JPH05224405A - Heat-developable photosensitive material - Google Patents

Abstract

PURPOSE:To provide a heat-developable photosensitive material capable of obtaining an image excellent in discrimination within a short time and stably forming the image against the fluctuation of heat-developable processing temp. CONSTITUTION:In the heat-developable photosensitive material having a photosensitive layer containing silver halide, a reducing agent, a polymerizable compound and a basic precursor, the photosensitive layer contains further a polyacrylate and/or polyacrylamide-based oil-soluble high molecular compound having amino group and/or imino group in the same molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material capable of obtaining an image with excellent discrimination. Further, the present invention relates to a photothermographic material in which an obtained image is hardly affected by fluctuations in heat development processing conditions.

[0002]

A latent image is formed by exposing a light-sensitive material having a light-sensitive layer comprising a light-sensitive silver halide, a reducing agent, a polymerizable compound and a binder on a support to form a latent image, and then heat-developing it to form a halogen image. An image forming method for forming a polymer compound on a portion where a latent image of silver halide is formed is disclosed in JP-A-61-69.
062 and the like.

Further, a light-sensitive material comprising a silver halide, a reducing agent, a color image-forming substance and a polymerizable compound contained in microcapsules (photosensitive microcapsules) is disclosed in Japanese Patent Laid-Open Publication No. Sho 6-62.
Nos. 1-275742 and 61-278849. An image forming method using the light-sensitive material having the above-described structure is as follows. First, the light-sensitive material is exposed imagewise to form a latent image, and then this is heat-developed, so that the polymerizable compound in the portion where the latent image is formed And further superimpose the light-sensitive material with an image-receiving material having an image-receiving layer, and pressurize in this state to transfer the color image-forming substance together with the unpolymerized polymerizable compound to the image-receiving material to obtain a transferred image on the image-receiving material. This method is generally used.

On the contrary, a method of polymerizing a polymerizable compound in a portion where a latent image is not formed is disclosed in JP-A-62-62.
-70836, 62-81635, JP-A 2-1
No. 41756 and No. 2-141757.

On the other hand, the development or polymerization reaction in the development processing of the above-mentioned image forming method proceeds smoothly under alkaline conditions. Therefore, a light-sensitive material containing a base or a base precursor is described in JP-A-62-264041. In this case, the base or base precursor is preferably contained in the photosensitive microcapsules.

A light-sensitive material characterized by containing a base precursor in microcapsules is disclosed in JP-A-64 / 1988.
No. 32251, JP-A-1-263641, and 2-1.
The solid base precursor described in each publication such as No. 46041 and No. 1-263641 is contained in a microcapsule. Thus, by accommodating the base or the base precursor in the microcapsules, image formation is promoted, and a photosensitive material which gives a clear image in a short time can be obtained. In this case, when the base is contained in the microcapsules. However, it is preferable to store the base precursor instead of the base in the microcapsules, because the deterioration of the light-sensitive material over storage becomes remarkable.

As the base precursor used in such a light-sensitive material, a compound which decomposes by heating during heat development to form a base is generally used. In order to obtain an image with excellent discrimination in a short time, it is preferable that the base precursor is stable at the temperature of storage of the light-sensitive material and instantly decomposes at the heat development temperature as a property required. Such a base precursor generally has a large activation energy for the decomposition reaction, and the decomposition rate tends to be easily influenced by the temperature fluctuation during heat development. As a result, the image forming reaction may fluctuate and the resulting image may have uneven density. This phenomenon is prominent at an intermediate density and is a particular problem when an image is formed from a continuous-tone original such as a photograph, and means for solving the problem has been desired.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photothermographic material which can obtain an image having excellent discrimination in a short time, and the obtained image is not easily affected by fluctuations in processing conditions. The object is to provide a material, and further to provide a photothermographic material which is less likely to deteriorate with storage.

[0009]

An object of the present invention is to provide a photothermographic material having a photosensitive layer containing at least a silver halide, a reducing agent, a polymerizable compound and a base precursor on a support, the photosensitive layer having the same molecule. This has been achieved by containing a polyacrylate and / or polyacrylamide-based oil-soluble polymer compound having an amino group and / or an imino group therein. The details of the mechanism of action of this polymer compound are not clear, but the base precursor and polymer compound interact very strongly in the temperature region during storage, and the decomposition reaction is difficult to proceed in the temperature region of heat development. Is estimated to weaken and the decomposition reaction proceeds smoothly. That is, since the activation energy of the decomposition reaction of the base precursor is very large in the temperature range during storage over time, the photosensitive material does not deteriorate, and in the temperature range of heat development, the above-mentioned activation energy is small, so the obtained image is heat developed. It seems that it is not easily affected by changes in processing conditions. The polyacrylate and / or polyacrylamide oil-soluble polymer compound having an amino group and / or an imino group in the same molecule that can be used in the present invention will be described in detail below.

Polyacrylate having an amino group and / or an imino group used in the present invention and /
Alternatively, the polyacrylamide-based oil-soluble polymer compound is composed of at least one acrylate-based monomer and / or acrylamide-based monomer. Among them, various compounds are known, among which esters and amides of acrylic acid and methacrylic acid, and further reaction products of acrylic acid and methacrylic acid with ethylene oxide and / or propylene oxide are known. It is preferably used. Preferred specific examples include methyl methacrylate, ethyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
Hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monomethacrylate, ( Examples thereof include ethylene oxide)-(propylene oxide) -monomethacrylate, acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and t-butylacrylamide.

As the amino group / imino group contained in the polymer compound of the present invention, a compound having both a vinyl group and the functional group is used to directly carry out a copolymerization reaction with the acrylate and / or acrylamide monomer. Or by subsequent attachment of the functional groups to polymer chains bearing the corresponding reactive functional groups. The amino group and imino group according to the polymer compound of the present invention are cyclic,
Although it may be acyclic, it is preferably an amino group having no hydrogen atom on the nitrogen atom, an imino group, or a nitrogen-containing heterocyclic compound residue. In this case, the nitrogen-containing heterocyclic compound may be a 5- or 6-membered heterocyclic ring which may further contain an oxygen atom or a sulfur atom, and a benzene ring may be further condensed. More preferably, the amino group or the heterocyclic compound residue has 20 or less carbon atoms.

Specific examples of preferred compounds for directly polymerizing with acrylate and / or acrylamide type monomers include vinylimidazole, vinylpyridine, vinylpyrrolidone, vinylcarbazole, dimethylaminoethylmethacrylate, diethylaminoethylmethacrylate, dimethylaminomethylstyrene, diethylamino. Methyl styrene, dibutyl aminomethyl styrene, etc. are mentioned.

The compound having an amino group, an imino group and capable of being bonded to the polymer chain later must have at least one reactive functional group. This functional group is, for example,
OH, -NH _2, -SH, a -COOH, Preferred specific examples, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine,
N, N-dimethylethanediamine, N, N-dimethylpropanediamine, 1- (2-aminoethyl) -piperazine, N-ethyl-3-piperidinol, 4-amino-2
-Methoxypyrimidine, 2-dimethylaminoethanol, N- (2-hydroxyethyl) morpholine, 2-mercaptopyrimidine, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 4- (2-aminoethyl) pyridine, 2-amino -6-methoxybenzothiazole, 4- (aminomethyl) pyridine, 3-amino-1,2,4-triazole, N- (3-aminopropyl) imidazole, 4- (2-hydroxyethyl)
Pyridine, 4- (2-hydroxyethyl) imidazole, 3-mercapto-1,2,4-triazole and the like can be mentioned.

The above-mentioned compound having an amino group or an imino group can be directly bonded to the polymer chain, or can be bonded via a compound having a reactive functional group such as an isocyanate group. Preferred specific examples of the monomer constituting the polymer chain suitable for this purpose include:
Glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-
Examples thereof include hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Specific preferred examples of the compound containing an isocyanate group are shown below.

[0015]

[Chemical 1]

The compounds of the present invention may further contain other than acrylate-based compounds such as vinyl aromatic monomers (styrene, α-methylstyrene, vinyltoluene, etc.), vinyl esters (vinyl acetate, etc.), acrylonitrile, etc. in order to adjust photographic performance. It may contain a monomer. The polymer compound of the present invention may have various molecular weights.
00000 or less, preferably 2000 or more, 50
Those of 000 or less are particularly preferable.

Examples of preferable polymer compounds used in the present invention are listed below, but since they cannot be represented as a single structure,
It is described as a combination of a monomer, a compound having an amino group and / or an imino group, and a compound having an isocyanate group.

1. Monomer: Isobutyl methacrylate Octyl acrylate Hydroxyethyl methacrylate Polyethylene glycol monomethacrylate Compound having amino group, imino group: 1- (3-aminopropyl) imidazole Compound having isocyanate group: Isophorone diisocyanate 2. Monomer: isobornyl methacrylate 2-ethylhexyl acrylate hydroxyethyl methacrylate styrene A compound having an amino group and an imino group: 3-amino-1,
2,4-triazole Compound having an isocyanate group: Tolylene-2,4-
Diisocyanate

3. 3. Monomer: isobornyl methacrylate, cyclohexyl methacrylate, ethyl acrylate, hydroxyethyl methacrylate, a compound having an amino group and an imino group: N, N-dimethylpropanediamine, a compound having an isocyanate group: isophorone diisocyanate 4. Monomer: isobornyl methacrylate 2-ethylhexyl acrylate vinyl toluene methyl methacrylate Compound having amino group, imino group: vinyl imidazole 5. Monomer: Isobornyl methacrylate 2-Ethylhexyl acrylate Polyethylene glycol monomethacrylate Cyclohexyl methacrylate Vinyltoluene Compound having amino group / imino group: Vinylimidazole

6. Monomer: t-butylacrylamide methylmethacrylate Styrene A compound having an amino group and an imino group: vinylimidazole 7. Monomer: t-butylacrylamide Compound having amino group, imino group: Dimethylaminoethyl methacrylate 8. Monomer: t-butylacrylamide Compound having amino group, imino group: Dimethylaminomethylstyrene 9. Monomer: t-butyl acrylamide glycidyl methacrylate A compound having an amino group and an imino group: 1- (3-aminopropyl) imidazole 10. Monomer: t-butylacrylamide hydroxyethyl methacrylate 2-ethylhexyl acrylate A compound having an amino group and an imino group: N, N-dimethylpropanediamine 1- (3-aminopropyl) imidazole A compound having an isocyanate group: isophorone diisocyanate

In addition to these, the following are commercially available polyacrylate compounds that can be used as the polymer compound of the present invention. 11. EFKA-400 (trade name EFKA Chemical
s company) 12. EFKA-401 (trade name same as above
) For the synthesis of these compounds, see JP-A 1-1644
It can be easily carried out according to No. 29.

These polymer compounds can be added to any position in the photosensitive layer, but it is more preferable to add them to the microcapsules. The amount of these polymer compounds used is 0.001 with respect to 1 part by weight of the base precursor.
To 100 parts by weight, more preferably 0.05 to
10 parts by weight.

The photothermographic material of the present invention preferably contains a silver halide, a reducing agent, a polymerizable compound and a base precursor in microcapsules, and further contains a color image forming substance in the microcapsules. Preferably. The silver halide, the reducing agent, the polymerizable compound, the base precursor, the color image-forming substance, the microcapsule, and the support which are used in the photothermographic material (hereinafter simply referred to as photosensitive material) of the present invention will be described below.

The silver halide emulsion contained in the photosensitive microcapsule of the present invention includes silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and chloroiodo odor. Any silver halide grains can be used. Silver halide grains include those having regular crystals such as cubes, octahedra, dodecahedrons and tetrahedra, those having an irregular crystal system such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.01 micron or less, or large grains having a projected area diameter of up to about 10 microns, and it may be a polydisperse emulsion or US Pat. No. 3,574,628. No., 3,655,394
And monodisperse emulsions described in British Patent No. 1,413,748 and the like may be used. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic by Gatov.
Science and Engineering), Volume 14, 248-257
Page (1970); U.S. Pat. No. 4,434,226,
4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,1.
It can be easily prepared by the method described in No. 57, etc.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, the halogen composition,
Two or more kinds of silver halide grains having different crystal habits, grain sizes and the like can be used in combination. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (December 1978), 2
2-23, "I. Emulsion preparation a
nd types) ", and No. 18716 (1979, 1
January), page 648, and the like.

The silver halide emulsion is usually used after physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. Additive type RD17643 RD18716 Chemical sensitizer, page 23, page 648, right column, sensitivity enhancer, same as above, spectral sensitizer, page 23-24, page 648, right column, supersensitizer, page 649, right column, antifoggant, page 24-25, 649 Right column on page ~ and stabilizer

Details of the above silver halide emulsion and photographic additives are described in "Public Technology No. 5" (Aztec Co., Ltd., issued March 22, 1991), pages 2 to 17. The amount of silver halide used is 1
0.001 to 10 g, preferably 0.0 per m ^{2 in} terms of silver
It is 5 to 2 g. Further, in the present invention, an organic silver salt can be used together with silver halide. The organic silver salt is described on pages 17 to 18 of "Public Technology No. 5" mentioned above.

The reducing agent which can be used by being housed in the photosensitive microcapsules of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. Examples of the reducing agent having the above function include hydroquinones, catechols, p-
Aminophenols, p-phenylenediamines, 3-
Pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-
Dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,
4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, Examples include sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines. The various reducing agents described above are described in detail on pages 18 to 35 of the above-mentioned "Known Technology No. 5".
The addition amount of the reducing agent can be widely varied, but is generally 0.1 to 1500 mol%, preferably 10 to 10 mol% with respect to the silver salt.
It is 300 mol%.

The polymerizable compound that can be used in the light-sensitive material of the present invention is not particularly limited, and known polymerizable compounds can be used. It is preferable to use a polymerizable compound having a high boiling point (for example, a boiling point of 80 ° C. or higher) that is less likely to volatilize during heating because it is subjected to heat development treatment. Further, since the present invention is intended to immobilize the color image forming substance by polymerizing and curing the polymerizable compound, the polymerizable compound is preferably a crosslinkable compound having a plurality of functional groups in the molecule. The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group, but a compound having an ethylenically unsaturated group is particularly preferable. Examples of compounds having an ethylenically unsaturated group include acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydrides, maleic acid esters, and itacone. There are acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives. The various polymerizable compounds described above are described in detail in "Public Technology No. 5", pages 51 to 55, and Japanese Patent Application No. 3-116667.

There are no particular restrictions on the color image forming substance that can be used in the light-sensitive material of the present invention, and various types can be used. That is, the substance itself is colored (dye or pigment), or the substance itself is colorless or light-colored but external energy (heating, pressure, light irradiation, etc.) or another component (developing agent) A substance (color former) that develops a color upon contact with is also included in the color image forming substance. As the color image-forming substance of the present invention, as described in JP-A-62-187346, dyes and pigments which are excellent in image stability and colored themselves are preferable.

As the color image forming substance used in the present invention, as dyes and pigments, commercially available substances and known substances described in various documents can be used. Regarding literature, Color Index (CI) handbook, "Latest Pigment Handbook" edited by Japan Pigment Technology Association (1977), "Latest Pigment Application Technology" CMC Publishing (1986), "Printing Ink Technology" (CMC Publishing) , 1984). Details of the color image-forming substance that can be used in the present invention and the technique for using the same are described in the above-mentioned "Known Technology No. 5", pp. Pigments are particularly preferable because they have excellent light fastness. The pigment is 5-6 with respect to 100 parts by weight of the polymerizable compound.
It is preferable to use 0 part by weight. When a pigment is used, a known dispersant can be used in combination for the purpose of increasing dispersibility in the polymerizable compound. Details of the dispersant are described in "Dispersion Technology Comprehensive Material Collection" (Business Development Center Publishing Department) and the like.

As the base precursor that can be used in the light-sensitive material of the present invention, inorganic base and organic base base precursors (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used. For details of these base precursors and their use techniques, refer to the above-mentioned "Public Art No. 5".
No. ”pp. 55-86. Preferred base precursors are JP-A-59-180549, JP-A-59-180537, JP-A-59-195237, and JP-A-59-180537.
1-328844, 61-36743, 61-5
No. 1140, No. 61-52638, No. 61-5263
No. 9, No. 61-53631, No. 61-53634,
61-53635, 61-53636, 61
-53637, 61-53638, 61-53
No. 639, No. 61-53640, No. 61-55644.
No. 61, No. 61-55645, No. 61-55646, No. 61-84640, No. 61-107240, No. 61.
-219950, 61-251840, 61-
No. 252544, No. 61-313431, No. 63-3
16740, 64-68746 and Japanese Patent Application No. 1-
Salts of organic acids and bases which are decarboxylated by heating as described in JP-A-54452, and JP-A-59-15763.
No. 7, No. 59-166943, and No. 63-96159, the compounds capable of eliminating a base by heating are mentioned.

The base precursor of the present invention is 50
It is preferable to release the base at ℃ to 200 ℃, 80
More preferably, the release is carried out at a temperature of 180 to 180 ° C. The base precursor used in the light-sensitive material of the present invention is housed in a light-sensitive microcapsule.
No. 70159, a base precursor consisting of a salt of a carboxylic acid and an organic base as described below, which has a solubility of 1% or less in water and a polymerizable compound at 25 ° C., is particularly preferable.

In the present invention, when the base precursor is accommodated in the microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used (Japanese Patent Laid-Open No. Sho 32-3251). Kaihei 1-2
It is particularly preferable to use a photosensitive composition in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (JP-A-63-21
8964, JP-A Nos. 2-146041, and 3-2.
No. 5444, each publication) Here, in dispersing the base precursor in water, a nonionic or amphoteric water-soluble polymer described in “Public Technology No. 5”, pages 128 to 135 can be used. ..

The above water-soluble polymer is preferably contained in the base precursor in a proportion of 0.1 to 100% by weight, more preferably 1 to 50% by weight. The base precursor is preferably contained in the dispersion in an amount of 5 to 60% by weight, more preferably 10 to 50% by weight. The base precursor is preferably contained in a proportion of 2 to 50% by weight with respect to the polymerizable compound,
It is more preferable that the content is 5 to 30% by weight.

Various known techniques can be applied to the microcapsules that can be used as the photosensitive microcapsules that can be used in the present invention without particular limitation. The method described can be used. In the present invention, it is particularly preferable to use a melamine-formaldehyde resin, since a highly dense capsule can be obtained. Further, JP-A-2-216151 discloses a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group in order to obtain a capsule having particularly excellent wall compactness. A microcapsule in which a polymer wall of a high molecular compound such as melamine / formaldehyde resin is provided around the membrane is disclosed, which is preferable for the present invention.

When aminoaldehyde-based microcapsules are used, it is preferable that the amount of residual aldehyde is not more than a certain value, as in the light-sensitive material described in JP-A-63-32535. The method is disclosed in JP-A-63-14.
No. 2343, etc. The average particle size of the photosensitive microcapsules is 1 to 50 μm, preferably 3 to 25 μm.
μm. The particle size distribution of the photosensitive microcapsules is preferably uniform over a certain value, as in the photosensitive material described in JP-A-63-5334.
Further, the film thickness of the photosensitive microcapsule is as described in JP-A-63-
As in the light-sensitive material described in Japanese Patent No. 81336, it is preferable that the particle diameter is within a certain range.

When the silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably not more than 1/5 of the average size of the photosensitive microcapsules, and preferably 10 min. It is more preferable to set it to 1 or less. By setting the average grain size of the silver halide grains to be one fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained. When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. A light-sensitive material containing silver halide in the microcapsule wall material is described in JP-A-62-169147.

In the production of the photosensitive microcapsules of the present invention, an oily liquid composed of a silver halide, a reducing agent, a color image-forming substance and a polymerizable compound containing a base precursor is dispersed in an aqueous medium to form a capsule shell. When forming, it is preferable that the aqueous medium contains a nonionic water-soluble polymer and an anionic water-soluble polymer. In this case, the oily liquid containing the polymerizable compound is preferably 10 to 120% by weight with respect to the aqueous medium,
˜90% by weight is more preferred.

Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. Examples of the anionic water-soluble polymer include polystyrene sulfinic acid, copolymer of styrene sulfinate, polystyrene sulfonate, copolymer of styrene sulfonate, polyvinyl sulfate ester salt, polyvinyl sulfonate, maleic anhydride. -Styrene copolymers, maleic anhydride / inbutylene copolymers and the like can be mentioned. In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight. In the above case, it is particularly preferable to use the nonionic water-soluble polymer in combination with the water-soluble polymer having a small amount of sulfinic acid groups. Further, in order to reduce the solubility of the base precursor in the polymerizable compound, in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexylurea, octyl alcohol, dodecyl alcohol, stearyl alcohol, -OH such as stearamide,-. SO ₂ NH ₂ , −
CONH _2, it is also possible to add a compound having a hydrophilic group such as -NHCONH _2.

In the present invention, in addition to the reducing agent, a known antioxidant may be used together with the polymerizable compound for preventing oxidative deterioration of the polymerizable compound and for preventing oxygen oxidation during heat development. As such an antioxidant, 2,2 '
-Methylene-bis- (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, 2,
2'-butylidene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4
-Methylphenyl acrylate, 4,4'-thio-bis- (3-methyl-6-t-butylphenol) and other phenolic antioxidants; diphenyldecyl phosphite,
Triphenyl phosphite, tris- (2,4-di-t
-Butylphenyl) phosphite, tris- (2-ethylhexyl) phosphite and other phosphite antioxidants; dilauryl-3,3'-thio-dipropionic acid ester, pentaerythritol-tetrakis- (β-lauryl-thio -Propionate), thio-dipropionic acid and other sulfur-based antioxidants; phenyl-1-naphthylamine, 6-ethoxy-2,2,4-trimethyl-
Examples include amine antioxidants such as 1,2-dihydroquinoline and dioctyliminodibenzyl.

Materials usable for the support include glass, paper, wood free paper, baryta paper, coated paper, cast coated paper, synthetic paper, metal and its analogues, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose. Ester, polyvinyl acetal,
Examples thereof include films such as polystyrene, polycarbonate, polyethylene terephthalate, and polyimide, and paper laminated with a resin material or a polymer such as polyethylene. For details, refer to “Public Technology No. 5”
No. "pp. 144-149. Among them, the preferred support of the present invention is a polymer film, and it is particularly preferred that it is a polymer film of 50 μm or less in view of the above-mentioned thermal conductivity.

Further, in order to apply a photosensitive layer to the support,
It is preferable to provide the undercoat layer described in JP-A-61-113058 on the polymer film, or to provide a metal vapor deposition film of aluminum or the like on the polymer film.
Therefore, as the support of the light-sensitive material of the present invention, 50 μm
A polymer film having a thickness of m or less and having an aluminum vapor deposition film is particularly preferable.

Other components that can be used in the light-sensitive material of the present invention will be described below. Details of these components are described in the above-mentioned "Known Technology No. 5", pp. 98-144 and 86-.
It is described on page 88. The binder that can be used in the light-sensitive material can be contained in the light-sensitive layer alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical. For example, natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. Synthetic polymers such as water-soluble polyvinyl compounds. Other synthetic polymeric materials include dispersed polyvinyl compounds in the form of latices, which in particular increase the dimensional stability of photographic materials. The light-sensitive material using a binder is described in JP-A-61-69062. Further, regarding a light-sensitive material using a binder together with microcapsules, see JP-A-62-209525.
It is described in the official gazette.

The anti-smudge agent used in the light-sensitive material is preferably solid particles at room temperature. Specific examples thereof include starch particles described in British Patent No. 1232347, polymer fine powder described in U.S. Pat. No. 3,625,736, and microcapsule particles containing no color former described in British Patent No. 12359991. US Patent No. 2
Examples include cellulose fine powder described in No. 711375, talc, kaolin, bentonite, wax, inorganic particles such as zinc oxide, titanium oxide and alumina. The average particle size of the particles is preferably in the range of 3 to 50 μm in volume average diameter, and more preferably in the range of 5 to 40 μm. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules. Various image formation accelerators can be used in the light-sensitive material.

The image forming accelerator has a function of promoting the transfer of a base or a base precursor, promoting the reaction of a reducing agent with a silver salt, and promoting the immobilization of a dye-donor substance by polymerization. Are classified into the above-mentioned bases or base precursors, nucleophilic compounds, oils, thermal solvents, surfactants, compounds that interact with silver or silver salts, compounds having an oxygen scavenging function, and the like. However, these substance groups generally have a composite function and usually have some of the above-mentioned accelerating effects together. Details thereof are described in the specifications and publications of U.S. Pat. No. 4,678,739, columns 38 to 40, JP-A-62-209443 and the like. The hexavalent metal compound described in Japanese Patent Application No. 2-272878 is also effective.

A photosensitive material is prepared by polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed,
A heat or photopolymerization initiator can be used for the purpose of initiating polymerization or for polymerizing an unpolymerized polymerizable compound after image transfer. Examples of thermal polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, sulfinic acids and the like. Details thereof are described on pages 6 to 18 of “Addition Polymerization / Ring-Opening Polymerization” (1983, Kyoritsu Shuppan) edited by the Society for Polymer Science, Editorial Committee for Polymer Experiments.

Examples of the photopolymerization initiator include benzophenones, acetophenones, benzoins, thioxanthones and the like. Details thereof are described in "UV Curing System" (1989, Comprehensive Technical Center), pages 63 to 147, and the like. Various surfactants may be used in the light-sensitive material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173.
463, 62-183457 and the like.

An antistatic agent may be used in the light-sensitive material for the purpose of antistatic. As an antistatic agent, it is described in Research Disclosure Magazine, November 1978, No. 17643 (page 27). In the photosensitive layer of the photosensitive material,
Dyes or pigments may be added for the purpose of preventing halation or irradiation. A light-sensitive material having a white pigment added to the light-sensitive layer is disclosed in JP-A-63-29748.
It is described in the official gazette.

A dye having the property of being decolorized by heating or light irradiation may be contained in the microcapsules of the light-sensitive material. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. A light-sensitive material using a dye having the property of being decolorized by heating or irradiation with light as described above is described in JP-A-63-974940.

When a solvent of a polymerizable compound is used in the light-sensitive material, it is preferable to use it by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound.
A photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules is disclosed in Japanese Patent Laid-Open No.
It is described in JP-A-2-209524.

Various antifoggants or photographic stabilizers can be used in the present invention. For example,
Azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-168442.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-111636, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used. .

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction of a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-253159, pages (31) to (32), Japanese Patent Application No. 1-724
No. 79, No. 1-3471, etc. are described.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and the usage thereof are also described in the specification of the above-mentioned series of photosensitive materials and Research Disclosure Vol. 170, 197.
No. 17029 (pages 9 to 15), June 1996. As the layer that can be optionally provided in the photosensitive material,
Examples thereof include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or a protective layer, and an antihalation layer (colored layer).

A photosensitive material using a heating element layer is disclosed in JP-A-61-294434, and a photosensitive material provided with a cover sheet or a protective layer is disclosed in JP-A-62-2.
Japanese Patent Application Laid-Open No. 63-101842 discloses a light-sensitive material provided with a coloring layer as an antihalation layer.
Each of them is described in Japanese Patent Publication No. Further, examples of other auxiliary layers and usage modes thereof are also described in the publications or application specifications relating to the series of photosensitive materials described above.
In the image forming method using the photosensitive material of the present invention, it is general to use the image receiving material together with the photosensitive material. The image receiving material will be described below. The details are described in "Public Technology No. 5", pages 149 to 178. The image receiving material may be only the support, but it is preferable to provide an image receiving layer on the support. The support for the image-receiving material is not particularly limited, but glass, paper,
High-quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, cloth, metal and its analogs, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, and other films, and Examples include paper laminated with a resin material or a polymer such as polyethylene.

When a porous material such as paper is used as a support for the image receiving material, it is disclosed in JP-A-62-20953.
It is preferable that the image-receiving material described in JP-A-No. Further, an image receiving material using a transparent support is described in JP-A-62-209531. The image-receiving layer of the image-receiving material is composed of a white pigment, a binder, and other additives, and the white pigment itself or voids between the particles of the white pigment enhance the receptivity of the polymerizable compound.

The white pigment used in the image-receiving layer is an inorganic white pigment, for example, oxides of silicon oxide, titanium oxide, zinc oxide, magnesium oxide, aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate, carbonic acid. Alkaline earth metal salts such as magnesium, barium carbonate, calcium carbonate, calcium silicate, magnesium hydroxide, magnesium phosphate, and magnesium hydrogen phosphate, as well as aluminum silicate, aluminum hydroxide, zinc sulfide, various clays, talc, Examples include kaolin, zeolite, acid clay, activated clay, glass and the like. Organic white pigments include polyethylene, polystyrene, benzoguanamine resins, urea-formalin resins,
Examples thereof include melamine-formalin resin and polyamide resin. These white pigments may be used alone or in combination, but those having a high oil absorption amount with respect to the polymerizable compound are preferable.

As the binder used in the image-receiving layer of the present invention, a water-soluble polymer, a polymer latex, a polymer soluble in an organic solvent or the like can be used. As the water-soluble polymer, for example, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as methyl cellulose, gelatin, phthalated gelatin, casein, proteins such as ovalbumin, starches such as dextrin, etherified starch, polyvinyl alcohol,
Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, synthetic polymers such as polyvinyl imidazole, polyvinyl pyrazole, polystyrene sulfonic acid, etc., locust bean gum, pullulan, gum arabic, alginic acid Examples include soda.

As the polymer latex, for example, a styrene-butadiene copolymer latex, a methyl methacrylate / butadiene copolymer latex, a polymer of acrylic acid ester and / or methacrylic acid ester, or a copolymer latex, ethylene / vinyl acetate copolymer is used. Polymer latex etc. are mentioned. Examples of the polymer soluble in an organic solvent include polyester resin, polyurethane resin, polyvinyl chloride resin, polyacrylonitrile resin and the like.

As the method of using the above binders, two or more kinds can be used in combination, and further, two kinds of binders can also be used in a ratio such that phase separation occurs. An example of such usage is described in JP-A-1-154789. The average particle size of the white pigment is 0.1
˜20 μ, preferably 0.1 to 10 μ, and the coating amount is 0.1 g to 60 g, preferably 0.5 g to 30 g.
The range is. The weight ratio of the white pigment to the binder is preferably 0.01 to 0.4, more preferably 0.03 to 0.3, relative to 1 pigment.

The image-receiving layer may contain various additives as described below, in addition to the binder and the white pigment. For example, when a color-developing system including a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent. Typical developers include phenols, organic acids or salts thereof, or esters, but when a leuco dye is used as a color image forming substance, a zinc salt of a salicylic acid derivative is preferable, Above all,
Zinc 3,5-di-α-methylbenzyl salicylate is preferred. The above color developer is preferably contained in the image receiving layer in a coating amount of 0.1 to 50 g / m ² . More preferably, it is in the range of 0.5 to 20 g / m ² .

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation.
The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from known plastic resins (plastics) and waxes. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or lower. Regarding the image-receiving material having the image-receiving layer containing the above-mentioned fine particles of a thermoplastic compound, Japanese Patent Application Laid-Open Publication No. 6-58242
2-280071 and 62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material, a color image forming substance is transferred together with an unpolymerized polymerizable compound. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of curing (fixing) the unpolymerized polymerizable compound. An image receiving material having an image receiving layer containing a photopolymerization initiator is disclosed in JP-A-62-161149, and an image receiving material having an image receiving layer containing a thermal polymerization initiator is disclosed in JP-A-62-161149.
Each of them is described in Japanese Patent Publication No. 210444.

In the following, the step of imagewise exposure in the image forming method of the present invention, the imagewise exposure, or after the imagewise exposure, the photosensitive material is heated from the surface of the support having no photosensitive layer coated thereon. And a series of steps such as a step of superposing the surface of the photosensitive material coated with the photosensitive layer and the image receiving material and pressurizing the same.

As the exposure method in the imagewise exposure step, various exposure means can be used, but in general, a latent image of silver halide is obtained by imagewise exposure to radiation including visible light. The type of light source and the amount of exposure depend on the photosensitive wavelength of silver halide (the wavelength sensitized when dye-sensitized)
Alternatively, it can be selected according to the sensitivity.

Typical light sources include low-energy radiation sources such as natural light, ultraviolet rays, visible light, infrared rays, fluorescent lamps, tungsten lamps, mercury lamps, halogen lamps, xenon flash lamps, laser light sources (gas laser, solid laser, Chemical lasers, semiconductor lasers, etc.), light emitting diodes, plasma arc tubes, FOTs and the like. In special cases, it is possible to use X-rays, γ-rays, electron beams, etc., which are high-energy ray sources.

The light-sensitive material of the present invention, particularly in the case of a full-color light-sensitive material, is composed of microcapsules having photosensitivity in a plurality of spectral regions, and therefore it is necessary to perform image exposure with a plurality of corresponding spectral lines. Is. Therefore, the light sources may be used alone or in combination of two or more. When selecting the light source,
It goes without saying that a light source suitable for the photosensitive wavelength of the photosensitive material is selected, but it can be selected in consideration of whether image information passes through an electric signal, the processing speed of the entire system, compactness, power consumption, and the like.

When the image information does not pass through an electric signal, for example, direct photographing of landscapes and people, direct copying of original images,
In the case of exposing through a positive such as a reversal film, an exposure device for printing such as a camera, a printer or an enlarger, an exposure device for a copying machine or the like can be used. In this case, a two-dimensional image can be simultaneously exposed by so-called one shot, and scanning exposure can also be performed through a slit or the like. You can also stretch or reduce the original image. In this case, the light source is not a monochromatic light source such as a laser but a light source such as a tungsten lamp or a fluorescent lamp, or a combination of a plurality of monochromatic light sources.

When image information is recorded via an electric signal, as the image exposure device, a light emitting diode and various lasers may be used in combination according to the color sensitivity of the heat-developable color photosensitive material. Various devices known as an image display device (CRT, liquid crystal display, electroluminescence display, electrochromic display, plasma display, etc.) can also be used. In this case, the image information is an image signal obtained from a video camera or an electronic still camera, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels with a scanner or the like, or an image signal stored in a recording material such as a magnetic tape or a disk can be used.

When exposing a color image, LEDs, lasers, fluorescent tubes, etc. are used in combination according to the color sensitivity of the light-sensitive material. However, the same materials may be used in combination or different kinds may be used in combination. May be. The color sensitivity of the light-sensitive material is R (red), G (green), B (blue) in the photographic field.
Photosensitivity is normal, but in recent years, it is often used in combination with UV, IR, etc., and the range of use of the light source is expanding. For example, the color sensitivity of the photosensitive material is (G, R, IR)
Or (R, IR (short wave), IR (long wave)),
(UV (short wave), UV (medium wave), UV (long wave)), (U
Spectral regions such as V, B, G) are utilized. The light source may also be a combination of different types such as a combination of two LED colors and a laser. The light emitting tube or element may be scanned and exposed by using a single tube or element for each color, or an array tube may be used to increase the exposure speed. Examples of usable arrays include an LED array, a liquid crystal shutter array, and a magneto-optical element shutter array.

The image display device described above is a CRT.
As described above, there is a color display and a monochrome display, but a method of performing exposure several times by combining a color display with a color filter may be adopted. Existing 2
The three-dimensional image display device may be used by making it one-dimensional like FOT, or by dividing one screen into several pieces and using them in combination with scanning.

By the above imagewise exposure, a latent image is obtained on the silver halide contained in the microcapsules. The image forming method of the present invention includes a step of heating the photosensitive material at the same time as the imagewise exposure or after the imagewise exposure to thermally develop the photosensitive material. Thermal development is preferably performed by heating from the surface of the support on which the photosensitive layer of the photosensitive material is not coated.

As this heating means, there is disclosed in JP-A-61-29.
As in the light-sensitive material described in Japanese Patent No. 4434, a heating element layer may be provided on the surface of the support on which the light-sensitive layer of the light-sensitive material is not coated to heat it. Further, as described in JP-A-61-147244, a hot plate, an iron, and a heat roller are used, or as described in JP-A-62-144166, a photosensitive material is sandwiched between a heat roller and a belt. You may use the method of heating.

That is, the photosensitive material may be brought into contact with a heating element having a surface area larger than that of the photosensitive material to heat the entire surface at the same time, or a heating element having a smaller surface area (heating plate,
The entire surface may be heated over time by bringing it into contact with a heat roller, a heat drum, etc. and scanning it.
In addition to the heating method in which the heating element and the photosensitive material are brought into direct contact with each other as described above, electromagnetic waves, infrared rays, hot air or the like may be applied to the photosensitive material to heat it in a non-contact state.

In the image forming method of the present invention, thermal development is carried out by heating the surface of the photosensitive material on the support on which the photosensitive layer is not coated. At this time, the photosensitive layer is coated. The surface that is marked may be in direct contact with the air,
It may be covered with a heat insulating material or the like in order to keep it warm so as not to release heat. In this case, it is preferable not to apply a strong pressure (10 kg / cm ² or more) to the photosensitive layer so as not to destroy the microcapsules contained in the photosensitive layer.

The heat development by heating is carried out at the same time as or after the imagewise exposure, but it is preferable that the heating is carried out at least 0.1 seconds after the imagewise exposure. The heating temperature is generally 60 ° C to 250 ° C, preferably 80 ° C to 180 ° C.
And the heating time is between 0.1 and 20 seconds, preferably between 0.1 and 5 seconds.

The photosensitive material can be subjected to heat development as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. In the case where a polymerization inhibitor is formed in the latent image formed portion of silver halide by the reaction with a reducing agent, heat or photopolymerization initiation which has been added in advance in the photosensitive layer, preferably in microcapsules. It is also possible to disperse the agent by heating or irradiating with light to uniformly generate radicals and polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed. In this case, in addition to the above-mentioned imagewise exposure step and heat development step, if necessary, a whole surface heating or whole surface exposure step is required, and the method is the same as the imagewise exposure step or the heat development step.

In the image-forming method of the present invention, the unpolymerized polymerizable compound is transferred to the image-receiving material by the step of applying pressure in the state where the light-sensitive material having a polymer image and the image-receiving material are superposed on the photosensitive layer, A color image can be obtained on the image receiving material. A conventionally known method can be used as the pressurizing method.

For example, the photosensitive material and the image receiving material may be sandwiched between press plates such as a presser, or pressure may be applied while being conveyed by using a pressure roller such as a nip roll. The pressure may be intermittently applied by a dot impact device or the like.
Further, high pressure air can be blown by an air gun or the like, or can be pressurized by an ultrasonic generator, a piezoelectric element or the like. The pressure required for pressurization is 500 kg / cm ² or more,
It is preferably 800 kg / cm ² or more. However, 500 kg / cm when pressure is applied together with heating at 40 ° to 120 ° C
It may be ² or less.

The light-sensitive material of the present invention has many uses such as color photographing and printing light-sensitive materials, printing light-sensitive materials, computer graphic hard copy light-sensitive materials, and copying machine light-sensitive materials. It is possible to create compact and inexpensive image forming systems such as copiers, printers, and simple printers.

[0082]

【Example】

Example 1 Preparation of silver halide emulsion (EB-1) 24 g of lime-treated inert gelatin was added to distilled water, and 4
After dissolution at 0 ° C. for 1 hour, 3 g of NaCl was added, and 1N sulfuric acid was added thereto to adjust the pH to 3.2.

After 10 mg of (AGS-1) was added to this solution, the solution I and the solution II were maintained at 60 ° C. by the control double jet method while keeping pAg = 8.5, and at the same time, it took 45 minutes until the solution I disappeared. Added. After the addition is complete, p
H was adjusted to 6.0 with 1N NaOH and (AZ-1) 6.
4 mg and (AZ-2) 4.8 mg were added to 60 at 60 ° C.
Aged. After aging, 480 mg of (SB-1) was added, and 100 g of an aqueous solution containing 4.1 g of KI was added at an equal flow rate from 20 minutes to 3 minutes after the addition.

To this emulsion, 1.1 g of (CK-1) was added, precipitated, washed with water and desalted, and then 6 g of lime-processed gelatin was added and dissolved, and a 3.5% aqueous solution of (ATR-3) 1. The pH was adjusted to 6.2 by adding 5 cc. 550 g of a monodisperse silver iodobromide emulsion (EB-1) having an average grain size of 0.24 μm and a coefficient of variation of 20% was prepared.

Liquid I AgNO ₃ 120 g Distilled water 550 cc Liquid II KBr 85 g Distilled water 550 cc

Preparation of silver halide emulsion (EG-1) Same as silver halide emulsion (EB-1) except that solution I
Solution II was added for 15 minutes, and 450 mg of (SG-1) was added instead of (SB-1). 550 g of a monodisperse silver iodobromide emulsion (EG-1) having an average grain size of 0.18 μm and a coefficient of variation of 20% was prepared.

Preparation of Silver Halide Emulsion (ER-1) Same as silver halide emulsion (EB-1) except for Solution I and II.
The addition time of the liquid was set to 15 minutes, and instead of (SB-1), 450 mg of (SR-1) and 100 mg of (SR-2)
Was added. Average particle size 0.18 μm, coefficient of variation 2
550 g of a 2% monodisperse silver iodobromide emulsion (ER-1) was prepared.

[0088]

[Chemical 2]

[0089]

[Chemical 3]

(CK-1) Poly (isobutylene-co-
Monosodium maleate)

Preparation of solid dispersion (KB-1) 5.4 of lime-processed gelatin in a 300 ml dispersion container.
% Aqueous solution 110 g, polyethylene glycol (average molecular weight 2000) 5% aqueous solution 20 g, base precursor (BG-1) 70 g, and glass beads 200 ml having a diameter of 0.5 to 0.75 mm are added, and 300 using a Dynomill.
Disperse for 30 minutes at 0 rpm and adjust the pH to 6.5 with 2N sulfuric acid.
Adjusted to 1.0 μm or less and a base precursor (B
A solid dispersion (KB-1) of G-1) was obtained.

[0092]

[Chemical 4]

Preparation of Pigment Dispersion (GY-1) To 255 g of the polymerizable compound (MN-1), 45 g of Chromofine Yellow 5900 (trade name, manufactured by Dainichiseika Seiki Co., Ltd.) was mixed, and an Eiger Motor Mill (Eiger -Agitation was used for 1 hour at 5000 rpm to obtain a dispersion (GY-1). Polymerizable compound (MN-1) Compound described in Synthesis Example 1 of JP-A-64-68339 (manufactured by Nippon Kayaku Co., Ltd.)

Preparation of Pigment Dispersion (GM-1) Rubin F6B was added to 270 g of the polymerizable compound (MN-1).
(Product name, manufactured by Hoechst Co., Ltd.) 30 g was mixed and stirred for 1 hour at 5000 rpm using an Eiger Motor Mill (manufactured by Eiger Engineering Co.) to obtain a dispersion (GM-
1) was obtained.

Preparation of Pigment Dispersion (GC-1) Polymerizable compound (MN-1) (255 g) was mixed with copper phthalocyanine (CI Pigment 15) (45 g) and an Eiger Motor Mill (Eiger Engineering Co., Ltd.) was used. The dispersion (GC-
1) was obtained.

Preparation of Photosensitive Composition (PB-1) 45 g of pigment dispersion (GY-1) was added to (1P-4) of (SV
-1) 9 g of 10% (wt%) solution, (RD-1) 2.
3 g, (RD-3) 3.1 g, (FF-3) (SV-
1) 2 g of 0.5% (wt%) solution, (ST-1) 0.
5 g and 3 g of the compound example 3 of the present invention were added and dissolved to prepare an oily solution. 7.6 g of silver halide emulsion (EB-1) and 24 g of solid dispersion (KB-1) were added to this solution.
g was added, and the mixture was stirred at 10,000 rpm for 5 minutes using a 40φ dissolver while maintaining the temperature at 60 ° C. to obtain a photosensitive composition (PB-1) of W / O emulsion.

Preparation of Photosensitive Composition (PG-1) 45 g of pigment dispersion (GM-1) was added with (SV of (1P-4)).
-1) 9 g of 10% (wt%) solution, (RD-1) 1.
2g, (RD-3) 1.6g, (FF-3) (SV-
1) 2 g of 0.5% (wt%) solution, (ST-2) 0.
5 g and 4.5 g of Compound Example 4 of the present invention were added and dissolved to prepare an oily solution. 7.6 g of silver halide emulsion (EG-1) and solid dispersion (KB-1) 2 were added to this solution.
Add 4 g and stir at 10000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 60 ° C., W / O
An emulsion photosensitive composition (PG-1) was obtained.

Preparation of Photosensitive Composition (PR-1) 45 g of the pigment dispersion (GC-1) was added with (S) of (1P-4).
V-1) 9 g of 10% (wt%) solution, (RD-1)
1.2g, (RD-2) 1.6g, (FF-3) (S
V-1) 2 g of 0.5% (wt%) solution, (ST-1)
0.5 g and 4.5 g of Compound Example 5 of the invention are added,
An oily solution was prepared by dissolving. 7.6 g of a silver halide emulsion (ER-1) and a solid dispersion (KB-
1) 24 g was added, and while maintaining the temperature at 50 ° C., using a 40φ dissolver, stirring was performed at 10,000 rpm for 5 minutes,
A photosensitive composition (PR-1) of W / O emulsion was obtained.

[0099]

[Chemical 5]

[0100]

[Chemical 6]

[0101]

[Chemical 7]

Photosensitive microcapsule dispersion (CB-
Preparation of 1) 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
To this solution, 50 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. This mixed solution was added to the above-mentioned photosensitive composition (PB-1) and stirred at 60 ° C. for 20 minutes at 6000 rpm using a 40φ dissolver, and
An emulsion in the form of a / O / W emulsion was obtained. Separately, 5% of 37% aqueous formaldehyde solution was added to 31.5 g of melamine.
2.2 g and 170.3 g of water were added, the mixture was heated to 60 ° C. and stirred for 30 minutes to obtain a transparent aqueous solution of the melamine-formaldehyde initial condensate.

25 g of this initial condensate was added to the emulsion in the state of the above W / O / W emulsion cooled to 40 ° C.,
The pH was adjusted to 5.0 with 2N sulfuric acid while stirring at 1200 rpm with a propeller blade. Next, the temperature of this liquid was raised to 70 ° C. in 30 minutes, and further stirred for 30 minutes.
To this was added 10.3 g of a 40% aqueous solution of urea, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring was continued at 70 ° C. for another 40 minutes. This solution was cooled to 40 ° C., 9 g of a 3% aqueous solution of κ-carrageenan was added, the mixture was stirred for 10 minutes, and the pH was adjusted to 6.5 with a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB- 1) was prepared.

Photosensitive microcapsule dispersion (CG-
Preparation of 1) 36 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
To this solution, 60 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. The photosensitive composition (PG-1) was added to this mixed solution, and the mixture was stirred at 60 ° C. for 20 minutes at 6000 rpm using a 40φ dissolver, and was then mixed with W.
An emulsion in the form of a / O / W emulsion was obtained. Polymer (2P-4) Polyvinylbenzene potassium sulfinate-co-acrylamide Polymer (2P-2) Polyvinylpyrrolidone K-90 Polymer (PC-3) PVA KL318 (Kuraray Co., Ltd., carboxy-modified PVA)

4 g of 15% aqueous solution of polymer (2P-4)
46g of water was added to the mixture, and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
Adjusted to. To this solution, 50 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. The above photosensitive composition (PR-1) was added to this mixed solution, and the mixture was stirred at 60 ° C. for 20 minutes at 6000 rpm using a 40φ dissolver to obtain an emulsion state emulsion. Apart from
52.2 g of 37% aqueous formaldehyde solution and 170.3 g of water were added to 31.5 g of melamine, and the mixture was heated to 60 ° C. and stirred for 30 minutes to obtain a transparent aqueous solution of melamine-formaldehyde initial condensation product.

25 g of this initial condensate was added to the emulsion in the state of the emulsion cooled to 40 ° C., and the pH was adjusted with 2N sulfuric acid while stirring with a propeller blade at 1200 rpm.
Adjusted to 5.0. Then, this solution is heated to 70 ° C for 30 minutes.
The temperature was raised to 0 and the mixture was further stirred for 30 minutes. To this was added 10.3 g of a 40% aqueous solution of urea, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring was continued at 70 ° C. for another 40 minutes. This solution was cooled to 40 ° C., 9 g of a 3% aqueous solution of κ-carrageenan was added, the mixture was stirred for 10 minutes, and the pH was adjusted to 6.5 with a 2N aqueous sodium hydroxide solution to prepare a photosensitive capsule dispersion (CG-1). ) Was prepared.

Then, in the preparation of (CB-1), (P
A photosensitive microcapsule dispersion (CR-1) was prepared in the same manner except that (PR-1) was used instead of B-1).

Oil-based liquid-containing microcapsule dispersion (CA
-1) Preparation of Metroses 65SH50 (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxypupylmethylcellulose) in 100 g of 3% aqueous solution, 100 g of the polymerizable compound (MN-1) and Takenate D11.
A mixture of 5 g of 0N (manufactured by Takeda Pharmaceutical Co., Ltd., polyisocyanate) was added, and a 40φ dissolver was used at 40 ° C./min.
The mixture was stirred at 00 revolutions for 5 minutes to obtain an emulsion in the state of O / W emulsion. This solution was stirred at 1200 ° C. for 1 hour at 60 ° C. using a propeller blade to obtain MN-1 containing polyurea capsules. The volume average particle diameter was 9.2μ.

Photosensitive material 101 15 g of photosensitive microcapsules (CB-1), (CG
-1) 15 g, (CR-1) 15 g, and (CA
-1) is mixed with 25 g, and 5% of the surfactant (WW-1)
An aqueous solution (6.5 g) and water (15 g) were added, the mixture was stirred at 40 ° C. for 10 minutes, and this solution was filtered through a 44 μm filter cloth to prepare a capsule coating solution 101.

[0110]

[Chemical 8]

This coating solution was applied to the aluminum vapor-deposited surface of a support obtained by vapor-depositing aluminum on a polyethylene terephthalate film having a thickness of 25 μm by an extrusion method.
A photosensitive material 101 was prepared by coating the coating material so that the coating amount was 140 cc / m ² , drying it at 60 ° C., and winding it under the condition of 25 ° C. and 60% so that the coated surface was the back side.

Preparation of image receiving material (RS-1) Calcium carbonate (PC700, manufactured by Shiraishi Industry Co., Ltd.) 24
0 g, surfactant (Poise 520, manufactured by Kao Corporation) 5.
After stirring and mixing 6 g and 354.4 ml of water, a disperser (trade name: Ultra Disperser (LK-41
Type), manufactured by Yamato Scientific Co., Ltd.) and dispersed at 8000 rpm for 3 minutes. 52 g of this dispersion and 10% polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.) aqueous solution 4
0g and 1% of surfactant (WW-3)
An aqueous solution (4 ml) and water (22 ml) were added to prepare a coating solution for forming an image receiving layer.

This coating solution was weighed 80 g / m ^{2 on} a paper support (as a fiber length distribution defined by JIS-P-8207, the sum of the weight% of the 24 mesh residue and the weight% of the 42 mesh residue was 30). A paper support having a fiber length distribution such that the fiber length distribution is from 60 to 60% [JP-A-63-18623]
No. 9)]) was uniformly coated on the surface of the plate at 65 g / m ² and then dried at 60 ° C. to prepare an image receiving material (RS-1).

[0114]

[Chemical 9]

Example 2 In the preparation of the pigment dispersion (GM-1) in Example 1, 45 g of Hostaperm Pink E02 (trade name, manufactured by Hoechst) was used instead of Rubin F6B, and the photosensitive composition was used. Photosensitive material 102 was prepared in the same manner as in Example 1 except that 15 g of Compound Example 1 of the present invention was used instead of Compound Example 4 of the present invention in the preparation of (PG-1).

Example 3 In preparation of the pigment dispersion (GM-1) in Example 1, Microlith Magenta 2BA was used instead of Rubin F6B.
And (SV-1) (23 g) to prepare a dispersion, and when the photosensitive composition is prepared, 48 g of the above dispersion is used, and when the pigment dispersion (GY-1) is prepared, chromofine yellow 5900 Instead, Seika First 2300 (trade name, manufactured by Dainichiseika Co., Ltd.) was used, and the photosensitive composition (PR-
1) EFKA instead of Compound Example 5 of the present invention at the time of preparation
A light-sensitive material 103 was prepared in the same manner as in Example 1 except that 11 g of -400 (trade name, manufactured by EFKA Chemicals, active ingredient 40%) was used.

Example 4 In the preparation of the pigment dispersion (GY-1) in Example 1, Seikafast 2400 (trade name, manufactured by Dainippon Seika Chemicals Co., Ltd.) was used in place of Chromofine Yellow 5900, and In preparing the composition, for (PB-1), instead of Compound Example 3 of the present invention, EFKA-400 (trade name, E
Made by FKA Chemicals, active ingredient 40%) 8 g, (P
Regarding G-1), instead of Compound Example 4 of the present invention, E
FKA-401 (trade name, manufactured by EFKA Chemicals,
Example 1 except that 16 g of active ingredient 50%) is used.
A light-sensitive material 104 was prepared in the same manner as in.

Comparative Example A photosensitive material 105 for comparison was prepared in the same manner as in Example 1 except that Compound Examples 3, 4 and 5 of the present invention were not added when the photosensitive composition was prepared in Example 1. did.

Image formation Using a halogen lamp adjusted to a color temperature of 3100 ° K,
A black silver image was continuously exposed through a wedge having a transmission density varying from 0 to 4.0 under exposure conditions of 5000 lux and 1 second. Immediately after the exposure, the opposite side of the coated surface of the light-sensitive material was brought into close contact with a drum heated to 150 ° C. or 155 ° C. and heat-developed for 1.0 second. After 30 seconds, superimpose the image receiving material (RS-1) and the coated surfaces on top of each other and 2 cm /
The image receiving material was peeled off from the photosensitive material immediately after passing through a pressure roller (surface temperature 70 ° C.) having a diameter of 3 cm and a pressure of 250 kg / cm ² at a speed of 2 seconds. The density (D1 150%) of the maximum density (Dmax 150) of the image obtained by heating at 150 ° C.
50) is measured and the exposure is measured to give 15 at the same exposure.
The image density (D155) obtained by heating at 5 ° C. was determined, and ΔD = (D150−D155) / D150 was used as a measure of image stability against temperature fluctuations in the heat development processing. (The smaller ΔD is, the less likely it is to be affected by temperature fluctuations in the heat development processing.) The results obtained are shown in Table 1.

[0120]

[Table 1]

From the above results, it can be seen that with the light-sensitive material of the present invention, even if there is a temperature change during the heat development processing, the density change is small and therefore a stable image can be obtained. Further, the light-sensitive materials 101 to 104 of the present invention showed little deterioration even when stored for a long time before the development processing, and stable and clear images were obtained. Furthermore, although the details of the mechanism of action are not clear, it was found that the sensitivity tends to be higher in any of the examples as compared with the photosensitive material 105 as the comparative example.

Claims (2)

[Claims] 1. A photothermographic material having a photosensitive layer containing at least a silver halide, a reducing agent, a polymerizable compound and a base precursor on a support, wherein the photosensitive layer has an amino group and / or an imino group in the same molecule. A photothermographic material comprising a group-containing polyacrylate and / or a polyacrylamide oil-soluble polymer compound. 2. A silver halide, a reducing agent, a polysynthetic compound,
The base precursor and the polymer compound are contained in microcapsules, and the microcapsules further contain a color image forming substance.
The photothermographic material described in 1.