JPH04249257A - Production of heat developable photosensitive recording material - Google Patents

Abstract

PURPOSE:To produce a perfectly dry black-and-white or color heat heat developable photosensitive recording material producing no unnecessary waste, not requiring the use of a developing soln., etc., and capable of giving an image having high resolution and to also produce a developable photosensitive recording material capable of giving a clear image free from unevenness, crawling, pinholes, etc. CONSTITUTION:A substrate is coated with at least one photosensitive and heat sensitive layer 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. A protective layer is then formed on the photosensitive and heat sensitive layer by applying a soln. contg. at least one kind of nonionic or anionic surfactant having a fluorinated alkyl group in the molecule to obtain a heat developable photosensitive recording material.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a heat-developable photosensitive recording material which can be used for color or black-and-white proofs, second originals, copiers, facsimile machines, and the like.

0002

[Prior Art] For convenience, the prior art will be explained using color proofing as an example, but 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, thermal processing is characterized in that a latent image is formed on the photocurable composition by exposure, 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 developable photosensitive recording material,
The photosensitive recording material is exposed to light through the image original, photocuring occurs in the exposed area to form a latent image, and then the recording material is heated to remove the uncured portions that are involved in coloring or decoloring. By using a color image creation method that is characterized by diffusion and forming a visible image, a completely dry system that does not generate waste can be realized. 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 of the non-image area is, for example, a photopolymerizable composition comprising a vinyl monomer having an acidic group and a photopolymerization initiator, as disclosed in JP-A-61-123838. A recording material is known in which a layer containing a substance, an isolation layer, and a layer consisting of an electron-donating colorless dye are laminated. 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. As a method for obtaining a negative image using a similar method, 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 coloring of non-image areas and low image density is disclosed in Japanese Patent Application No. 1-2249 filed by the present applicant.
There are recording materials described in No. 30. 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 the same concept,
There is a recording material described in Japanese Patent Application No. 2-19710 filed by the present applicant. A photocurable 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.

Since these recording materials form images by irradiation with light, they can be expected to provide high-resolution images in principle, but in order to obtain the expected high-resolution images,
It is necessary to form each layer of these recording materials, including the photosensitive layer, uniformly and accurately without defects such as repelling or pinholes. Even if it is a monochromatic recording material, it usually requires two layers: a photosensitive layer and a protective layer, and these layers must be precisely formed. , all these layers must be precisely formed. To illustrate a typical layer structure of a multicolor recording material, at least six layers are required: a cyan coloring layer, an intermediate layer, a magenta coloring layer, an intermediate layer, a yellow coloring layer, and a protective layer. In this way, when two or more layers are precisely coated simultaneously or sequentially, repellents and pinholes are likely to occur in the outermost layer or the last coated protective layer, and these defects can cause the recording material to deteriorate. Resolution and homogeneity were often impaired, and improvements were needed.

[0006]

[Problems to be Solved by the Invention] An object of the present invention is to provide a completely dry black-and-white or color heat-developable photosensitive recording material that does not generate unnecessary waste and does not require the use of a developer or the like. An object of the present invention is to provide a method for producing a heat-developable photosensitive recording material that can provide high-resolution images. Another object of the present invention is to provide a method for producing a heat-developable photosensitive recording material that can provide clear images free of unevenness, repelling, pinholes, and the like.

[0007]

[Means for Solving the Problems] As a result of intensive research, the inventors of the present invention have found that the above object is achieved by forming a latent image on a photocurable composition by exposure to light, and by heating a component involved in coloring or decoloring. A heat-developable photosensitive recording material that has at least one photosensitive/thermosensitive layer on a support that moves within the recording material to form an image according to a latent image, and has a protective layer thereon. The method for producing the protective layer is characterized in that the protective layer is provided by applying a liquid containing at least one nonionic or anionic surfactant having a fluorinated alkyl group in the molecule. It has been discovered that this can be achieved by a method for producing a heat-developable photosensitive recording material, and the present invention has been completed.

As a specific example of the recording material according to the present invention, for example, an electron-accepting portion and a polymerizable vinyl monomer portion are provided outside the microcapsule described in Japanese Patent Application No. 1-224930. Examples include a recording material coated with a layer containing a photocurable 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 portion of the photocurable composition outside the microcapsules polymerizes 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
The microcapsules described in the specification of No. 0 include a photocurable composition containing an electron-accepting compound, a polymerizable vinyl monomer, and a photopolymerization initiator, and an electron-donating colorless dye. Examples include recording materials coated with a layer containing . When this recording material is exposed to light, the exposed parts of the photocurable 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 a heat-developable photosensitive recording material. 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 that is sensitive to wavelength λ1 is provided on a support, and a layer is placed on the support.
A layer containing microcapsules containing an electron-donating colorless dye that develops a zenta color and a photocurable composition that is sensitive to wavelength λ2 is provided, and on top of that a layer containing an electron-donating colorless dye that develops a yellow color is provided. Microcapsules and wavelength λ3
It is possible to use a structure in which a layer containing a photocurable composition sensitive to light is provided, a structure in which an intermediate layer is further provided between each layer, a structure in which this intermediate layer further contains an ultraviolet absorber, etc. . In the case of a multicolor recording material, a structure containing an ultraviolet absorber in the intermediate layer is particularly preferred. Its composition is as follows:
For example, a layer containing microcapsules containing an electron-donating colorless dye that develops a cyan color and a photocurable composition that is sensitive to a wavelength of λ1 is provided on a support, and a layer containing a photocurable composition that is sensitive to a wavelength of λ1 is provided on the support.
An intermediate layer containing an ultraviolet absorber that absorbs light with a shorter wavelength than 1 is provided, and a microcapsule containing an electron-donating colorless dye that develops a magenta color and a photocurable composition that is sensitive to wavelength λ2 are provided thereon. On top of that is an intermediate layer containing an ultraviolet absorber that absorbs light with a wavelength shorter than wavelength λ2, and on top of that is a layer containing microcapsules containing an electron-donating colorless dye that produces a yellow color and a layer with a wavelength of λ3. There is a structure in which a layer containing a photosensitive photocurable composition is provided, and a protective layer is further provided on top of the layer.

In the present invention, when forming this protective layer, a coating liquid containing at least one nonionic or anionic surfactant having a fluorinated alkyl group in the molecule is used. use. A preferred example of the surfactant is an aliphatic fluoro compound represented by the general formula RF-Z. Here, RF is 3 to 12 carbon atoms
Z is an alkyl group partially or entirely substituted with fluorine atoms, and Z is further a carboxylic acid group or a sulfonic acid group. Preferably it is F-(CF2)n- or H-(CF2)n-. Here, n is an integer from 3 to 9. Specifically, they are fluorinated aliphatic carboxylic acids, sulfonic acids, carboxylic acid-amide carboxylic acids, sulfonic acid-amide sulfonic acids, or salts thereof, or sulfonic acid amides, carboxylic acid amides, and carboxylic acid esters.

Anionic or anionically active fluorocompounds include, for example, those of the general formula RF-CO-O-X
and RF-SO2-N(R2)-R1CO-O-X. Preferably,
RF-CO-ME, RF-SO2-O-ME, RF-CO-N(R5)(CH2)m-Y, RF-SO
2-N(R5)(CH2)m-Y. RF is as described above, R1 is an alkylene group, R2 is a hydrogen atom or an alkyl group, and R5 is a hydrogen atom or a carbon number of 1 to 1.
9 alkyl group, m is an integer of 1 to 6, ME is an alkali metal atom, X is a hydrogen atom or an alkali metal atom, Y
is -CO OME, -SO3ME or -OSO3M
It is E. Nonionic or nonelectrolytic fluoro compounds include, for example, the general formula RF -O-OC-R4,
and RF-O-OC-RF. Preferably RF-SO2-N(R5)(CH2)m-O-(CH2
-CH2O-)p-H, RF-SO2-N(R5)(CH2)m-O-OC-R
4, RF-CO-N(R5)(CH2)m-O-(CH
2-CH2O-)p-H, RF-SO2-N[(CH2-CH2O-)p-H]2
, RF-CO-O-(CH2-CH2O-)p-H. RF and R5 are the same as above, R4 is an alkyl group, and p is at most 20. The alkyl group represented by R2 or R4 may be further substituted with another functional group.

Esters of aliphatic carboxylic acids with fluorinated carboxylic acids, their alkali metal salts or fluoroalcohols are of particular interest. These fluoro compounds include general formulas F-(CF2)n-CO-O-X, H-(CF2)n-CO-O-X, F-(CF2)n-CH2-O-CO-R5, H-(C
F2) n-CH2-O-CO-R5, and particularly preferred is F3-(CF2)7-SO2-N(CH2-C
OOK)(CH2-CH3). R5, n, and X are the same as above. These surfactants are available, for example from Minnesota Mining and Manufacturing Company, in the FC type, such as perfluorocarboxylic ammoniums such as FC126 (anionic) and perfluoroalkylsulfonates such as FC95 (anionic). as FC98 (anionic) or as E.
I. It is commercially available as Zonyl S13 from Dupond, Nemerus & Company. Preferred specific compounds are illustrated below.

[0013]

[Chemical formula 1]

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 types of 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 photoinitiator is preferably 0.01 to 20% by weight, and more preferably 0.2 to 20% by weight, based on the total weight of the photocurable composition.
The content is 15% by weight, and the most preferable content is 1 to 10% by weight. If it is less than 0.01% by weight, the sensitivity will be insufficient and 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 photocurable 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 photocurable 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.

[0021] In the photocurable composition of the negative recording material used in the present invention, a monomer having at least one vinyl group in the molecule can be used. For example, acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, itaconic esters; styrenes; Vinyl ethers; vinyl esters; N-vinyl heterocycles; aryl ethers; allyl esters, 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 triphenylmethanephthalide 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.

When the electron-donating colorless dye of the recording material of the present invention is microencapsulated, it can be prepared by a method known in the art. The electron-donating colorless dye of the recording material of the present invention can be microencapsulated using methods known in the art. For example, US Patent Nos. 2,800,457 and 2,800
0458, U.S. Pat. No. 3,287,15
No. 4, British Patent No. 990443, Special Publication No. 38-195
74, 42-446, and 42-771; polymer precipitation methods as in U.S. Pat. No. 3,418,250 and 3,660,304; isocyanate as in U.S. Pat. No. 3,796,669 Method of using polyol wall materials, U.S. Patent No. 3914
511, U.S. Pat. Nos. 4,001,140 and 4,087,376;
A method using wall-forming materials such as urea-formaldehyde-based and urea-formaldehyde-resorcinol-based materials as seen in U.S. Pat. 36
-9168 and JP-A-51-9079, an in-situ method by polymerization of monomers; British Patent No. 952,807 and British Patent No. 965,074, an electrolytic dispersion cooling method; US Pat. No. 3,111,407, UK There is a spray drying method as seen in Japanese Patent No. 930422. 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 recording material of the present invention is particularly effective when using a microencapsulation method by polymerizing a reactant from inside an oil droplet. That is, it is possible to obtain capsules, which are desirable as a recording material and have a uniform particle size and excellent storage stability, within a short time. For example, when polyurethane is used as the capsule wall material, a polyvalent isocyanate and, if necessary, a second substance that reacts with it to form the capsule wall (e.g., polyol, polyamine) are mixed into the oily liquid to be encapsulated and emulsified in water. By dispersing and then increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming 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, the polyvalent isocyanate used and the polyol and polyamine to be reacted with it are described in US Pat. No. 328
No. 1383, No. 3773695, No. 3793268, Special Publication No. 48-40347, No. 49-24159,
It is disclosed in JP-A-48-80191 and JP-A-48-84086, and these can also be used.

As the polyvalent isocyanate, for example, m
-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,
4-Tolylene diisocyanate, naphthalene-1,4-
Diisocyanate, 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, There are isocyanate prepolymers such as adducts of 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. 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.

When making microcapsules, water-soluble polymers can be used, and the water-soluble polymers may be any of water-soluble anionic polymers, nonionic polymers, and amphoteric polymers. Both natural and synthetic anionic polymers can be used, such as -COO-
, -SO2 - groups, and the like. Specific anionic natural polymers include gum arabic, alginic acid, pectin, etc., and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfonic acid, etc. In addition, synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, and vinylbenzenesulfonic acid-based polymers and copolymers. , carboxy-modified polyvinyl alcohol, etc. Examples of nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose. Examples of amphoteric compounds include gelatin. These water-soluble polymers are 0.01 to 10% by weight
It is used as an aqueous solution. The average particle diameter of the capsules used in the recording material of the present invention is 20 μm or less, and preferably 5 μm or less from the viewpoint of resolution. 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.

Further, 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. Thyroid AL-1, 65, 72, 79, 74
, 404, 620, 308, 978, 161, 162,
244, 255, 266, 150, etc. are preferred. The amount of 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. Patent 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.

The process and effects of the latex dispersion method and specific examples of 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 most preferably used ultraviolet absorber in the recording material of the present invention is 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, the dispersion of the photocurable composition and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer. The water-soluble polymer that can be produced is preferably a compound that dissolves at least 5% by weight in water at 25°C, and specifically includes proteins such as gelatin, gelatin derivatives, albumin, and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, Sodium alginate, sugar derivatives such as starches (including modified starches), gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, vinyl acetate-polyacrylic acid copolymer Synthetic polymers such as saponified polymers and polystyrene sulfonates can be mentioned. Among these, gelatin and polyvinyl alcohol are preferred.

[0042] In the recording material of the present invention, the protective layer, the photosensitive
Binders for each layer of the recording material, such as the heat-sensitive layer and the intermediate layer, include the above-mentioned water-soluble polymers, polystyrene, polyvinyl formal, polyvinyl butyral, acrylic resins such as polymethyl acrylate, polybutyl acrylate,
Solvent-soluble polymers such as polymethyl methacrylate, polybutyl methacrylate, copolymers thereof, phenol resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, urethane resins, 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 heat-developable photosensitive 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 -acyl-N-alkyltaurines,
Anionic surfactants such as sulfosuccinic acid esters and sulfoalkyl polyoxyethylenelkyl phenyl ethers, amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines, aliphatic or aromatic quaternary ammonium salts, etc. A cationic surfactant can be used if necessary.

Various additives, including the additives mentioned above, can be added to the recording material of the present invention as necessary. For example, 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 liquid for the photosensitive/thermosensitive layer of the recording material of the present invention and the coating liquid for each layer mentioned 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.

[0046] 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 7 minutes, preferably 3 seconds to 3 minutes. 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.

[0052]

[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 mixed with 42 g of 8% phthalated gelatin and 1.0 g of 10% sodium dodecylbenzenesulfonate solution. Add to 4g of mixture, 2
The mixture was emulsified and dispersed at 0°C to obtain an emulsion. Add 1 part water to the resulting emulsion
4g and 72g of 2.9% triethylenepentamine aqueous solution
was added and heated to 60°C with stirring, and after 2 hours, the electron-donating colorless dye (1) was added to the core and the average particle size was 0.5.
A μm capsule liquid was obtained.

1-b. Electron-donating colorless dye (2) Preparation of capsules 1-a. 1-a. except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (2). 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.

[0055]

[Case 2]

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), (3) and the spectral sensitizing dye (1) are shown below.

[0060]

[Chemical formula 3]

[0061] Below, polymerizable electron-accepting compound (1)
The chemical structural formula of

[0062]

[C4]

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

[0064]

[C5]

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

[0067]

[C6]

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 (1) 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 (3), 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 4.5 g of 10% gelatin aqueous solution and 4.5 g of distilled water Table 1
Or 0.5 g of a 2% aqueous solution of the surfactant shown in Table 2.
and 2% surfactant (4) aqueous solution 0.3g and 2% hardener (
1) 0.5g of aqueous solution and Thyroid 72 (FUJI-DE
VISON CHEMICAL LTD. A coating solution for a protective layer used in Examples and Comparative Examples was prepared by mixing 1 g of Snowtex N with an amount of 50 mg/m2 of 50 mg/m2. Below, surfactant (1), (
The chemical structural formulas of 2), (3), (4), (5) and (6) are shown.

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[C7]

Examples 1-2, Comparative Examples 1-3 Preparation and evaluation of positive heat-developable photosensitive recording materials Lumirror E-60 (manufactured by Toray Industries, Inc.) was used as a support.
Polyester film filled with white pigment, thickness 100
A heat-developable photosensitive recording material was prepared in the following manner. Coating solution (1) for photosensitive/thermosensitive layer was applied onto the support using a coating bar until the dry weight of the coating layer was 8 g/m.
2 and dried at 30°C for 10 minutes. On top of this layer, the intermediate layer (1) was applied and dried to a dry weight of 2 g/m2, and then the photosensitive/thermosensitive layer coating liquid (
2) was coated and dried to a dry weight of 8 g/m2, then the intermediate layer (2) was coated and dried to a dry weight of 2 g/m2, and the photosensitive/thermosensitive layer coating liquid ( 3) was applied and dried to a dry weight of 8 g/m2, and then a protective layer coating solution containing the surfactant shown in Table 1 was applied using a coating bar to a coating layer dry weight of 8 g/m2. 2g/m
2 and dried at 30°C for 10 minutes to obtain samples for Examples and Comparative Examples.

The resulting heat-developable photosensitive recording material is coated with a lith film in which a yellow image is developed and an optical filter (SC-41 filter:
The film was exposed to ultraviolet light from a 2000 W high-frequency lighting type ultra-high pressure mercury lamp (Printer P627GA, manufactured by Dai-nihon Screen Co., Ltd.) through a 2000 W high-frequency lighting type ultra-high pressure mercury lamp (Printer P627GA, manufactured by Dai-nihon Screen Co., Ltd.). Next, a lith film with a developed image for magenta and 365 nm~
Exposure to mercury lamp light through an interference filter that transmits only 400 nm light, and then expose to mercury lamp light through a lith film developed with a cyan image and an interference filter that transmits only 340 nm to 365 nm light. Obtained a statue of Buddha. Thereafter, it was heated for 5 seconds on a hot plate at 120°C. The surface homogeneity and image homogeneity of the obtained recording material were evaluated. The results are shown in Table 1.

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[Table 1]

Example 3, Comparative Example 4 Preparation and Evaluation of Negative Heat-Developable Photosensitive Recording Material Coating solution (4) for photosensitive/thermosensitive layer was applied to the above support using a coating bar to measure the dry weight of the coated layer. It was applied at a concentration of 8 g/m2 and dried at 30°C for 10 minutes. Next, a coating solution for a protective layer prepared using the surfactants shown in Table 2 was applied thereon using a coating bar so that the dry weight of the coating layer was 5 g/m2, and the coating solution was heated at 30°C. After drying for 10 minutes, samples of Examples and Comparative Examples were obtained.

The obtained heat-developable photosensitive 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 exposure, evaluation was performed according to the method of Example 1. The results are shown in Table 2.

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[Table 2]

[0082]

Effects of the Invention According to the manufacturing method of the present invention, a completely dry black-and-white or color heat-developable photosensitive recording material that does not generate unnecessary waste and does not require the use of a developer, etc. It is possible to produce a heat-developable photosensitive recording material that provides clear images without unevenness, repelling, pinholes, etc.

Claims (5)

[Claims] 1. A photosensitive/thermosensitive layer in which a latent image is formed on a photocurable composition by exposure to light, and a component involved in color development or decolorization moves within a recording material according to the latent image by heating to form an image. In the method for producing a heat-developable photosensitive recording material having at least one layer on a support and a protective layer thereon, at least one nonionic or anionic, intramolecular 1. A method for producing a heat-developable photosensitive recording material, which comprises applying a liquid containing a surfactant having a fluorinated alkyl group to the surface of the material to provide the protective layer. 2. A pattern image is formed on the photocurable composition outside the microcapsules by exposure, and by heating the electron-accepting compound moves within the recording material according to the pattern image, thereby donating electrons within the microcapsules. In the method for producing a heat-developable photosensitive recording material, the material has at least one photosensitive/thermosensitive layer on a support that forms an image by coloring a colorless dye, and has a protective layer thereon, A heat-developable photosensitive material characterized in that the protective layer is provided by applying a liquid containing at least one nonionic or anionic surfactant having a fluorinated alkyl group in the molecule. Method of manufacturing recording material. 3. A photocurable product containing a microcapsule containing an electron-donating colorless dye, a compound having an electron-accepting part and a polymerizable vinyl monomer part in the same molecule outside the microcapsule, and a photopolymerization initiator. has at least one photosensitive/thermosensitive layer on the support, and
In a method for producing a heat-developable photosensitive recording material having a protective layer thereon, at least one nonionic or anionic surfactant having a fluorinated alkyl group in the molecule is used. 1. A method for producing a heat-developable photosensitive recording material, which comprises applying a liquid containing the protective layer to provide the protective layer. [Claim 4] Claim 1, Claim 2 or Claim 3
A method for producing a heat-developable photosensitive recording material, wherein the heat-developable photosensitive recording material is a multicolor recording material. 5. The heat-developable photosensitive recording material according to claim 4, wherein the first photosensitive layer is sensitive to light having a center wavelength λ1 from the exposure light source side toward the support side of the recording material.
An intermediate layer that absorbs light with a center wavelength λ1, 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, ... absorbs light with a center wavelength λi-1. at least two or more layers in the following order: an intermediate layer that is sensitive to light with a center wavelength λi, and an i-th photosensitive layer that is sensitive to light with a center wavelength λi and develops a color different from the i-1th photosensitive layer. The photosensitive layer has a layer structure laminated on a support, and the center wavelength λ1<λ2
<...<λi. A method for producing a heat-developable photosensitive recording material. Here, i is an integer of 2 or more.