JPH05107750A - Heat developable photosensitive material and image forming method - Google Patents

Abstract

PURPOSE:To increase the density of transferred images by using the photosensitive material contg. photosensitive microcapsules contg. silver halides, reducing agents, etc., and another microcapsules contg. an oily liquid and having heat permeable walls. CONSTITUTION:Photosensitive layers contg. the photosensitive microcapsules contg. the oily liquid contg. at least the silver halides, reducing agents, polymerizable compds., pigments and base precursors and having 5 to 20mum average particle size (volume average size) together with another microcapsules contg. the oily liquid and having the heat permeable walls are provided on a base. A silver chloride, silver bromide, silver iodide or any among silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide, are usable as the silver halide of this photosensitive material. The silver halide particles in the photographic emulsions may be the particles having regular crystal systems, such as cube, octahedron, docecahedron, and fourteen-faced polygon or the particles having crystal defects, such as twins, or may be the composite type thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material having a photosensitive microcapsule on a support and an image forming method.

[0002]

2. Description of the Related Art A light-sensitive material having microcapsules (photosensitive microcapsules) containing a silver halide, a reducing agent, a polymerizable compound and a color image-forming substance on a support is described in JP-A-61-275742. Has been done. In this photosensitive material, after the microcapsules are cured into an image by imagewise exposure and heat development, the uncured microcapsules are ruptured by superimposing the photosensitive material and the image receiving material and pressurizing them to form a color image-forming substance (leuco dye). By transferring the dye) to the image receiving material, a color image can be obtained. When a pigment is used as a color image-forming substance in the above light-sensitive material, the fading property of the obtained image is improved, but such a light-sensitive material is disclosed in JP-A-62-187.
No. 346.

Further, a light-sensitive material containing a base precursor in a light-sensitive microcapsule as an image forming accelerator is disclosed in JP-A-64-322151 and JP-A-1-2636.
No. 41, which can provide a clear image in a short time. A light-sensitive material which uses a pigment as a color image-forming substance and further has microcapsules containing a base precursor on a support is already known, and is described in JP-A-3-69953.

[0004]

When a transfer image is obtained by using a pigment as a color image-forming substance and a photosensitive material having microcapsules encapsulating a base precursor on a support, a transfer density is low. The densities of the yellow, magenta, and cyan monochromatic areas were insufficient. This tendency was remarkable especially when the transfer pressure was lowered. Therefore, an object of the present invention is to use a pigment as a color image-forming substance and a photosensitive material having microcapsules containing a base precursor on a support, and transfer density, particularly yellow, magenta, and cyan single color portions. Is to be good.

[0005]

The object of the present invention is as follows.
At least silver halide, reducing agent, polymerizable compound, pigment,
And an oily liquid containing a base precursor, and a photosensitive microcapsule having an average particle size (volume average diameter) of 5 to 20 μm, and another microcapsule containing an oily liquid and having a wall having thermal permeability. It was achieved by a photothermographic material having a photosensitive layer containing on a support. When the light-sensitive material of the present invention is imagewise exposed and then heat-developed, the microcapsules containing the silver halide, the reducing agent, the polymerizable compound, the pigment, and the base precursor are imagewise cured, and a microcapsule containing another oily liquid. The internal phase is released from the capsule through the wall. When this is superposed on the image-receiving material and transferred under pressure or pressure-heated transfer, the above-mentioned released oily liquid acts as a transfer aid, increasing the transfer amount, resulting in an increase in transfer density and further a single color of yellow, magenta, and cyan. The color of the part was also good.

[0006] Conventionally, as an example of mixing a capsule other than the photosensitive microcapsules of this type, Japanese Patent Laid-Open No. 62-2 is known.
No. 09524 describes an example of using a urea / resorcin / formalin capsule containing an organic solvent (dibutyl phthalate) that is miscible with a polymerizable compound, but in this example, it bursts at the time of transfer to release the internal phase, It is intended to act as a transfer aid. In such a case, the particle size of another capsule is usually equal to or larger than that of the photosensitive microcapsule. However, when a large capsule was mixed, the transferred image tended to be rough. The separate capsule used in the present invention does not necessarily have to be ruptured at the time of transfer and releases the internal phase through the wall at the time of thermal development, and thus may have a small particle size. Therefore, the obtained image is also less rough. As described above, the average particle size of the separate capsules is preferably smaller than that of the photosensitive microcapsules having an average of 5 to 20 μm. However, it is preferably 1 μm or more.

It is preferable that the wall of the separate capsule containing the oily liquid does not show permeability at room temperature but quickly exhibits heat permeability at the heat development temperature of the light-sensitive material. Examples of the microcapsules having such a clear thermal response are JP-A-59-91438 and JP-A-59-190.
Microcapsules composed of polyurea or polyurethane resin walls as described in Japanese Patent No. 886 are known and can be preferably used in the present invention. The oily liquid contained in the inner phase of another capsule is not particularly limited. However, since the light-sensitive material of the present invention is used after being developed by heating, it is preferably a liquid having a high boiling point that hardly volatilizes during heating. You may use the same thing as the polymeric compound used for a photosensitive microcapsule. The separate capsules are preferably used in a proportion of 10% to 200%, more preferably 30% to 150%, with respect to the photosensitive microcapsules.

The silver halide, reducing agent, polymerizable compound, pigment, base precursor, microcapsule and support used in the photothermographic material of the invention will be described below. In the light-sensitive material of the present invention, as silver halide, any grains of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide are used. be able to. The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra, dodecahedrons and tetradecahedrons, grains having an irregular crystal system such as spheres and plates. It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.0
Fine particles of 1 micron or less or large size grains having a projected area diameter of up to about 10 microns may be used, and polydisperse emulsions may also be used in US Pat. Nos. 3,574,628 and 3,65.
The monodisperse emulsions described in 5,394 and British Patent 1,413,748 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 Science and Engineering.
Engineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157. 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, or may be joined with a compound other than silver halide such as rhodan silver and lead oxide. Further, two or more kinds of silver halide grains having different halogen compositions, 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) No1.
7643 (Dec. 1978), pp. 22-23, "I.
"Emulsion preparation and types", and No. 18716 (November 1979), page 648, etc. The silver halide emulsion is usually prepared by physical ripening or chemical ripening. The ones that have been aged and spectrally sensitized are used, and the additives used in such a process are Research Disclosure No. 176.
43 and No. 18716, and the relevant parts 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 to 24, page 648, right column ~ Supersensitizer, page 649, right column, antifoggant 24- See page 25, page 649, right column and stabilizers. For details of the above silver halide emulsion and photographic additives, refer to "Public Technology No. 5" (Aztec Co., Ltd.,
(Published March 22, 1991) 2 to 17 pages. The amount of silver halide used is 0.001 to 10 g, preferably 0.05 to ² g, in terms of silver per 1 m ² of the light-sensitive material. 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 that can be used in the light-sensitive material 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 and 5-amino. Uracils, 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-
Sulfonamide indanones, 4-sulfonamido-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. 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 it is generally 0.1 to 1500 mol%, preferably 10 to 300 mol% with respect to the silver salt.

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. A compound having an ethylenically unsaturated group is particularly preferable. The compound having an ethylenically unsaturated group that can be used in the light-sensitive material, acrylic acid and its salts, acrylic acid esters,
Acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-
Examples include vinyl heterocycles, allyl ethers, allyl esters and their derivatives.

Specific examples of preferable polymerizable compounds that can be used in the light-sensitive material include acrylic acid esters, such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxyethyl. Acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylenated bisphenol A diacrylate,
2- (2-hydroxy-1,1-dimethylethyl) -5
-Hydroxymethyl-5-ethyl-1,3-dioxane acrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5,5-dihydroxymethyl-1,3-dioxane triacrylate, propylene of trimethylolpropane Examples thereof include triacrylate of an oxide adduct, hexaacrylate of a caprolactone adduct of dipentaerythritol, polyacrylate of hydroxypolyether, polyester acrylate and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Examples thereof include pentaerythritol tetramethacrylate and dioxymethacrylate of polyoxyalkylenated bisphenol A.

The above polymerizable compounds may be used alone or in combination of two or more kinds. Regarding a light-sensitive material in which two or more kinds of polymerizable compounds are used in combination, see JP-A-62-210445.
It is described in the official gazette. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the reducing agent described above can also be used as the polymerizable compound.

As the pigment used in the present invention, in addition to commercially available pigments, known pigments described in various documents can be used. Regarding the literature, the Color Index (C.
I. ) Handbook, "Latest Pigment Handbook" edited by Japan Pigment Technology Association (1
1977), "Latest pigment application technology" CMC Publishing (19
1986, "Printing ink technology" (CMC Publishing, 198)
4 years) etc. For details of the pigment that can be used in the present invention and the technology for using the pigment, refer to the above-mentioned "Known technology No. 5" 41
Pp.-49. The pigment is a polymerizable compound 1
It is preferable to use 5 to 60 parts by weight with respect to 00 parts by weight.

As the base precursor that can be used in the light-sensitive material of the present invention, base precursors of inorganic bases and organic bases (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, 59-180537, 59-195237, 61-32844 and 61.
-36743, 61-51140, 61-52.
No. 638, No. 61-52639, No. 61-53631.
No. 61-53634, No. 61-53635, No. 61-53636, No. 61-53637, No. 61-
53638, 61-53639, 61-536.
40, 61-55644, 61-55645.
No. 61, No. 61-55646, No. 61-84640, No. 61-107240, No. 61-2119950, No. 6
1-251840, 61-252544, 61
-313431, 63-316740, 64-
No. 68746 and Japanese Patent Application No. 1-54452, salts of organic acids and bases that are decarboxylated by heating.
Further, JP-A-59-157637 and JP-A-59-1669.
The compounds described in JP-A-43-63 and JP-A-63-96159, which eliminate a base by heating, can be 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. Since the base precursor used in the light-sensitive material of the present invention is contained in microcapsules, it is disclosed in Japanese Patent Application No. 2-270159.
Particularly preferred are base precursors consisting of a salt of a carboxylic acid and an organic base having a solubility of 1% or less in water and a polymerizable compound at 25 ° C.

In the present invention, when the base precursor is contained in the microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used (Japanese Patent Application Laid-Open No. 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
No. 8964, Japanese Patent Application No. 1-182245, Japanese Patent Application No. 1-1
No. 60148, each publication and specification) When dispersing the base precursor in water, it is preferable to use a nonionic or amphoteric water-soluble polymer.

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. Further, as the amphoteric water-soluble polymer,
Mention may be made of gelatin.

The above water-soluble polymer is preferably contained in the base precursor in a proportion of 0.1 to 100% by weight, and more preferably in a proportion of 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.

No particular limitation is imposed on the encapsulation method that can be used for the photosensitive microcapsules of the present invention, and various known techniques can be applied.
It is described in detail on pages 88 to 98. 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 microcapsules is 5 to 20 μm, preferably 7 to 15 μm. The particle size distribution of microcapsules is described in JP-A-63 / 1988.
As in the light-sensitive material described in JP-A-5334, it is preferable that the light-sensitive material is uniformly distributed over a certain value. The film thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the light-sensitive material described in JP-A-63-81336.

When the silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably 1/5 or less of the average size of the microcapsules, and preferably 1/10 or less. More preferably, 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. Regarding a light-sensitive material containing a silver halide in the wall material of the microcapsule, JP-A-62-62
No. 169147.

In the production of the photosensitive microcapsules of the present invention, an oily liquid comprising a polymerizable compound containing a silver halide, a reducing agent, a pigment and a base precursor is dispersed in an aqueous medium to form an outer shell of the capsule. The aqueous medium preferably 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, preferably 20 to 90% by weight, based on the aqueous medium.
Is more preferable.

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. Examples thereof include styrene copolymers and maleic anhydride / isobutylene copolymers. 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.

As described above, the wall of the thermoresponsive microcapsule of the present invention is preferably made of polyurea resin or polyurethane resin. These capsules are made by reacting the polyisocyanate contained in the oily liquid with water, polyamines, or polyols. Polyisocyanates, polyamines and polyols used in this case are described in US Pat. No. 3,135,7.
No. 16, No. 3,281,383, No. 3,468,92
No. 2, No. 3,773,695, No. 3,793,268
No. 48/40347 and 49-24159
JP-A-48-80191 and JP-A-48-84086, and they can also be used.

In order to reduce the solubility of the base precursor in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexylurea, octyl alcohol, dodecyl alcohol, stearyl alcohol, stearoamide, etc.-in the polymerizable compound, OH, -SO ₂ NH _2, -CONH
_{It is} also possible to add a compound having a hydrophilic group such as ₂ , ₂ , -NHCONH ₂ .

In the present invention, in addition to the reducing agent, known antioxidants for preventing oxidative deterioration of the polymerizable compound and for preventing oxygen oxidation during heat development can be used together with the polymerizable compound. 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
-Phenolic antioxidants such as -methylphenyl acrylate and 4,4'-thio-bis- (3-methyl-6-t-butylbutenol); 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 -Puspionic acid ester), 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, woodfree paper, baryta paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, 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 coat the support with a photosensitive layer,
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 the following thickness 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.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. 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 accelerating the transfer of the base or the base precursor, accelerating the reaction of the reducing agent and the silver salt, and accelerating the immobilization of the 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.

In the photosensitive material, a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized,
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 in 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 surface active agents can 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 a property of being decolorized by heating or irradiation with light may be contained in the photosensitive microcapsules. 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. Regarding a light-sensitive material using a dye having the property of being decolorized by heating or irradiation with light as described above, Japanese Patent Laid-Open No.
It is described in JP-A-3-974940.

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.
Carboxylic acids and phosphoric acids containing nitrogen described in JP-A No. 59-111636, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957.

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), JP-A-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 modes of use 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 specification of the series of photosensitive materials described above.

In the image forming method using the light-sensitive material of the present invention, it is general to use the image-receiving material together with the light-sensitive 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 of the image receiving material is not particularly limited, but like the support of the light-sensitive material, 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,
Examples thereof include films such as polystyrene, polycarbonate and polyethylene terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

When a porous material such as paper is used as the support of 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, sugar clay, talc , 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.

Examples of the polymer latex include styrene-butadiene copolymer latex, methylmethacrylate / butadiene copolymer latex, polymers of acrylic acid ester and / or methacrylic acid ester, copolymer latex, ethylene / vinyl acetate copolymer. 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.

The above binders may be used in combination of two or more kinds, and may also be used together in such a ratio that the two kinds of binders cause phase separation. As an example of such usage, JP-A-1-154789
There is a description in the official gazette. The average particle size of the white pigment is 0.
1 to 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 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. The image receiving material having the image receiving layer containing the thermoplastic compound fine particles as described above is described in JP-A Nos. 62-280071 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 imagewise exposure step in the image forming method of the present invention, simultaneously with imagewise exposure, or after imagewise exposure, heating the photosensitive material from the surface of the support not coated with a photosensitive layer, Then, 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 applying pressure will be described. 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 can be selected according to the photosensitive wavelength of silver halide (wavelength sensitized when dye sensitization is performed) and sensitivity.

Typical light sources include low-energy radiation sources such as natural light, ultraviolet light, visible light, infrared light, 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 thus 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 photography 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, or scanning exposure can 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.

Upon exposure of a color image, LEDs, lasers, fluorescent tubes and the like are used in combination according to the color sensitivity of the light-sensitive material, but a plurality of the same materials may be used in combination, or different kinds of materials 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 monochrome 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 the area 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, etc. can be applied to the photosensitive material to heat them in a non-contact state.

In the image forming method of the present invention, thermal development is carried out by heating the photosensitive material from the surface 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. Further, the heat development by heating is carried out simultaneously with or after the imagewise exposure, but it is preferable to perform the heating after 0.1 seconds or more has passed after the imagewise exposure. Heating temperature is generally 60 ℃
To 250 ° C, preferably 80 ° C to 180 ° C,
The heating time is between 0.1 and 20 seconds, preferably between 0.5 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. When 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 the microcapsules. It is also possible to decompose the agent by heating or irradiating it 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 pigment is transferred to the image-receiving material together with the unpolymerized polymerizable compound 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. Then, 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 wiped with an air gun or the like, or can be pressurized with an ultrasonic wave 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 light-sensitive materials for copying machines. It is possible to create compact and inexpensive image forming systems such as copiers, printers, and simple printers.

[0066]

【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 to adjust the pH to 3.2.

After adding 10 mg of (AGS-1) to this solution, the solution I and the solution II were kept at pAg = 8.5 by the control double jet method at 60 ° C., and at the same time, the solution I was consumed for 45 minutes. Added. PH after addition
Was adjusted to 6.0 with 1N NaOH and (AZ-1) 6.4
mg and (AZ-2) 4.8 mg were added and the mixture was aged at 60 ° C. for 60 minutes. 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 poly (isobutylene-co-maleate monosodium) was added, precipitated, washed with water and desalted, and then 6 g of lime-processed gelatin was added to dissolve, and further 3 of (ATR-3) was added. The pH was adjusted to 6.2 by adding 1.5 cc of a 5% aqueous solution. Average particle size 0.24μ
m, monodisperse silver iodobromide emulsion having a coefficient of variation of 20% (EB-1)
550 g 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 the addition time of Solution I and Solution II was 15 minutes, and instead of (SB-1) (SG-1)
450 mg was added. Monodisperse silver iodobromide emulsion (EG-1) 550 having an average grain size of 0.18 μm and a coefficient of variation of 20%.
g 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.

[0072]

[Chemical 1]

[0073]

[Chemical 2]

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 at 0 rpm for 30 minutes, adjust the pH to 6.5 with 2N sulfuric acid and adjust the base precursor (BG
A solid dispersion (KB-1) of -1) was obtained.

[0075]

[Chemical 3]

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 Co., Ltd.) was mixed, and an Eiger Motor Mill (Eiger. (Manufactured by Engineering Co., Ltd.) was stirred at 5000 rpm for 1 hour 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) Polymerizable compound (MN-1) (255 g) was mixed with Microlith Magenta 174K (trade name, manufactured by Ciba Geigy) and (SV-1) 23 g, and a dissolver was used. Then, the mixture was stirred at 5000 rpm for 30 minutes, and the dispersion (GM-
1) was obtained.

Preparation of Pigment Dispersion (GC-1) Polymerizable compound (MN-1) (255 g), copper phthalocyanine (CI Pigment 15) (45 g), Solsperse 500
0 (manufactured by ICI) 1.13 g, Sols Perth 24000
3.37 g (manufactured by ICI) was mixed and stirred for 1 hour at 5000 rpm using an Eiger motor mill (manufactured by Eiger Engineering) to obtain a dispersion (GC-1).

Preparation of Photosensitive Composition (PB-1) 180 g of pigment dispersion (GY-1) was added with (S of 1P-4).
V-1) 36 g of 10% (wt%) solution, (RD-1)
4.6 g, (RD-3) 18.6 g, (FF-3) (SV-1) 0.5% (wt%) solution in 4 cc and (S).
2 g of T-1) was added and dissolved to prepare an oily solution.
To this solution, 30 g of silver halide emulsion (EB-1) and 96 g of solid dispersion (KB-1) were added, and the mixture was stirred at 8000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 60 ° C. A photosensitive composition (PB-1) of W / O emulsion was obtained.

Preparation of Photosensitive Composition (PG-1) Pigment dispersion (GM-1) was added to 194 g of (1P-4) (S
V-1) 36 g of 10% (wt%) solution, (RD-1)
4.6 g, (RD-3) 12.4 g, (SV-1) 0.5% (wt%) solution of 8 cc and polyethylene glycol 2000 2 g were added and dissolved to prepare an oily solution. did. Silver halide emulsion (E
G-1) (50 g) and solid dispersion (KB-1) (96 g) were added, and the mixture was stirred at 8000 rpm for 5 minutes using a 50φ dissolver while maintaining the temperature at 60 ° C. to prepare a photosensitive composition of W / O emulsion. (PG-1) was obtained.

Preparation of Photosensitive Composition (PR-1) To 180 g of pigment dispersion (GC-1), 36 g of 10% (wt%) solution of (SV-1) of (1P-4), (RD-
1) 4.6 g, (RD-2) 12.4 g, (FF-3)
(SV-1) 0.5% (wt%) solution of 8 cc and (ST-1) 2 g were added and dissolved to prepare an oily solution.

A silver halide emulsion (ER-1) was added to this solution.
30 g and 96 g of the solid dispersion (KB-1) were added, and 50
6 minutes per minute using a 40φ dissolver while keeping the temperature at ℃
The mixture was stirred at 000 rpm for 5 minutes to obtain a W / O emulsion photosensitive composition (PR-1).

[0083]

[Chemical 4]

[0084]

[Chemical 5]

[0085]

[Chemical 6]

Photosensitive microcapsule dispersion (CB-
Preparation of 1) Water was added to 18 g of a 12% aqueous solution of the polymer (2P-1).
2 g was added and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. A 10% aqueous solution of polymer (2P-2) 24
0 g 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. at 8000 rpm for 20 minutes using a 40φ dissolver to obtain an emulsion in the form of a W / O / W emulsion. Separately, 52.2 g of a 37% aqueous solution of formaldehyde 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 a melamine-formaldehyde initial condensation product.

132 g of this initial condensate was added to the emulsion in the W / O / W emulsion state cooled to 40 ° C., and 32 cc of 1N sulfuric acid was added while stirring at 1200 rpm with a propeller blade. 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, 54g of 40% aqueous solution of urea was added, and 24cc of 1N sulfuric acid was added.
Stirring at 70 ° C. was continued for another 40 minutes. 60 in this liquid
36 g of a 3% aqueous solution of K-carrageenan at 10 ° C was added, and
After stirring for 1 minute and cooling to 50 ° C., 40 cc of 1N aqueous sodium hydroxide solution was added to prepare a photosensitive microcapsule dispersion (CB-1). Coulter Multisizer
The volume average particle diameter measured by II (Coulter) is 12.3.
It was μ.

Photosensitive microcapsule dispersion (CG-
Preparation of 1) 93 g of water was added to 27 g of a 12% aqueous solution of the polymer (2P-1).
g, and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid.
280 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid.
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 with a 50φ dissolver at 60 ° C. for 20 minutes at 8000 rpm.
An emulsion in the form of a W / O / W emulsion was obtained. Then, a photosensitive microcapsule dispersion liquid (CG-1) was prepared in the same manner as the preparation of (CB-1). Volume average particle size is 1
It was 1.8μ.

Photosensitive microcapsule dispersion (CR-
Preparation of 1) Water was added to 18 g of a 12% aqueous solution of the polymer (2P-1).
2 g was added and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. A 10% aqueous solution of polymer (2P-2) 24
0 g was added and mixed at 60 ° C. for 30 minutes. The above-mentioned photosensitive composition (PR-1) was added to this mixed solution, and the mixture was stirred at 60 ° C. for 20 minutes at 8000 rpm using a 40φ dissolver to obtain an emulsion in the form of a W / O / W emulsion.

Then, a photosensitive microcapsule dispersion liquid (CR-1) was prepared in the same manner as in the preparation of (CB-1).
The volume average particle diameter was 12.5μ. Polymer (2P-2) Polyvinylpyrrolidone K-9
0 Polymer (2P-4) Polyvinylbenzenesulfinate potassium-co-acrylamide

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 at 25 ° C.
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. Preparation of (CA-2) after dispersion of oily microcapsules (CA-1) In the preparation of (CA-1), except that the stirring point at 5000 rpm is 2000 rpm at the time of obtaining an O / W emulsion. In the same manner, (CA-2) was prepared after dispersion of oily liquid-containing microcapsules. The volume average particle diameter was 14.3μ.

Preparation of photosensitive materials 101, 102 and 103 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)
6.5 g of an aqueous solution was added and mixed. This liquid is 25μ thick
The polyethylene terephthalate film was coated with aluminum on the aluminum vapor-deposited surface of the support by an extrusion method so that the coating amount was 120 cc / m ^2, and dried to prepare a light-sensitive material 101 of the present invention. Further, in the preparation of the photosensitive material 101, (CA-1) 25 g
A light-sensitive material 102 was prepared in exactly the same manner except that (CA-2) 25 g was used instead of. In addition, (CA-
1) Using 25 g of water instead of 25 g, a light-sensitive material 103 was similarly prepared.

[0093]

[Chemical 7]

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 applied to a paper support having a basis weight of 80 g / m ² (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 calculated as follows. A paper support using atoms having a fiber length distribution such as 30 to 60% [JP 63-18623 A].
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).

[0096]

[Chemical 8]

Image formation Using a halogen lamp in which the light-sensitive materials 101 to 103 are adjusted to a color temperature of 3100K, transparent yellow, magenta,
An exposure of 2000 lux for 1 second was made through a wedge having a cyan part and a part of the transmission density which varies continuously from 0 to 4.0. After 5 seconds from exposure, the opposite side of the coated surface of the photosensitive material was brought into close contact with a drum heated to 150 ° C. and heat-developed for 1 second, and then the image receiving material (RS-1) and the coated surface were superposed. At a speed of 2 cm / sec, a diameter of 3 cm,
Pressure roller with a pressure of 220 kg / cm ² (surface temperature 70 ° C)
Passed through. When the image receiving material was peeled off from the light-sensitive material immediately after passing, a positive image was obtained on the image receiving material. The results of measuring the temperature of this image with X-Rite 310 are shown in Table 1.

[0098]

[Table 1]

From Table 1, it can be seen that the light-sensitive material of the present invention has a high transfer density and is excellent in the density of yellow, magenta and cyan. When the photosensitive material 102 is used,
From No. 101, it was found that the grain size was slightly larger in the intermediate density portion, and the particle size of the heat-permeable microcapsules was smaller than that of the photosensitive microcapsules in terms of roughness.

Example 2 Using the light-sensitive materials 101 to 103, an image formation based on a reflection original was carried out using the apparatus shown in FIG. When 101 or 102 was used, a clear image was obtained, but in 103, the transfer density was low and the image was poor.

[Brief description of drawings]

FIG. 1 is a configuration diagram of an image forming apparatus used in a second embodiment.

[Explanation of symbols]

 1: Original Plate 2: Original Document 3: Lamp 4: Lens 5: Exposure Table 6: Photosensitive Member 7: Cartridge 8: Conveying Roller 9: Heat Developing Device 10: Pressure Transfer Device 11: Take-up Shaft 12: Separation Roller 13: Supply Paper tray 14: Transfer member 15: Paper feeding device 16: Paper discharging roller 17: Paper discharging tray 18: Gas removing device

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 22, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

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 wiped with an air gun or the like, or can be pressurized with an ultrasonic wave generator, a piezoelectric element or the like. The pressure required for pressurization is 500 kg / cm ² or more, preferably 800 kg / cm ² or more. However, it is 5 when heating is also used at 40 ° to 120 ° C during pressurization.
It may be 00 kg / cm ² or less. More preferably 300
It is not more than kg / cm ² .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

Photosensitive microcapsule dispersion (CB-
Preparation of 1) Water was added to 18 g of a 12% aqueous solution of the polymer (2P-4).
2 g was added and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. A 10% aqueous solution of polymer (2P-2) 24
0 g 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. at 8000 rpm for 20 minutes using a 40φ dissolver to obtain an emulsion in the form of a W / O / W emulsion. Separately, 52.2 g of a 37% aqueous solution of formaldehyde 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 a melamine-formaldehyde initial condensation product.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0091

[Correction method] Change

[Correction content]

Oil-based liquid-containing microcapsule dispersion (CA
-1) Preparation of Metroze 65SH50 (manufactured by Shin-Etsu Chemical, hydroxypropylmethylcellulose) 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. Preparation of (CA-2) after dispersion of oily microcapsules (CA-1) In the preparation of (CA-1), except that the stirring point at 5000 rpm is 2000 rpm at the time of obtaining an O / W emulsion, (CA-1). In the same manner, (CA-2) was prepared after dispersion of oily liquid-containing microcapsules. The volume average particle diameter was 14.3μ.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction content]

Image formation Using a halogen lamp in which the light-sensitive materials 101 to 103 are adjusted to a color temperature of 3100K, transparent yellow, magenta,
An exposure of 2000 lux for 1 second was made through a wedge having a cyan part and a part of the transmission density which varies continuously from 0 to 4.0. After 5 seconds from exposure, the opposite side of the coated surface of the photosensitive material was brought into close contact with a drum heated to 150 ° C. and heat-developed for 1 second, and then the image receiving material (RS-1) and the coated surface were superposed. At a speed of 2 cm / sec and a diameter of 3 c
m and a pressure of 220 kg / cm ² through a pressure roller (surface temperature 70 ° C.). When the image receiving material was peeled off from the light-sensitive material immediately after passing, a positive image was obtained on the image receiving material. The results of measuring the density of this image with X-Rite 310 are shown in Table 1.

Claims (4)

[Claims] 1. A photosensitive microcapsule containing an oily liquid containing at least silver halide, a reducing agent, a polymerizable compound, a pigment and a base precursor, and having an average particle diameter (volume average diameter) of 5 to 20 μm, and A photothermographic material having a photosensitive layer on a support, which contains an oily liquid and also contains other microcapsules whose walls are heat permeable. 2. The photothermographic material according to claim 1, wherein the average particle diameter (volume average diameter) of the heat-permeable microcapsules is smaller than the average particle diameter of the photosensitive microcapsules. 3. The photothermographic material according to claim 1, wherein the walls of the heat-permeable microcapsules are made of polyurea resin or polyurethane resin. 4. A photosensitive microcapsule containing an oily liquid containing at least silver halide, a reducing agent, a polymerizable compound, a pigment and a base precursor, and having an average particle diameter (volume average diameter) of 5 to 20 μm, and After imagewise exposing a photosensitive material having a photosensitive layer on a support which contains another microcapsule having an oily liquid and whose walls are heat permeable, the photosensitive material is subjected to heat development at 80 ° C. or higher, and then the photosensitive material is used as an image receiving material. An image forming method in which an image is obtained by applying pressure transfer at a pressure of 500 kg / cm ² or less while heating at a temperature of 40 ° C. or more in a state of being superposed.