JPH05265203A - Photosensitive material - Google Patents

Abstract

PURPOSE:To improve the graininess of a transfer image and heighten the highest density by making the mean particle diameter of micro capsules, included in a near photosensitive layer to a base body, an assigned size. CONSTITUTION:Two layers or more of photosensitive layer including at least a polymerizing compound, silver halide, a reducing agent, and pigment are laminated on a base body, and the mean particle diameter of micro capsules, included in a near photosensitive layer to the base body, is made to be larger than the mean particle diameter of the micro capsules, included in a far side layer from the base body. In the case of color image forming photosensitive material using three kinds of capsules respectively containing three colors of yellow, magenta, and cyan, it is not always necessary for the respective particle diameters of the respective colors included in the near photosensitive layer to the base body to be larger than the respective particle diameters of the respective colors included in the far layer from the base body, and it is enough if the particle diameters of one color or two colors are same, and the rest two colors or one colors met the above mentioned size relation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material for image formation, which has photosensitive microcapsules on a support.

[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) onto the image receiving material, a color image can be obtained. On the other hand, in the light-sensitive material as described above,
When a pigment is used as a color image forming substance, the fading property of the obtained image is improved, but such a light-sensitive material is disclosed in JP-A-62-62.
No. 187346. Further, JP-A-3-69954 discloses a light-sensitive material for forming a color image using three types of microcapsules containing pigments of three colors of yellow, magenta and cyan, respectively. A problem with a transferred image formed using such a photosensitive material is graininess. As a method for improving this, there is a method described in Japanese Patent Application No. 3-268575, in which the surface roughness of the photosensitive material is set to a certain value or less. As one of the concrete methods, an attempt to reduce the volume average particle diameter of microcapsules is described. According to the research by the present inventor,
When the volume average particle diameter of the microcapsules is reduced, the graininess is certainly improved, but the transfer efficiency of the coloring material is lowered, and the maximum density (Dmax) tends to be lowered.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material comprising a support and a light-sensitive layer containing microcapsules containing at least a polymerizable compound, a silver halide, a reducing agent, and a pigment. To improve the graininess of the transferred image obtained by using it and to increase the maximum density (Dmax).

[0004]

The object of the present invention is as follows.
Two or more photosensitive layers containing microcapsules containing at least a polymerizable compound, a silver halide, a reducing agent, and a pigment are laminated on a support, and the microcapsules contained in the photosensitive layer on the side closer to the support. It has been achieved by a light-sensitive material characterized in that the volume average particle diameter is larger than the volume average particle diameter of the microcapsules contained in the photosensitive layer on the side remote from the support. According to the research conducted by the present inventor, the photosensitive layer has a multi-layered structure of two or more layers, and the volume average particle diameter of the microcapsules contained in the photosensitive layer on the surface side is reduced to reduce the surface roughness and reduce the graininess. Can be improved. Further, by increasing the volume average particle diameter of the microcapsules contained in the photosensitive layer on the support side, the transfer efficiency can be increased and the maximum density (Dmax) can be increased. That is, by using the light-sensitive material of the present invention, it is possible to improve the graininess and increase the maximum density (Dmax) at the same time.

The volume average particle diameter of the microcapsules is preferably at least 1 μm or more different between adjacent photosensitive layers. The volume average particle size of the microcapsules contained in the uppermost photosensitive layer is preferably in the range of 2 μm to 10 μm. The volume average particle diameter of the microcapsules contained in the lowermost photosensitive layer is 5 μm to 20 μm.
It is preferably in the range of. In the case of a color image forming photosensitive material using three types of microcapsules containing pigments of three colors of yellow, magenta and cyan, respectively,
It is not always necessary that the particle size of each of yellow, magenta, and cyan contained in the photosensitive layer on the side closer to the support be larger than the particle size of each of yellow, magenta, and cyan contained in the photosensitive layer on the side far from the support. Rather, the particle diameters of one color or two colors are the same, and the particle diameters of the remaining two colors or one color only have to satisfy the size relationship as described above.

The silver halide, reducing agent, polymerizable compound, pigment, microcapsule, support and other components used in the light-sensitive material of the present invention will be described below.

The silver halides, reducing agents, polymerizable compounds, pigments used in the light-sensitive material for color image formation of the present invention are described below.
The microcapsule, support and other components will be described. 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 the photographic emulsion are cubic,
Those having regular crystals such as octahedron, dodecahedron and tetradecahedron, those having an irregular crystal system such as spheres and plates, those having crystal defects such as twin planes, or A composite form of them may be used. The grain size of silver halide is about 0.
Fine particles of less than 01 micron 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 23-24, 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 for 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, commercially available pigments and 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.

In the light-sensitive material of the present invention, a base precursor can be used as an image formation accelerator. 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. Details of these base precursors and the techniques for using them are described in "Public Technology No. 5," pages 55-86.

Preferred base precursors are JP-A Nos. 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-
68746 and 64-54452, salts of organic acids and bases which are decarboxylated by heating, and JP-A-59-157637 and 59-16694.
Examples thereof include compounds capable of eliminating a base by heating as described in JP-A Nos. 3 and 63-96159.

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. 64-32521, 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
8964, JP-A Nos. 2-146041, and 3-2.
No. 5444). Here, in 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, 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.

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 type 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.

When the silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably ⅕ or less, and preferably ⅕ or less of the average size of the microcapsules. 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, when 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 the 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.

In the present invention, for the purpose of accelerating transfer, it is preferable to use microcapsules containing an oily liquid in combination, and in this capsule, the wall is preferably made of polyurea resin or polyurethane resin. These capsules, polyisocyanate contained in the oily liquid,
Made by reacting with water, polyamines, or polyols. Regarding the polyisocyanate, polyamine, and polyol used in this case, US Pat.
35,716, 3,281,383, 3,46
8,922, 3,773,695, 3,79
No. 3,268, Japanese Patent Publication Nos. 4040347, 49-2
4159, JP-A-48-80191, and JP-A-48-84.
No. 086, and they can also be used. The volume average particle diameter of the oil-based liquid encapsulation capsule is 1 μm to
It is preferably in the range of 20 μm.

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 and the like are added 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 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 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.

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 transfer of a base or base precursor, promoting reaction of a reducing agent and a silver salt, and promoting 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.

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 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-62-17.
No. 3463, No. 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 light irradiation 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 with 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 the usage thereof are also described in the application specification regarding the series of photosensitive materials described above, 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 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 or a polymer soluble in an organic solvent 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, methyl methacrylate / 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.

As the method of using the above-mentioned binder, two or more kinds may be used in combination, and further, two kinds of binders may be used in a ratio such that phase separation occurs. 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 / m ² , preferably 0.5 g to 3
It is in the range of 0 g / m ² . 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 200 ° C.
The following is preferable. 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 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, 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. However, 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 of the support on which the photosensitive layer is not coated, and 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 photosensitive 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 light-sensitive material and the image-receiving material may be sandwiched between press plates such as a presser, or pressure may be applied while being conveyed 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 a color photographing and printing light-sensitive material, a printing light-sensitive material, a computer graphic hard copy light-sensitive material, and a copying machine light-sensitive material. It is possible to create compact and inexpensive image forming systems such as copiers, printers, and simple printers.

[0065]

【Example】

Example 1 Preparation of Silver Halide Emulsion (EB-1) 24 g of lime-treated inert gelatin was added to 900 cc of distilled water and dissolved at 40 ° C. for 1 hour, and then KBrl. 5 g 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 allowed to precede the solution II by 10 seconds at 75 ° C.
The same flow rate was added over 0 minutes. Then, Solution III and IV
The solution was added in the same manner for 30 minutes, and the solutions V and VI were added in the same manner for 30 minutes. During the addition of these liquids
The pAg was 8.1. After the addition is complete, adjust the pH to 1N NaOH
Adjusted to 5.3 with (AZ-1) 1.5 mg and (AZ
-4) 1.8 mg was added and the mixture was aged at 75 ° C for 60 minutes. After aging (SB-1), 160 mg was added and aging was carried out for 20 minutes, then the temperature was lowered to 35 ° C., and VII solution was added at an equal flow rate over 5 minutes after addition for 5 minutes. After that, the temperature is 60 ℃
To 160 mg (SB-3), 16 (SB-6)
0 mg was added and the mixture was aged for 20 minutes. To this emulsion (CK-1)
1.1 g was added and allowed to settle, washed with water so as to have a target electric conductivity, desalted, and then added with 6 g of lime-treated gelatin to dissolve, and 0.8 cc of a 3.5% aqueous solution of (ATR-3) and (ATR-1) 72% solution 1.5 cc and KBr
Was added to adjust the pH to 6.2 and pAg 8.7. Average particle size 0.60 μm, coefficient of variation 12%, conductivity 3.5 mS
550 g of a cm- ¹ monodisperse silver iodobromide emulsion (EB-1) was prepared.

Liquid I AgNO ₃ 17 g Distilled water 180 cc Liquid II KBr 12.5 g Distilled water 180 cc III liquid AgNO ₃ 34 g Distilled water 180 cc IV liquid KBr 24.4 g Distilled water 180 cc V liquid AgNO ₃ 69 g Distilled water 360 cc VI liquid KBr 49. 4g Distilled water 360cc VII liquid KI 4.1g Distilled water 650cc (CK-1) polyisobutylene-co-maleate monosodium

[0067]

[Chemical 1]

[0068]

[Chemical 2]

Preparation of Silver Halide Emulsion (EG-1) 24 g of lime-treated inert gelatin was added to 900 cc of distilled water and dissolved at 40 ° C. for 1 hour, and then KBrl. 5 g 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, solution I and solution II were added at 75 ° C. for 5 seconds with solution II preceded by 5 minutes at the same flow rate. The pAg during addition of these solutions was 8.1. After the addition was complete, the pH was adjusted to 5.3 with 1N NaOH, 2.5 mg (AZ-1) and 3.3 mg (AZ-4).
Was added and the mixture was aged at 75 ° C. for 60 minutes. After aging (SB-1)
160 mg was added, and 20 minutes after the addition, the temperature was raised to 35 ° C., and an aqueous solution containing 4.1 g of KI was added over 5 minutes.
cc was added at an equal flow rate. After that, raise the temperature to 75 ℃,
320 mg of (SG-1) was added and the mixture was aged for 20 minutes. To this emulsion, 1.1 g of (CK-1) was added, precipitated, washed with water to desalt, and then 6 g of lime-processed gelatin was added to dissolve, and 0.8 cc of 3.5% aqueous solution of (ATR-3) was added.
Further, 1.5 cc of 72% solution of (ATR-1) was added to adjust pH to 6.2 and pAg to 8.8. Average particle size 0.
Monodisperse silver iodobromide emulsion with 20 μm and coefficient of variation of 18% (EG
-1) 550 g was prepared.

Liquid I AgNO ₃ 120 g Distilled water 880 cc Liquid II KBr 85.2 g Distilled water 675 cc

[0071]

[Chemical 3]

Preparation of silver halide emulsion (ER-1) 24 g of deionized gelatin was added to 900 cc of distilled water, and
After dissolution at 0 ° C. for 1 hour, 1.5 g of KBr was added, and 1N sulfuric acid was added to adjust the pH to 3.2. In this liquid (A
After adding 10 mg of GS-1), the liquids I and II were added to 75
The liquid II was added at 10 ° C. for 10 seconds at the same flow rate for 15 minutes. The pAg during the addition was 8.2. After the addition is complete
The pH was adjusted to 5.5 with 1N NaOH and (AZ-1) 5.
0 mg and 6.5 mg of (AZ-4) were added, and the mixture was added at 60 ° C at 60 ° C.
Aged. After aging (SR-1) 80 mg, (SR-6)
40 mg and (SR-2) 2 mg were added, and 20 minutes after the addition, the temperature was brought to 35 ° C., and then KI 4.
200 g of an aqueous solution containing 1 g was added at an equal flow rate. After that, the temperature was raised to 65 ° C. (SR-1) 80 mg, (SR-
6) 80 mg and (SR-2) 3 mg were added and aged for 20 minutes.

To this emulsion, 1.1 g of (CK-1) was added, precipitated, washed with water for desalting, and then 6 g of deionized gelatin was added to dissolve it, and a 3.5% aqueous solution of (ATR-3) was added. 8 cc and 1.5 cc of 72% solution of (ATR-1) were added to adjust pH to 6.2 and pAg to 8.6. 550 g of a monodisperse silver iodobromide emulsion (ER-1) having an average grain size of 0.22 μm and a coefficient of variation of 18% was prepared.

Liquid I AgNO ₃ 120 g Distilled water 870 cc Liquid II KBr 85.2 g Distilled water 775 cc

[0075]

[Chemical 4]

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.

[0077]

[Chemical 5]

Preparation of Pigment Dispersion (GY-1) To 240 g of the polymerizable compound (MN-1), 60 g of Seika Fast Yellow 2300 (trade name, manufactured by Dainichiseika Co., Ltd.)
Were mixed and stirred at 5000 rpm for 1 hour using an Eiger motor mill (manufactured by Eiger Engineering Co.) 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) To 255 g of the polymerizable compound (MN-1), 45 g of Microlith Magenta 2BA (trade name, manufactured by Ciba Geigy) and 23 g of (SV-1) were mixed, 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) 240 g of the polymerizable compound (MN-1) was mixed with 60 g of copper phthalocyanine (CI Pigment 15), and the mixture was mixed with an Eiger Motor Mill (manufactured by Eiger Engineering Co., Ltd.) at 5000 minutes per minute. The mixture was stirred for 1 hour by rotation, and the dispersion (GC-
1) was obtained.

Preparation of Photosensitive Composition (PB-1) Pigment Dispersion (GY-1) 136 g (MN-1) 44
g, 36 g of (SV-1) 10% (wt%) solution of (1P-4), (RD-1) 4.6 g, (RD-4) 18.
6 g, (FF-3) (SV-1) 0.5% (wt%)
4 cc of the solution and 2 g of (ST-1) were added and dissolved to prepare an oily solution. Silver halide emulsion (E
30 g of B-1) and 96 g of solid dispersion (KB-1) were added, and the mixture was stirred at 7,000 rpm for 5 minutes using a 50φ dissolver while keeping the temperature at 60 ° C. to obtain a photosensitive composition of W / O emulsion. The thing (PB-1) was obtained.

Preparation of Photosensitive Composition (PG-1) 194 g of pigment dispersion (GM-1) was added with (S) of (1P-4).
V-1) 36 g of 10% (wt%) solution, (RD-1)
4.6 g, (RD-4) 13.9 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
30 g of G-1) and 96 g of solid dispersion (KB-1) were added, and the mixture was stirred at 7000 rpm for 5 minutes using a 50φ dissolver while keeping 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 136 g of pigment dispersion (GC-1) (MN-1) 44
g, 36 g of a (SV-1) 10% (wt%) solution of (1P-4), (RD-1) 4.6 g, (RD-4) 13.
9 g, (SV-1) of (FF-3) 0.5% (wt%)
8 cc of the solution and 2 g of (ST-1) were added and dissolved to prepare an oily solution. Silver halide emulsion (E
30 g of R-1) and 96 g of solid dispersion (KB-1) were added, and the mixture was stirred at 7,000 rpm for 5 minutes using a 50φ dissolver while keeping the temperature at 40 ° C. to prepare a photosensitive composition of W / O emulsion. (PR-1) was obtained.

[0083]

[Chemical 6]

[0084]

[Chemical 7]

Photosensitive microcapsule dispersion (CB-
Preparation of 1) 1% water was added to 4.5 g of a 15% aqueous solution of the polymer (2P-4).
15.5 g was added and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. Add 1 part of polyvinylpyrrolidone K-90 to this solution.
280 g of 0% aqueous solution was added and mixed at 60 ° C. for 30 minutes. This mixed solution was added to the above-mentioned photosensitive composition (PB-1), and the mixture was mixed with a 50φ dissolver at 60 ° C. at 7,000 rpm.
The mixture was stirred for 20 minutes by rotation to obtain an emulsion in the state of W / O / W emulsion. Separately, melamine 31.5 g, formaldehyde 37% aqueous solution 52.2 g and water 170.3
g, heated to 60 ° C., and stirred for 30 minutes to obtain a transparent aqueous solution of the melamine-formaldehyde initial condensation product.
132 g of this initial condensate was cooled to 40 ° C. and the above W /
In addition to the emulsion in the form of an O / W emulsion, 32 cc of 1N sulfuric acid was added 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, 54 g of 40% aqueous solution of urea was added, and 24 cc of 1N sulfuric acid was added.
Stirring at 70 ° C was continued. To this solution, 36 g of a 3% aqueous solution of κ-carrageenan at 60 ° C. was added, and the mixture was stirred for 10 minutes, and 5
After cooling to 0 ° C, add 1N aqueous sodium hydroxide solution to 40cc
In addition, a photosensitive microcapsule dispersion liquid (CB-1) was prepared. The volume average particle diameter measured by Coulter Multisizer II (Coulter, Inc.) was 9.5 μm.

[0086]

[Chemical 8]

Photosensitive microcapsule dispersion (CG-
Preparation of 1) Water was added to 6.8 g of a 15% aqueous solution of the polymer (2P-4).
3.2 g was added, and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. Add 10% of polyvinylpyrrolidone K-90 to this solution.
300 g of an aqueous solution was added and mixed at 60 ° C. for 30 minutes. 50 to the above-mentioned photosensitive composition (PG-1),
2 at 8000 rpm with a φ dissolver at 60 ° C
The mixture was stirred for 0 minutes to obtain an emulsion in the state of W / O / W emulsion. Then, a photosensitive microcapsule dispersion liquid (CG-1) was prepared in the same manner as the preparation of (CB-1). The volume average particle diameter was 9.2 μm.

Photosensitive microcapsule dispersion (CG-
Preparation of 2) 86.4 g of water was added to 13.6 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. Add 10 parts of polyvinylpyrrolidone K-90 to this solution.
% Aqueous solution 300 g was added and mixed at 60 ° C. for 30 minutes.
This mixed solution was added to the above-mentioned photosensitive composition (PG-1), and 5
Using a 0φ dissolver, the mixture was stirred at 60 ° C. at 8000 rpm for 20 minutes to obtain an emulsion in the state of W / O / W emulsion. Then, a photosensitive microcapsule dispersion liquid (CG-2) was prepared in the same manner as the preparation of (CB-1). The volume average particle diameter was 7.1 μm.

Photosensitive microcapsule dispersion (CR-
Preparation of 1) Water was added to 3.6 g of a 15% aqueous solution of the polymer (2P-4).
36.4 g was added, and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. Add 10 parts of polyvinylpyrrolidone K-90 to this solution.
% Aqueous solution 260 g was added and mixed at 60 ° C. for 30 minutes.
The photosensitive composition (PR
-1) and 750 min / min using a 50φ dissolver
The mixture was stirred at 0 rotation for 20 minutes to obtain an emulsion in the state of W / O / W emulsion. Then, a photosensitive microcapsule dispersion liquid (CR-1) was prepared in the same manner as the preparation of (CB-1). The volume average particle diameter was 9.1 μm.

Photosensitive microcapsule dispersion (CR-
Preparation of 2) 1 g of water was added to 7.2 g of a 15% aqueous solution of the polymer (2P-4).
32.8 g was added, and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. Add 10 parts of polyvinylpyrrolidone K-90 to this solution.
% Aqueous solution 260 g was added and mixed at 60 ° C. for 30 minutes.
The photosensitive composition (PR-
In addition to 1), using a 50φ dissolver, 7500 / min
The mixture was stirred for 20 minutes by rotation to obtain an emulsion in the state of W / O / W emulsion. Then, a photosensitive microcapsule dispersion liquid (CR-1) was prepared in the same manner as the preparation of (CB-1). The volume average particle diameter was 7.2 μm.

Oil-based liquid-containing microcapsule dispersion (CA
-2) Preparation: 486 g of a polymerizable compound (MN-1) and Takenate D110 were added to 518 g of a 3% aqueous solution of Metroze 65SH50 (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxypropylmethylcellulose).
A mixture of 32 g of N (manufactured by Takeda Pharmaceutical Co., Ltd., polyisocyanate) was added, and a 40φ dissolver was used at 25 ° C. for 16 minutes per minute
The mixture was stirred at 00 rpm for 20 minutes to obtain an O / W emulsion. This solution was stirred with a propeller blade at 25 ° C. at 1,200 rpm while stirring a 6% solution of 2% diethylenetriamine in water.
0 g was added. After stirring for another 30 minutes, the temperature was raised to 40 ° C. over 30 minutes while continuing stirring. After further stirring for 90 minutes, the temperature was lowered to 25 ° C. and 6 cc of 2N sulfuric acid was added to obtain MN-1-containing polyurea capsules. Volume average particle size is 9.8μ
It was m.

Preparation of Photosensitive Materials 101-103 24 g of photosensitive microcapsules (CB-1), (CG
-1) 36 g, (CR-1) 30 g, and (CA
-2) is mixed with 35.2 g of the surfactant (WW-1).
13.2 g of 5% aqueous solution and 13.6 g of water were added and mixed.
(Coating liquid (L₁)). This liquid is applied to a 25 μm thick poly
Aluminum deposited on ethylene terephthalate film
Extrude on the aluminum deposition surface of the
Coating amount of 92cc / m²And apply to dry
Then, a photosensitive material 101 for a comparative example was prepared. Photosensitive My
(CG-2) instead of black capsule (CG-1),
Except for using (CR-2) instead of (CR-1)
The coating liquid (L₂) Prepared
Then, a photosensitive material 102 for comparison was prepared. Photosensitive material 10
Coating liquid used for 1 (L₁) And 102
Cloth liquid (L ₂) On a similar aluminum deposition support
To L₁Is 55cc / m², L on it ₂Is 37cc / m²Becomes
As described above, the photosensitive material 103 of the present invention is applied by drying at the same time.
Created.

[0093]

[Chemical 9]

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 30 to 60). %, Using paper atoms having a fiber length distribution such as [Patent No. 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).

[0095]

[Chemical 10]

Image formation By using a halogen lamp in which the light-sensitive materials 101 to 103 are adjusted to a color temperature of 3100K, continuously changing 0 to 4.0.
1 at 2000 lux through a wedge with a transmission density of
Exposed for 2 seconds. Thereafter, the opposite side of the coated surface of the light-sensitive 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 on each other and the speed was 2 cm / sec. Diameter 3 cm, pressure 220 kg /
It was passed through a pressure roller of cm ² (surface temperature 70 ° C.). X-
Table 1 shows the relative evaluation of Dmax measured by Rite and roughness (granularity) in the intermediate density portion.

[0097]

[Table 1]

From Table 1, it can be seen that the light-sensitive material of the present invention is excellent in both Dmax and graininess.

Claims (1)

[Claims] 1. A photosensitive layer containing at least two microcapsules containing at least a polymerizable compound, a silver halide, a reducing agent, and a pigment is laminated on a support, and the photosensitive layer on the side closer to the support is formed. A photosensitive material characterized in that the volume average particle diameter of the microcapsules contained therein is larger than the volume average particle diameter of the microcapsules contained in the photosensitive layer on the side remote from the support.