JPH05113660A - Photosensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material obtaining a color image prevented from becoming blackish owing to printing-out of silver halide. CONSTITUTION:This photosensitive material has a photosensitive layer contg. microcapsules on the base and the photosensitive layer contains at least one-of compds. represented by the formula besides the microcapsules housing at least silver halide, a reducing agent, a polymerizable compd., a color image forming material and a precursor of a base. In the formula, M is H, a cation or an alkali-cleavable mercapto protecting group, R1 is alkyl, cycloalkyl, aralkyl, alkenyl or aryl and the group represented by R1 has at least one sulfonic acid or sulfonate group, at least one carboxylic acid or carboxylate group or at least one phosphonic acid or phosphonate group as a substituent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a light-sensitive material using microcapsules containing a polymerizable compound.

[0002]

2. Description of the Related Art A highly sensitive light-sensitive material using microcapsules containing silver halide, a reducing agent, and a polymerizable compound is described in JP-A-61-275572. In the portion where the latent image of silver halide is formed,
An image is formed by polymerizing a polymerizable compound by the action of a reducing agent. When an image is formed using the above-mentioned light-sensitive material, a method is generally used in which a light-sensitive material that has been imagewise exposed and developed is superposed on an image-receiving material, and an unpolymerized polymerizable compound is transferred onto the image-receiving material. is there. The transferred image thus obtained has a high contrast. However, if the transferred image is exposed to white light for a while,
In the unpolymerized portion, the phenomenon that the entire image was darkened due to the printout of the silver halide transferred onto the image receiving material together with the polymerizable compound.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light-sensitive material which gives a high contrast and prevents darkening due to silver halide print-out to obtain a highly saturated image.

[0004]

The above-mentioned object is to provide a light-sensitive material having a light-sensitive layer containing microcapsules on which at least a silver halide, a reducing agent, a polymerizable compound, a color image-forming substance and a base precursor are encapsulated on a support. In the above, it is achieved by a photosensitive material characterized in that the photosensitive layer contains at least one compound selected from the compounds represented by the following general formula (1). General Formula (1) R ₁ —S—M In the above General Formula (1), M represents a hydrogen atom, a cation, or a protective group for a mercapto group that is cleaved by an alkali,
R ₁ is an alkyl group, a cycloalkyl group, an aralkyl group,
It represents an alkenyl group or an aryl group, and these groups further have at least one sulfonic acid or a salt thereof, carboxylic acid or a salt thereof, or phosphonic acid or a salt thereof as a substituent. According to the present invention, the probability that the silver halide grains will be transferred onto the image receiving material in the unpolymerized portion is significantly reduced. Therefore, almost no silver halide is transferred onto the image receiving material, and an image with high saturation can be obtained.

The compound represented by the general formula (1) of the present invention may have a substituent in R ₁ in addition to the above-mentioned sulfonic acid, carboxylic acid and phosphonic acid groups. Examples of the substituent include an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group,
Alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, amino group, N-substituted amino group, acylamino group, carbamoyl group, N-substituted carbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonylamino group, arylsulfonylamino group , Sulfamoyl group, N-substituted sulfamoyl group, cyano group, hydroxyl group, nitro group, halogen atom and the like.

More preferred compounds of the compound represented by the general formula (1) of the present invention are those represented by the general formula (2), the general formula (3) or the general formula (4).

[0007]

[Chemical 2]

In the general formula (2), Z represents a sulfur atom or an oxygen atom. In the general formulas (2), (3) and (4), the substituent X represents a sulfonic acid or a salt thereof, a carboxylic acid or a salt thereof, a phosphonic acid or a salt thereof, or a sulfo group, a carboxyl group or a phosphono group ( (Including salts thereof) substituted alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic residue, alkoxy group, aryloxy group,
Acyl group, acylamino group, sulfonylamino group, amino group, alkylthio group, arylthio group, sulfamoyl group, carbamoyl group, acyloxy group, ureido group,
It represents a substituent selected from a urethane group, an alkylsulfonyl group, an alkylsulfinyl group, an arylsulfonyl group, and an arylsulfinyl group.

Y is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group,
Aralkyl group, aryl group, acyl group, hydroxyl group, alkoxy group, aryloxy group, acyloxy group, urethane group, acylamino group, sulfonylamino group, amino group,
It represents a substituent selected from an ureido group, a nitro group, an alkylthio group, an arylthio group, a mercapto group, an alkylsulfinyl group, an alkylsulfonyl group, an arylsulfinyl group, an arylsulfonyl group and a cyano group. Further, the substituents X and Y may be bonded to each other to form a 5- or 6-membered ring. n represents an integer of 1 to 5, m represents 0 or an integer of 1 to 5. M represents a hydrogen atom, a cation or a protective group for a mercapto group which is cleaved by an alkali.

Specific examples of the compound represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

The compound of the present invention is a known compound and can be synthesized by a usual method. These compounds may be used alone or in combination of two or more. These compounds can be added anywhere in the photosensitive layer,
It is particularly preferable to add it to the inner phase of the photosensitive microcapsules. The addition amount is 10 with respect to 1 mol of silver (including silver halide described below and an organic silver salt which is an optional component).
^-6 It is preferable to use in the range of 100 mol, and 10
It is particularly preferable to use it in the range of ^{-3 to} 10 mol.

The silver halide, reducing agent, color image-forming substance, base precursor, microcapsule, and support used in the light-sensitive material of the present invention will be described below.

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

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

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, compounds other than silver halide such as silver rhodanide and lead oxide may be bonded. Also, the halogen composition,
Two or more kinds of silver halide grains having different crystal habits, grain sizes and the like can be used in combination. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (December 1978), 2
2-23, "I. Emulsion preparation an
d types) ”and ibid. No. 18716 (1979, 11)
Mon.), page 648, and the like.

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

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

The reducing agent which can be used by being housed in the photosensitive microcapsules of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. Examples of the reducing agent having the above function include hydroquinones, catechols, p-
Aminophenols, p-phenylenediamines, 3-
Pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-
Dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,
4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, Examples include sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines.

The various reducing agents are described in detail in "Public Technology No. 5", pages 18 to 35. 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 color image-forming substance that can be used in the light-sensitive material of the present invention is not particularly limited, and various types can be used. That is, the substance itself is colored (dye or pigment), or the substance itself is colorless or light-colored but external energy (heating, pressure, light irradiation, etc.) or another component (developing agent) A substance (color former) that develops a color upon contact with is also included in the color image forming substance. As the color image-forming substance of the present invention, as described in JP-A-62-187346, dyes and pigments which are excellent in image stability and colored themselves are preferable.

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

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

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

In the present invention, when the base precursor is 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, JP-A No. 64-32521). 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-2-146041, JP-A-3-3
No. 3748, each gazette) Here, when dispersing the base precursor in water, the nonionic or amphoteric water-soluble polymer is the one described on pages 128 to 135 of "Public Technology No. 5". Can be used.

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

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

When aminoaldehyde 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. The average particle size of the photosensitive microcapsules is 1 to 50 μm, preferably 3 to 25 μm.
μm. The particle size distribution of the photosensitive microcapsules is preferably a uniform value or more, as in the photosensitive material described in JP-A-63-5334.
Further, the film thickness of the photosensitive microcapsule is as described in JP-A-63-
As in the light-sensitive material described in Japanese Patent No. 81336, it is preferable that the particle diameter is within a certain range.

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

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

Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. Examples of the anionic water-soluble polymer include polystyrene sulfinic acid, copolymer of styrene sulfinate, polystyrene sulfonate, copolymer of styrene sulfonate, polyvinyl sulfate ester salt, polyvinyl sulfonate, maleic anhydride. 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. Further, in order to reduce the solubility of the base precursor in the polymerizable compound, in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexylurea, octyl alcohol, dodecyl alcohol, stearyl alcohol, -OH such as stearamide,-. SO ₂ NH _2, -C
ONH _2, it is also possible to add a compound having a hydrophilic group such as -NHCONH _2.

In the present invention, in addition to the reducing agent, a known antioxidant may be used together with the polymerizable compound for preventing oxidative deterioration of the polymerizable compound and for preventing oxygen oxidation during heat development. As such an antioxidant, 2,2 '
-Methylene-bis- (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, 2,
2'-butylidene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4
-Phenolic antioxidants such as -methylphenyl acrylate and 4,4'-thio-bis- (3-methyl-6-t-butylphenol); diphenyldecylphosphite,
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 -Propionic 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, wood free paper, baryta paper, coated paper, cast coated paper, synthetic paper, metal and its analogues, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose. Ester, polyvinyl acetal,
Examples thereof include films such as polystyrene, polycarbonate, polyethylene terephthalate, and polyimide, and paper laminated with a resin material or a polymer such as polyethylene. For details, refer to “Public Technology No. 5”
No. "pp. 144-149. Among them, the preferred support of the present invention is a polymer film, and it is particularly preferred that it is a polymer film of 50 μm or less in view of the above-mentioned thermal conductivity.

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

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

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

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

A photosensitive material is prepared by polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed,
A heat or photopolymerization initiator can be used for the purpose of initiating polymerization or for polymerizing an unpolymerized polymerizable compound after image transfer. Examples of thermal polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, sulfinic acids and the like. Details thereof are described 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. Research Disclosure No. 17643, November 1978 as an antistatic agent
(Page 27) etc. In the photosensitive layer of the photosensitive material,
Dyes or pigments may be added for the purpose of preventing halation or irradiation. A light-sensitive material having a white pigment added to the light-sensitive layer is disclosed in JP-A-63-29748.
It is described in the official gazette.

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

When a solvent of a polymerizable compound is used in the light-sensitive material, it is preferable to use it by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound.
A photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules is disclosed in Japanese Patent Laid-Open Publication No. Sho 6-62.
It is described in JP-A-2-209524.

Various antifoggants or photographic stabilizers can be used in the present invention. For example,
Azoles and azaindenes described in RD No. 17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-87957.
The acetylene compounds and the like described in the publication are used.

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Or a compound that reacts with a radical to terminate the polymerization.
Specifically, an acid precursor that releases an acid by heating,
Examples thereof include an electrophilic compound that causes a substitution reaction with a coexisting base by heating, a nitrogen-containing heterocyclic compound, a mercapto compound and its precursor, or a compound that releases a polymerization inhibitor by the action of heating or a base. More specifically, JP-A-62-253159 (31) to (32)
Page, JP-A-1-72479, JP-A 1-3471,
It is described in Japanese Patent Application No. 3-21411.

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 application specification relating to the series of photosensitive materials described above, and Research Disclosure Vol. 170, 179.
It is described in No. 17029 (pages 9 to 15) of June 8th. 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, the image-receiving material is generally used 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, 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.

As the white pigment used in the image receiving layer, inorganic white pigments such as oxides of silicon oxide, titanium oxide, zinc oxide, magnesium oxide, aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate and carbonic acid can be used. 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.

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

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

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

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

In the following, the step of imagewise exposure in the image forming method of the present invention, the imagewise exposure, or after the imagewise exposure, the photosensitive material is heated from the surface of the support not coated with a photosensitive layer. And a series of steps such as a step of superposing the surface of the photosensitive material coated with the photosensitive layer and the image receiving material and pressurizing the same.

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

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

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

When the image information does not pass through an electric signal, for example, direct shooting 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 the same materials may be used in combination or different kinds may be used in combination. May be. The color sensitivity of the light-sensitive material is R (red), G (green), B (blue) in the photographic field.
Photosensitivity is normal, but in recent years, it is often used in combination with UV, IR, etc., and the range of use of the light source is expanding. For example, the color sensitivity of the photosensitive material is (G, R, IR)
Or (R, IR (short wave), IR (long wave)),
(UV (short wave), UV (medium wave), UV (long wave)), (U
Spectral regions such as V, B, G) are utilized. The light source may 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 surface of the photosensitive material on the support on which the photosensitive layer is not coated. At this time, the photosensitive layer is coated. The surface that is marked may be in direct contact with the air,
It may be covered with a heat insulating material or the like in order to keep it warm so as not to release heat. In this case, it is preferable not to apply a strong pressure (10 kg / cm ² or more) to the photosensitive layer so as not to destroy the microcapsules contained in the photosensitive layer.

The heat development by heating is carried out at the same time as or after the imagewise exposure, but it is preferable to perform the heating after 0.1 seconds or more has passed after the imagewise exposure. The heating temperature is generally 60 ° C to 250 ° C, preferably 80 ° C to 180 ° C.
And the heating time is between 0.1 and 10 seconds, preferably between 0.1 and 5 seconds.

The light-sensitive 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 unpolymerized polymerizable compound is transferred to the image receiving material 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, A color image can be obtained on the image receiving material. A conventionally known method can be used as the pressurizing method.

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

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

[0083]

【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 dissolving at 0 ° C. for 1 hour, 1 g of KBr was added, and 1
The pH was adjusted to 3.2 by adding N-sulfuric acid.

After 10 mg of (AGS-1) was added to this solution, solutions I and II were simultaneously added at 75 ° C. over 15 minutes. Further, the liquid III and the liquid IV were added simultaneously at 75 ° C. over 15 minutes. After the addition is complete, adjust the pH to 1N Na
The pAg was adjusted to 9.4 with OH at 6.0 and also KBr, (AZ-1) 1.9 mg and (AZ-2) 2.3.
mg was added and the mixture was aged at 75 ° C. for 60 minutes. After aging (SB-
1) 480 mg was added, and 20 minutes after the addition, the temperature was adjusted to 35
Aqueous solution 2 containing 4.1 g of KI over 5 minutes
00 g was added at an equal flow rate.

To this emulsion, 1.1 g of (CK-1) was added, precipitated, washed with water and desalted, and then 6 g of lime-processed gelatin was added to dissolve it, and a 3.5% aqueous solution of (ATR-3) was added. The pH was adjusted to 6.2 by adding 5 cc. 550 g of a monodisperse silver iodobromide emulsion (EB-1) having an average grain size of 0.35 μm and a coefficient of variation of 15% was prepared.

Liquid I AgNO ₃ 40 g Distilled water 300 cc Liquid II KBr 36.4 g Distilled water 300 cc III Liquid AgNO ₃ 80 g Distilled water 300 cc IV Liquid KBr 72.8 g Distilled water 550 cc

[0087]

[Chemical 14]

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

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

[0090]

[Chemical 15]

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.)

Photosensitive composition (PB-1)-(PB-7)
Preparation of Pigment Dispersion (GY-1) 45 g (1P-4) (SV
-1) 9 g of 10% (wt%) solution, (RD-1) 2.
3 g, (RD-3) 3.1 g, and (ST-1) 0.
5 g was added and dissolved to prepare an oily solution. Further, the compound (AY-1)-(AY-7) was added in an amount of 1.6 × 10 ⁻⁴ mol. Silver halide emulsion (EB-1) was added to this solution.
7.6 g and 24 g of the solid dispersion (KB-1) were added, and 6
While maintaining the temperature at 0 ° C., a 40φ dissolver was used to stir at 10,000 rpm for 5 minutes to obtain a photosensitive composition (PB-1)-(PB-7) as a W / O emulsion.

[0093]

[Chemical 16]

Photosensitive microcapsule dispersion (CB-
1)-(CB-7) Preparation 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
To this solution, 50 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. This mixed solution was added to the above-mentioned photosensitive composition (PB-1)-(PB-7) to give 40φ.
20 at 6000 rpm with a dissolver at 60 ° C
After stirring for a minute, an emulsion in the state of W / O / W emulsion was obtained. Separately, 31.5 g of melamine and 3 parts of formaldehyde
52.2 g of a 7% aqueous solution and 170.3 g of water were added,
The mixture was heated to 60 ° C. and stirred for 30 minutes to obtain a transparent aqueous solution of melamine-formaldehyde initial condensation product.

25 g of this initial condensate was added to the emulsion in the state of the above W / O / W emulsion cooled to 40 ° C.,
The pH was adjusted to 5.0 with 2N sulfuric acid while stirring at 1200 rpm with a propeller blade. Next, the temperature of this liquid was raised to 70 ° C. in 30 minutes, and further stirred for 30 minutes.
To this was added 10.3 g of a 40% aqueous solution of urea, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring was continued at 70 ° C. for another 40 minutes. This solution was cooled to 40 ° C., 9 g of a 3% aqueous solution of κ-carrageenan was added, the mixture was stirred for 10 minutes, and the pH was adjusted to 6.5 with a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB- 1)-(CB-
7) was prepared. Polymer (2P-4) Polyvinylbenzenesulfinic acid potassium-co-acrylamide Polymer (2P-2) Polyvinylpyrrolidone K-90 Polymer (PC-3) PVA KL318 (Kuraray, carboxy-modified PVA)

Preparation of High Boiling Organic Compound Dispersion (HB-1) MN-1 was added to 50 g of a 10% aqueous solution of polymer (PC-3) kept at 60 ° C. and 15 g of a 5% aqueous solution of sodium dodecylbenzene sulfonate. 50 g was added and the mixture was dispersed with a homogenizer (Nippon Seiki) at 8000 rpm for 10 minutes.

Preparation of High Boiling Organic Compound Capsule (HC-1) As high boiling organic compound (MN-1) 45 g, (1P
-4) (SV-1) 10% (wt%) solution 9 g,
(RD-1) 1.6 g, (RD-2) 1.2 g, (FF
2 g of (SV-1) 0.5% (wt%) solution of 3) was added and dissolved to prepare an oily solution (YU-1). 36 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 60 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. The oily solution composition (YU-1) was added to this mixed solution, and the mixture was stirred at 60 ° C. at 6000 rpm for 20 minutes using a 40φ dissolver to obtain an emulsion in the form of an emulsion. Then, in the preparation of the photosensitive microcapsule dispersion (CB-1), the high boiling point organic compound was similarly prepared except that the oily solution composition (YU-1) was used instead of the photosensitive composition (PB-1). A capsule dispersion liquid (HC-1) was prepared.

Preparation of Photosensitive Materials 101-107 Photosensitive microcapsules (CB-1)-(CB of the present invention
After removing 45 g each of -7) and heating at 40 ° C. to dissolve them, 6.5 g of a 5% aqueous solution of a surfactant (WW-1) and a 1% aqueous solution of a surfactant (WW-2) 8
g, 7.5 g of (HB-1) dispersion and (HC-1)
7.5 g of the dispersion and 15 cc of water were added, and the mixture was stirred at 40 ° C. for 10 minutes. This solution was filtered with a filter cloth of 44 μm mesh to prepare capsule coating solutions 101-107.

[0099]

[Chemical 17]

This coating solution was applied on the aluminum-deposited surface of a support obtained by vapor-depositing aluminum on a polyethylene terephthalate film having a thickness of 12 μm by an extrusion method so that the coating amount was 100 cc / m ^2, and dried at 60 ° C. The photosensitive material 101-107 was prepared by winding the coated surface inside at 25 ° C. and 65%.

Comparative Example 1 Preparation of Photosensitive Composition (PB-8) 45 g of pigment dispersion (GY-1) was added to (SV of (1P-1)).
-1) 9 g of 10% (wt%) solution, (RD-1) 2.
3 g, (RD-3) 3.1 g, and (ST-1) 0.
5 g was added and dissolved to prepare an oily solution. Furthermore,
(FF-3) was added in an amount of 1.6 × 10 ⁻⁴ mol. To this solution, 7.6 g of a silver halide emulsion (EB-1) and 24 g of a solid dispersion (KB-1) were added, while keeping the temperature at 60 ° C., 4
Using a 0φ dissolver, stirring at 10,000 rpm for 5 minutes, the photosensitive composition of W / O emulsion (PB-
8) was obtained.

[0102]

[Chemical 18]

Photosensitive microcapsule dispersion (CB-
Preparation of 8) 46 g of water was added to 4 g of 15% aqueous solution of polymer (2P-4).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
To this solution, 50 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. This mixed solution was added to the above-mentioned photosensitive composition (PB-8), and the mixture was stirred with a 40φ dissolver at 60 ° C. at 6000 rpm for 20 minutes, and W
An emulsion in the form of a / O / W emulsion was obtained. Separately, 5% of 37% aqueous formaldehyde solution was added to 31.5 g of melamine.
2.2 g and 170.3 g of water were added, the mixture was heated to 60 ° C. and stirred for 30 minutes to obtain a transparent aqueous solution of the melamine-formaldehyde initial condensate.

25 g of this initial condensate was added to the emulsion in the state of the above W / O / W emulsion cooled to 40 ° C.,
The pH was adjusted to 5.0 with 2N sulfuric acid while stirring at 1200 rpm with a propeller blade. Next, the temperature of this liquid was raised to 70 ° C. in 30 minutes, and further stirred for 30 minutes.
To this was added 10.3 g of a 40% aqueous solution of urea, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring was continued at 70 ° C. for another 40 minutes. This solution was cooled to 40 ° C., 9 g of a 3% aqueous solution of κ-carrageenan was added, the mixture was stirred for 10 minutes, and the pH was adjusted to 6.5 with a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB- 8) was prepared.

Preparation of Photosensitive Material 108 A photosensitive material 108 was prepared in the same manner as the preparation of the photosensitive materials 101-107 except that (CB-8) was used as the photosensitive microcapsule dispersion liquid.

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

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

[0108]

[Chemical 19]

Image formation Using a halogen lamp adjusted to a color temperature of 3100 ° K,
A black silver image was continuously exposed through a wedge having a transmission density varying from 0 to 4.0 under exposure conditions of 5000 lux and 1 second. Immediately after the exposure, the side opposite to the coated surface of the light-sensitive material was brought into close contact with a drum heated to 150 ° C. and heat-developed for 1.0 second. After 8 seconds, the image receiving material (RS-
1) and the coated surface are overlaid and passed through a pressure roller with a diameter of 3 cm and a pressure of 200 kg / cm ² (surface temperature of 65 ° C) at a speed of 3.2 cm / sec, and the image receiving material is peeled off from the photosensitive material immediately after passing. did. Then, high-contrast positive images were obtained from the light-sensitive materials 101 to 108, respectively.

Evaluation as Photosensitive Material With respect to the yellow positive color image obtained on each image receiving material,
The maximum density (Dmax) and the minimum density (Dmin) were measured with a Macbeth reflection densitometer, and the contrasts of the images obtained by these numerical values were compared. Also, the amount of transferred Ag on each image receiving material was measured by a fluorescent X-ray measuring device, and this value and 3
The decrease in color saturation due to the printout of silver halide after a lapse of time of 0 was evaluated by comparing changes with time of the G concentration with a reflection densitometer. The above measurement results are summarized in Table 1.

[0111]

[Table 1]

As described above, with the light-sensitive material of the present invention, an image in which color turbidity due to silver halide print-out was reduced while maintaining high contrast was obtained.

Example 2 Preparation of Pigment Dispersion (GY-2) A polymerizable compound (MN-2) (255 g) was mixed with 45 g of Chromofine Yellow 5900 (trade name, manufactured by Dainichiseika Co., Ltd.) to prepare an Eiger motor. Using a mill (manufactured by Eiger Engineering Co.), the mixture was stirred at 5000 rpm for 1 hour to obtain a dispersion (GY-2).

[0114]

[Chemical 20]

In the preparation of the photosensitive composition in Example 1, the pigment dispersion (GY-2) was used in place of the pigment dispersion (GY-1), and the compounds of the present invention are shown in Table 2. Photosensitive materials 201-212 were prepared in the same manner as in Example 1 except that the above additions were made.

[0116]

[Table 2]

Table 3 shows the results of evaluation of the light-sensitive material conducted in the same manner as in Example 1.

[0118]

[Table 3]

Similar to the results of Example 1, the image showed little change in density due to printout of silver halide after 30 days, and there was no color turbidity.

Example 3 Preparation of Silver Halide Emulsion (EG-1) 24 g of gelatin and 1.25 g of sodium chloride in 1200 ml of water.
An aqueous solution (I) (600 ml of an aqueous solution containing 88 g of potassium bromide) and an aqueous solution (II) (silver nitrate 12
An aqueous solution containing 5 g (600 ml) was added simultaneously at the same flow rate over 15 minutes. Five minutes after this was completed, 47 ml of a 1% methanol solution of the sensitizing dye (SG-1) was added to 60
Stir for 15 minutes at ° C. To this emulsion, 1.2 g of poly (isobutylene-co-maleic acid monosodium salt) was added and allowed to settle, washed with water and desalted, and then 24 g of gelatin was added and dissolved, and further 1 mg of sodium thiosulfate was added to 60 ° C.
Chemical sensitization was conducted for 1 hour to prepare 530 g of an octahedral silver bromide emulsion having an average grain size of 0.1 μm.

[0121]

[Chemical 21]

Silver halide emulsions (EG-2) to (EG-
Preparation of 7) In the preparation of the silver halide emulsion (EG-1), an aqueous solution having the following composition is used instead of the aqueous solution (I), and the addition amount of sodium thiosulfate is changed as described below. In the same manner as in (1), silver halide emulsions (EG-2) to (EG-7) with a yield of 530 g were prepared. Preparation of silver halide emulsion (EG-8) In the preparation of silver halide emulsion (EG-1), potassium iodide 4.3 was added after the addition of aqueous solution (I) and aqueous solution (II).
An octahedral silver iodobromide emulsion having an average grain size of 0.1 μm (EG-) was prepared in the same manner as the silver halide emulsion (1) except that 200 ml of an aqueous solution containing g was added at an equal flow rate for 5 minutes.
8) 530 g was prepared. Preparation of silver halide emulsion (EG-9) In the preparation of silver halide emulsion (EG-1), 15 minutes after the addition of the methanol solution of the sensitizing dye (A), 200 ml of an aqueous solution containing 4.3 g of potassium iodide was added. 530 g of an octahedral silver iodobromide emulsion (EG-9) having an average grain size of 0.1 μm was prepared in the same manner as the silver halide emulsion (1) except that the addition was carried out at the same flow rate for 5 minutes. Preparation of silver halide emulsion (EG-10) In the preparation of silver halide emulsion (EG-9), the addition time of aqueous solution (I) and aqueous solution (II) was changed from 15 minutes to 45 minutes, and the addition amount of sodium thiosulfate was 1 mg. From 0.25mg
530 g of an octahedral silver iodobromide emulsion (EG-10) having an average grain size of 0.2 μm was prepared in the same manner as the silver halide emulsion (EG-8) except that the above was changed to. Preparation of silver halide emulsion (EG-11) In the preparation of silver halide emulsion (EG-10), the amount of sodium chloride in the aqueous gelatin solution is 1.2 g to 3 g.
The average grain size of 0 was obtained in the same manner as the silver halide emulsion (EG-10) except that the amount of the compound (a) was changed from 0.01 g to 0.02 g and the addition amount of sodium thiosulfate was changed to 0.1 mg. .3 μm octahedral silver iodobromide emulsion (EG-1
1) 530 g was prepared. Preparation of Silver Halide Emulsion (EG-12) In the preparation of silver halide emulsion (EG-10), the amount of sodium chloride in the aqueous gelatin solution was 1.2 g to 0.
0.01 g to 0.02 g of compound (a) in 3 g
530 g of a tetradecahedral silver iodobromide emulsion (EG-12) having an average grain size of 0.2 μm was prepared in the same manner as the silver halide emulsion (EG-10) except that the above was changed to. Preparation of silver halide emulsion (EG-13) In the preparation of silver halide emulsion (EG-10), pAg of aqueous gelatin solution was added during the addition of aqueous solutions (I) and (II).
In the same manner as in the silver halide emulsion (EG-10) except that the addition amount of the aqueous solution (II) was adjusted so that
Cubic silver iodobromide emulsion with an average grain size of 0.2 μm (EG
-13) 530 g was prepared. Preparation of Silver Halide Emulsion (EG-14) Silver halide (EG-) except that 1 mg of zinc chloride (hexahydrate) was used in place of sodium thiosulfate in the preparation of silver halide emulsion (EG-1). An octahedral silver bromide emulsion 53 having an average grain size of 0.1 μm as in 1).
0 g was prepared.

[0123]

[Table 4]

Preparation and Evaluation of Photosensitive Material Instead of the silver halide emulsion (EB-1) (EG-1)
(EG-14) were used to evaluate the effect of the compound of the present invention used in Example 1 in the same manner as in Example 1 to prepare and evaluate a light-sensitive material. As a result, the same effect as in Example 1 was obtained even when these silver halide emulsions were used.

Claims (2)

[Claims] 1. A light-sensitive material having a light-sensitive layer containing microcapsules containing at least a silver halide, a reducing agent, a polymerizable compound, a color image-forming substance and a base precursor on a support. A photosensitive material containing at least one compound selected from the compounds represented by formula (1). General Formula (1) R ₁ —S—M In the above General Formula (1), M represents a hydrogen atom, a cation, or a protective group for a mercapto group that is cleaved by an alkali,
R ₁ represents a heterocyclic group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group or an aryl group, and these groups each have at least one sulfonic acid or salt thereof, carboxylic acid or salt thereof as a substituent, Alternatively, it has phosphonic acid or a salt thereof. 2. The compound represented by the general formula (1) is a compound represented by the following general formula (2), general formula (3) or general formula (4). The light-sensitive material described. [Chemical 1] In the general formula (2), Z represents a sulfur atom or an oxygen atom. Substituent X in the general formulas (2), (3) and (4)
Represents a sulfonic acid or a salt thereof, a carboxylic acid or a salt thereof, or a phosphonic acid or a salt thereof, or an alkyl group or a cycloalkyl group substituted with a sulfo group, a carboxyl group, a phosphono group (including salts thereof),
Aralkyl group, alkenyl group, aryl group, heterocyclic residue, alkoxy group, aryloxy group, acyl group, acylamino group, sulfonylamino group, amino group, alkylthio group, arylthio group, sulfamoyl group, carbamoyl group, acyloxy group, ureido Represents a substituent selected from a group, a urethane group, an alkylsulfonyl group, an alkylsulfinyl group, an arylsulfonyl group, and an arylsulfinyl group. Y is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an acyl group, a hydroxyl group,
Alkoxy group, aryloxy group, acyloxy group, urethane group, acylamino group, sulfonylamino group, amino group, ureido group, nitro group, alkylthio group, arylthio group, mercapto group, alkylsulfinyl group, alkylsulfonyl group, arylsulfinyl group, It represents a substituent selected from an arylsulfonyl group and a cyano group. Further, the substituents X and Y may be bonded to each other to form a 5- or 6-membered ring. n is an integer from 1 to 5, m is 0
Alternatively, it represents an integer from 1 to 5. M represents a hydrogen atom, a cation or a protective group for a mercapto group which is cleaved by an alkali.