethyl-N-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:
There are benzoyl leucon methylene blue, p-nitrobenzyl leucomethylene blue, etc., and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, and 3-benzyl spiro-dinaphthopyran. -Dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)-
Examples include spiropyran and 3-propyl-spiro-dibenzopyran. In particular, when used in full-color recording materials, electron-donating colorless dyes for cyan, magenta, and yellow include U.S. Pat. etc.,
For the cyan coloring type, reference may be made to JP-A No. 63-53542. General methods of microencapsulating electron-donating colorless dyes are known in the art, particularly those using isocyanate polyol wall materials, as found in US Pat. No. 3,796,669; Microencapsulation methods by polymerization of reactants from within the oil droplets are preferred, such as methods using isocyanate wall materials. That is, it is possible to obtain microcapsules which are preferable as a recording material having a uniform particle size and excellent shelf life in a short period of 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 (
For example, a polyol, polyamine) is mixed into an oily liquid to be encapsulated, emulsified and dispersed in water, and then the temperature is raised to cause a polymer formation reaction at the oil droplet interface to form a microcapsule wall. 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 No. 48-80191, JP-A No. 48-8408
No. 6, and they can also be used. However, in the recording material of the present invention, gelatin is used as a water-soluble polymer protective colloid when microcapsulating the electron-donating colorless dye in order to enable multilayer coating as described above. However, the isocyanate used as the main reactant for the capsule wall forming material generally reacts very quickly with the amino groups contained in ordinary gelatin. Therefore, in this case, a reaction between the isocyanate and the amino group occurs at the initial stage of emulsification and dispersion, resulting in aggregation. In order to avoid this phenomenon, modified gelatin according to the method of the invention is used, ie gelatin in which the amino groups of gelatin are selectively replaced by other functional groups inert towards isocyanates. Examples of such modified gelatin include phthalated gelatin, acetylated gelatin, oxidized gelatin, malonated gelatin, succinated gelatin, glutarated gelatin, adipinated gelatin, pimelinated gelatin, maleated gelatin, fumarated gelatin, and benzoyl gelatin. Examples include modified gelatin. Among these, phthalated gelatin, acetylated gelatin, and succinated gelatin are particularly preferred. The modification rate of these modified gelatins is 50% of the total amino groups.
It is preferably 80% or more, particularly preferably 95% or more. These modified gelatins are used as a 0.01 to 15% by weight aqueous solution as a protective colloid for emulsification and dispersion. As the polyvalent isocyanate, for example, m
-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,
4-Tolylene diisocyanate, naphthalene-1,4-
Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4- Diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1
, 2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate, etc., 4,4',4''-triphenylmethane triisocyanate, toluene- Triisocyanates such as 2,4,6-triisocyanate, 4,4'-
Tetraisocyanates such as dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylene diisocyanate and trimethylolpropane, xylylene diisocyanate There are isocyanate prepolymers such as adducts of isocyanate and trimethylolpropane and adducts of tolylene diisocyanate and hexanetriol. Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers. Japanese Patent Application Publication 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, penta Erythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,
4-di(2-hydroxyethoxy)benzene, condensation products of aromatic polyhydric alcohols such as resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene glycol, m-xylylene glycol, α,
α'-dihydroxy-p-diisopropylbenzene, 4
, 4'-dihydroxy-diphenylmethane, 2-(p,
p'-dihydroxydiphenylmethyl)benzyl alcohol, an adduct of ethylene oxide to bisphenol A, an adduct of propylene oxide to bisphenol A, and the like. 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-methylpiperazine, 2,5-dimethylpiperazine, Examples include 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds. Polyvalent isocyanates can also react with water to form polymeric materials. The average particle diameter of the capsules used in the recording material of the present invention is 20 μm or less, particularly 5 μm from the viewpoint of resolution.
m or less is preferable. 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 recording material of the present invention may be present in the microcapsules in a solution state or in a solid state. When the electron-donating colorless dye is present in a solution state, the electron-donating colorless dye may be encapsulated in a state dissolved in a solvent. The amount of the solvent at this time is preferably 1 to 500 parts by weight per 100 parts by weight of the electron-donating colorless dye. As the solvent used during encapsulation, natural oil or synthetic oil can be used in combination. Examples of these solvents include, for example, cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes and 1-phenyl-1-xylylethanes, 1- Phenyl-1-p-
Diarylethanes such as ethyl phenylethane, 1,1'-ditolylethane, etc. 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), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters ( Examples include lower alkyl acetates such as tributyl trimesate), ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone. Furthermore, during microencapsulation, a volatile solvent may be used in combination with another solvent as an auxiliary solvent for dissolving the electron-donating colorless dye. Examples of this type of solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride, and the like. In the recording material of the present invention, it is preferable to add a matting agent to the protective layer. Examples of 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, carboxy starch, corn starch,
Examples include starch particles such as carboxynitrophenyl starch, 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 F
UJI-DEVISON CHEMICAL LT
D. Cyroid AL-1, 65, 72, 79, 74
, 404, 620, 308, 978, 161, 162,
244, 255, 266, 150, etc. are preferred. The amount of the matting agent added is preferably 2-500mg/m2,
Particularly preferred is 5-100 mg/m2. In the recording material of the present invention, it is preferable to use a curing agent in combination with each layer of the recording material of the present invention, such as the photosensitive/thermosensitive layer, the intermediate layer, and the 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. Compounds with halogens, compounds with reactive ethylenically unsaturated bonds described in U.S. Pat. No. 3,635,718 and others, aziridine compounds described in U.S. Pat. No. 3,017,280 and others, U.S. Pat. No. 30,915
Epoxy compounds described in No. 37 and others, halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, or vinyl sulfones described in U.S. Pat. No. 3,642,486 and U.S. Pat. No. 3,687,707. ,
Vinyl sulfone precursors as described in US Pat. No. 3,841,872, ketovinyls as described in US Pat. No. 3,640,720, or chromium alum, zirconium sulfate, boric acid, etc. can be used as inorganic hardeners. Among these curing agents, a particularly preferred compound is 1,3,5-triacroyl-hexahydro-
s-triazine, 1,2-bisvinylsulfonylmethane, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane, 2,4-dichloro-6-hydroxy-s-triazine・Sodium salt, 2,4,6-triethylenimino-
These are compounds such as 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 in order to reduce its adhesiveness. Preferable examples of colloidal silica include Snowtex 20, Snowtex 30, Snowtex C, Snowtex O, and Snowtex N manufactured by Nissan Chemical. The amount added is preferably 5 to 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 used in the present invention. In the case of a multicolor recording material used in the present invention, for example, microcapsules containing electron-donating colorless dyes that develop colors in different hues and photocurable compositions that are sensitive to light of different wavelengths are used in each layer. In addition, an intermediate layer containing an ultraviolet absorber may be provided between the photosensitive/thermosensitive 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, aminoarylidenemalonitrile compounds, and benzophenone compounds can be used. The ultraviolet absorber used in the recording material of the present invention can be emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method and then added to a desired layer, especially 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 include U.S. Patent No. 2,322,0
It is stated in issue 27 etc. 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. Examples of the latex dispersion process, effects, and latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) No. 2,541,274 and OLS No. 2,541,230, JP-A-49-745
No. 38, No. 51-59943, No. 54-32552, Research Disclosure,
Vol. 148, August 1976, Item 148
50 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 recording material of 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 Patent Nos. 127,819, JP-A-59-68731, JP-A-59-26733, and JP-A-59.
-23344, British Patent No. 2,118,315, Japanese Patent Application Publication No. 111942/1984, US Patent No. 4,307,184
No. 4,202,836, No. 4,202,834, No. 4,207,253, No. 4,178,303,
JP-A No. 47-560 can be referred to. 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 recording material of the present invention, when either one of the components involved in color development or color erasure is microencapsulated, dispersion of other photocurable compositions and dispersion of electron-donating colorless dyes is preferred. is carried out in a water-soluble polymer, and the water-soluble polymer that can be preferably used in the recording material of the present invention is preferably a compound that dissolves at least 5% by weight in water at 25°C, and specifically, gelatin. , gelatin derivatives are particularly preferred. In addition, these gelatins include proteins such as albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sugar derivatives such as sodium alginate, starches (including modified starches), gum arabic, polyvinyl alcohol, and styrene-maleic anhydride. copolymer hydrolyzate,
carboxy-modified polyvinyl alcohol, polyacrylamide, saponified product of vinyl acetate-polyacrylic acid copolymer,
Synthetic polymers such as polystyrene sulfonate can also be used in combination. [0038] In the recording material of the present invention, the protective layer, the photosensitive
Binders for each layer of this recording material, such as the heat-sensitive layer and the intermediate layer, include gelatin, gelatin derivatives, the above-mentioned water-soluble polymers, polystyrene, polyvinyl formal, polyvinyl butyral, and acrylic resins such as polymethyl acrylate, polybutyl acrylate, and polystyrene. Polymer latexes such as methyl methacrylate, polybutyl methacrylate, copolymers thereof, phenol resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, and urethane resins can also be used in combination. Various surfactants may be used in each layer of the photosensitive/thermosensitive recording material of the present invention for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, and preventing 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, 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. [0040] Various additives, including the additives mentioned 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 available in Research Disclosure.
, Vol. 176, December 1978, Item 1
7643, and the same Vol. 187, 1979 1
January, Item 18716. The coating solution for the photosensitive/thermosensitive layer of the recording material of the present invention and the coating solution for each layer described above are dissolved in a solvent as necessary, coated on a desired support, and dried. of recording material is obtained. Solvents used in this case include water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, methylcellosolve, 1-
Methoxy-2-propanol; halogenated solvents: e.g. methylene chloride, ethylene chloride; ketones:
Examples include acetone, cyclohexanone, methyl ethyl ketone; esters such as methyl cellosolve acetate, ethyl acetate, methyl acetate; toluene, xylene, and mixtures of two or more thereof. Among these, water is particularly preferred. [0042] To apply the coating liquid for each layer onto the support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a reverse roll coater,
A transfer roll coater, gravure coater, kiss roll coater, curtain coater, extrusion coater, etc. can be used. As a coating method, Research Disclosure, Vol.
．． 200, December 1980, Item 20036
You can refer to Section XV. The thickness of the recording layer is 0
．． A suitable thickness is 1 μm to 50 μm. The recording material of the present invention can be used for various purposes. For example, copiers, faxes, printers, labels, etc.
The recording material of the present invention can be used for purposes such as color proofs and second original drawings. Supports suitable for the recording material of the present invention include paper, coated paper, laminated paper, synthetic paper, etc., and films such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, and polycarbonate film. Examples include metal plates of aluminum, zinc, copper, etc., and those whose surfaces have been subjected to various treatments such as surface treatment, undercoating, and metal vapor deposition. Furthermore, Research
Disclosure, Vol. 200, December 1980, Item 20036, Section XVII may also be referred to. In addition, if necessary, an anti-halation layer on the front surface, a slip layer, an anti-static layer on the back surface, etc.
Layers such as 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. As a light source, a wide range of light sources can be used, including mercury lamps, ultra-high pressure mercury lamps, electrodeless discharge mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, various lasers such as argon lasers, helium neon lasers, and semiconductor lasers, LEDs, and fluorescent lamps. Image recording methods include close exposure of originals such as lithographic film, enlarged exposure of slides and liquid crystal images, etc.
Various exposure methods can be used, such as reflection exposure using reflected light from the original. When performing multicolor recording, single exposure or multiple image recording may be performed 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. 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. EXAMPLES The present invention will be explained in more detail below based on Examples, but the present invention is not limited thereto. [Example] <Preparation of coating liquid> 1. [Preparation of electron-donating colorless dye capsule] 1-a. Electron-donating colorless dye (1) Preparation of capsules 8.9 g of electron-donating colorless dye (1) was dissolved in 16.9 g of ethyl acetate.
Takenate D-110N (manufactured by Takeda Pharmaceutical Company Limited) 2
0 g and 2 g of Millionate MR200 (manufactured by Nippon Polyurethane Industries, Ltd.) were added. This solution was added to a mixture of 42 g of 8% aqueous phthalated gelatin solution and 1.4 g of 10% sodium dodecylbenzenesulfonate solution,
The mixture was emulsified and dispersed at 20°C to obtain an emulsion. To the resulting emulsion was added 14 g of water and 72 g of a 2.9% triethylenepentamine aqueous solution.
g was added and heated to 60°C with stirring, and after 2 hours, particles containing the electron-donating colorless dye (1) in the core with an average particle size of 0.
A 5 μm capsule liquid was obtained. When the obtained capsule liquid was filtered through a mesh filter with a pore size of about 50 μm, no residue was observed. 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). Capsules encapsulating the electron-donating colorless dye (2) with an average particle size of 0.5 μm were obtained by the same method 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). Capsules encapsulating the electron-donating colorless dye (3) with an average particle size of 0.5 μm were obtained by the same method as above. Below, the electron-donating colorless dye (1
), (2) and (3) are shown below. [Chemical formula 1] [0052]2. [Preparation of emulsion of photocurable composition] 2
-a. Preparation of emulsion of photocurable composition (1) 0.13 g of photopolymerization initiator (1), 0.1 g of spectral sensitizing dye (1), and 0.2 g of auxiliary agent (1) for promoting polymerization. Polymerizable electron-accepting compound (1) in a mixed solution of 3 g of isopropyl acetate
5g was added. Add this solution to 13% gelatin aqueous solution
3 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.). Emulsification was performed to obtain an emulsion of photocurable composition (1). 2-b. Preparation of emulsion of photocurable composition (2) 2-a. 2-a. except that 0.13 g of photopolymerization initiator (1) and 0.1 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (2). The photocurable composition (
An emulsion of 2) was obtained. 2-c. Preparation of emulsion of photocurable composition (3) 2-a. 2-a. except that 0.13 g of photopolymerization initiator (1) and 0.1 g of spectral sensitizing dye (1) were changed to 0.2 g of photopolymerization initiator (3). The photocurable composition (
An emulsion of 3) was obtained. 2-d. Preparation of emulsion of photocurable composition (4) 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1).
An electron-accepting compound, resorcinic acid (1-methyl-2
10 g of -phenoxy)ethyl and 8 g of trimethylolpropane triacrylate monomer were added. This solution was mixed with 19.2 g of 15% gelatin aqueous solution, 4.8 g of water, 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 revolutions using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion of photocurable composition (4). The chemical structural formulas of the photopolymerization initiators (1), (2), and (3) are shown below. [0056] [0057] Below, polymerizable electron-accepting compound (1)
The chemical structural formula of ##STR3## The chemical structural formula of the auxiliary agent (1) for promoting polymerization is shown below. ##STR4##3. [Preparation of ultraviolet absorber dispersion] 3-
a. Preparation of emulsion of ultraviolet absorber (1) Ultraviolet absorber (
1) A solution of 7.5 g and UV absorber (2) 2.4 g dissolved in 17.5 g of ethyl acetate was added to 62 g of 15% gelatin aqueous solution and 1 g of 62% dodecylbenzenesulfonic acid aqueous solution.
and emulsified for 5 minutes at 10,000 rpm using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion of ultraviolet absorber (1). 3-b. Preparation of emulsion of UV absorber (3) A solution of 5 g of UV absorber Hikari (3) dissolved in 19 g of ethyl acetate was added to a mixed solution of 65 g of 15% gelatin aqueous solution and 1 g of 62% dodecylbenzenesulfonic acid aqueous solution. 1000 using a homogenizer (manufactured by Nippon Seiki Co., Ltd.)
Emulsification was carried out for 5 minutes at 0 rotation to obtain an emulsion of ultraviolet absorber (3). Below, ultraviolet absorbers (1), (2) and (3)
The chemical structural formula of ##STR5## 4. [Preparation of coating solution for photosensitive/thermosensitive layer] 4-
a. Preparation of Coating Solution for Photosensitive/Thermosensitive Layer (1) 4 g of electron-donating colorless dye (1) capsules, 12 g of emulsion of photocurable composition (1), and 12 g of 15% gelatin aqueous solution were mixed to prepare the photosensitive/thermal layer (1). A coating solution for 1) was prepared. 4-b. Preparation of coating solution for photosensitive/thermosensitive layer (2) 4 g of electron-donating colorless dye (2) capsules, 12 g of emulsion of photocurable composition (2), and 12 g of 15% gelatin aqueous solution
A coating solution for the photosensitive/thermosensitive layer (2) was prepared by mixing the following. 4-c. Preparation of coating solution for photosensitive/thermosensitive layer (3) 4 g of electron-donating colorless dye (3) capsules, 12 g of emulsion of photocurable composition (3), and 12 g of 15% gelatin aqueous solution
A coating solution for the photosensitive/thermosensitive layer (3) was prepared by mixing the following. 4-d. Preparation of coating solution for photosensitive/thermosensitive layer (4) 1 g of electron-donating colorless dye (3) capsules and 10 g of emulsion of photocurable composition (4) are mixed to form photosensitive/thermosensitive layer (4).
A coating solution was prepared. 5. [Preparation of coating liquid for intermediate layer] 5-a. Preparation of coating solution for intermediate layer (1) 9 g of distilled water and 14 g of emulsion of ultraviolet absorber (1) and 2%
A coating solution for intermediate layer (1) was prepared by mixing 1.7 g of an aqueous solution of hardener (1). 5-b. Preparation of coating solution for intermediate layer (2) Mix 9 g of distilled water, 14 g of emulsion of ultraviolet absorber (2), and 1.7 g of 2% hardener (1) aqueous solution to prepare coating solution for intermediate layer (2). did. 6. [Preparation of coating liquid for protective layer] 6-a. Preparation of coating solution for protective layer (1) 4.5 g of 10% gelatin aqueous solution, 4.5 g of distilled water and 2%
0.5 g of surfactant (3) aqueous solution and 2% surfactant (4
) 0.3 g of aqueous solution and 2% hardener (1) 0.5 g of aqueous solution and Thyroid 72 (FUJI-DEVISON CHE
MICALLTD. A coating solution for the protective layer (1) was prepared by mixing 1 g of Snowtex N with a coating amount of 50 mg/m2. Below, surfactant (1)
, (2), (3) and (4) are shown below. ##STR6##6. [Preparation of support] A wood pulp consisting of 20 parts of LBSP and 80 parts of LBKP was beaten to a Canadian freeness of 300 cm3 using a disk-cliffing ironer, and 1 part of sodium stearate was added to the wood pulp.
．． 0 part, anionic polyacrylamide 0.5 part, aluminum sulfate 1.5 part, and polyamide polyamine epichlorohydrin 0.5 part were added in the absolute dry weight ratio to the wood pulp, and the basis weight was 80 g/m2 using a Fourdrinier paper machine. paper was made. The density is determined by the machine calender to 1
．． It was set to 0 g/cm3. After corona discharging this atom,
Low density polyethylene (MI=7g/10min, density 0.9
23g/cm3) containing 10% by weight of titanium oxide,
A polyethylene resin layer was formed by extrusion coating to a thickness of 20 μm. Next, after corona discharge treatment was applied to the other surface (back surface) of the substrate, high-density polyethylene (MI=8 g/10 min, density 0.950 g) was applied thereon.
/cm3) is extruded and coated to a thickness of 20μ.
A total of m polyethylene resin was formed to produce double-sided polyethylene laminated paper. Example 1 Preparation and evaluation of positive photosensitive/thermosensitive recording material Coating solution (1) for photosensitive/thermosensitive layer was applied onto this support using a coating bar until the dry weight of the coated layer was 8 g/m2. It was applied as follows and dried at 30°C for 10 minutes. On top of this layer, apply and dry the intermediate layer (1) to a dry weight of 2 g/m2, and then apply the photosensitive/thermosensitive layer coating liquid (2) to a dry weight of 8 g/m2. Dry, then
The intermediate layer (2) was coated and dried to a dry weight of 2 g/m2, and the photosensitive/thermosensitive layer coating solution (3) was coated to a dry weight of 8 g/m2.
g/m2, dry, and then apply the protective layer (1) coating solution using a coating bar so that the dry weight of the coated layer is 2 g/m2.
The sample of Example 1 was obtained by drying for 0 minutes. A 2000W high-frequency lighting ultra-high pressure mercury lamp was applied to the resulting photosensitive/thermosensitive recording material through a lithium film on which a yellow 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. (
It was exposed to ultraviolet light from a printer manufactured by Dai-Nippon Screen Co., Ltd. (P627GA). Next, a lithium film with a developed magenta image was exposed to light from a mercury lamp through an interference filter that transmits only light from 365 nm to 400 nm, and then a lithium film with a developed image for cyan and 340 nm was exposed.
It was exposed to light from a mercury lamp through an interference filter that transmits only light of ~365 nm to obtain a latent image. Thereafter, when it was heated for 5 seconds on a hot plate at 120° C., a clear full-color positive image with an OD (reflection density) of about 2.0 for each color was obtained. Furthermore, no density unevenness, repellency, aggregation, etc. were observed on the recording material surface. Example 2 Preparation and Evaluation of Negative Photosensitive/Thermosensitive Recording Material Coating liquid (4) for photosensitive/thermal layer was applied onto a support using a coating bar so that the dry weight of the coated layer was 8 g/m2. and dried at 30°C for 10 minutes. Next, 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 coating layer was 5 g/m2.
The sample of Example 2 was obtained by drying at ℃ for 10 minutes. The obtained photosensitive/thermosensitive recording material was exposed to ultraviolet light from a 1000 W high-pressure mercury lamp (Jet Light manufactured by Oak Co., Ltd.) through a lith film on which a black and white image had been developed. after that,
When heated for 5 seconds on a hot plate at 120° C., a clear negative monochrome (cyan) image was obtained. Examples 3 and 4 1-a. In the same manner as in the method for preparing the electron-donating colorless dye (1) capsule liquid, an 8% phthalated gelatin aqueous solution was mixed with 8%
% acetylated gelatin (Example 3) and 8% succinated gelatin (Example 4), 1-
a. A stable capsule liquid was obtained in the same manner as above, and no filtration residue was observed at all. Furthermore, an electron-donating colorless dye (1)
Similar good results were obtained even when (2) or (3) was substituted for the preparation. Comparative Example 1 1-a. In the same manner as in the method for preparing the electron-donating colorless dye (1) capsule liquid, an 8% phthalated gelatin aqueous solution was mixed with 8%
When emulsifying and dispersing the gelatin by replacing it with a normal gelatin aqueous solution of 1.5%, the gelatin aggregated within a few minutes after the start of emulsification. Therefore, any subsequent encapsulation reaction was impossible, and filtration through a filter could not be performed at all. This was the same even when the electron-donating colorless dye was replaced with (2) or (3) instead of (1). Effects of the Invention: According to the method for producing microcapsules of the present invention, very stable microcapsules can be obtained,
No aggregates are generated. By using microcapsules produced by this method, it is possible to produce photosensitive/thermosensitive recording materials that have clear images without density unevenness.

Claims (8)

[Claims] 1. A method for producing microcapsules, which comprises using modified gelatin in which the amino groups of gelatin are chemically modified as a hydrophilic protective colloid for emulsification and dispersion for forming microcapsules. 2. The method for producing microcapsules according to claim 1, wherein the modified gelatin is selected from at least one of phthalated gelatin, acetylated gelatin, and succinated gelatin. 3. Photosensitive/thermosensitive, in which a latent image is formed on the photocurable composition by exposure to light, and components involved in color development or decolorization move within the recording material according to the latent image by heating to form an image. A photosensitive/thermosensitive recording material, characterized in that one of the components involved in color development or decolorization upon heating is encapsulated in microcapsules produced by the method of claim 1 or claim 2. 4. Exposure to light forms a patterned image on the photocurable composition outside the microcapsules, and heating causes the electron-accepting compound to move within the recording material according to the patterned image, thereby donating electrons within the microcapsules. 3. A photosensitive/thermosensitive recording material in which an image is formed by coloring a colorless dye, wherein the microcapsules are produced by the method according to claim 1 or claim 2. [Claim 5] In claim 3 or claim 4,
A photosensitive/thermosensitive recording material characterized in that the photocurable composition contains a compound having an electron-accepting color developer part and a polymerizable vinyl monomer part in the same molecule, and a photopolymerization initiator. [Claim 6] In claim 3 or claim 4,
A photosensitive/thermosensitive recording material, wherein the photocurable composition contains an electron-accepting color developer, a polymerizable vinyl monomer, and a photopolymerization initiator. 7. The photosensitive/thermosensitive recording material according to claim 3, 4, 5, or 6, wherein the photosensitive/thermosensitive recording material is a multicolor recording material. 8. In claim 7, the photosensitive/thermosensitive recording material comprises a first photosensitive layer that is sensitive to light having a center wavelength λ1 from the exposure light source side toward the support side of the recording material, the center wavelength λ1 being sensitive to light having a center wavelength λ1. an intermediate layer that absorbs light with a center wavelength λ2, a second photosensitive layer that is sensitive to light with a center wavelength λ2 and develops a color different from that of the first photosensitive layer, ..., an intermediate layer that absorbs light with a center wavelength λi-1. , at least two or more photosensitive layers in the order of the first, second, . It has a layer structure laminated on a support, and the center wavelength λ1<λ2
A photosensitive/thermosensitive recording material characterized in that <...<λi. i is an integer of 2 or more.