JPH05289329A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material capable of stably giving an image excellent in discrimination in a short time and not causing discoloration immediately after image formation. CONSTITUTION:This photosensitive material has a photosensitive layer contg. microcapsules involving at least silver halide, a polymerizable compd., a color image forming material, a precursor of a base and a hydrazine deriv. represented by the formula on the substrate. In the formula, R1 is H, a halogen, alkyl, cycloalkyl, aralkyl, aryl, alkoxy, aryloxy, acylamino, sulfonylamino, ureido or amino, (n) is 0 or an integer of 1-5 and R2 is an alkyl, cycloalkyl, aralkyl, aryl or a heterocyclic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material capable of obtaining an image with excellent discrimination. Further, the present invention relates to a light-sensitive material having an excellent hue of the obtained image.

[0002]

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

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

On the contrary, a method of polymerizing a polymerizable compound in a portion where a latent image is not formed is disclosed in JP-A-62-62.
-70836, 62-81635, JP-A 2-1
No. 41756 and No. 2-141757. In the above light-sensitive materials, a hydrazine derivative is generally used as a reducing agent in order to obtain an image with excellent contrast.

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

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

It is presumed that the base precursor used for such a light-sensitive material is decomposed by heating during heat development to generate a base and dissociates a reducing agent, thereby promoting image formation. However, when an image is formed using such a light-sensitive material, it is colored in a hue different from that of the color image-forming substance in the highest density portion for a very short time after the image formation and gradually returns to the hue of the color image-forming substance itself. That is, it has been found that there is a problem that color change occurs.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a light-sensitive material which can stably obtain an image having excellent discrimination in a short time and which does not cause color change immediately after image formation.

[0009]

Means for Solving the Invention As a result of intensive studies on the cause of the above-mentioned color change, the present inventors have found that it is due to a reducing agent (hydrazine derivative) dissociated by the base generated during the decomposition of the base precursor. .. Furthermore, as a result of examining the means for solving the above problems, the present inventors have found that the object of the present invention is to accommodate at least a silver halide, a hydrazine derivative, a polymerizable compound, a color image-forming substance, and a base precursor on a support. It has been found that this can be achieved by using a compound of the following general formula [I] as a hydrazine derivative in a light-sensitive material having a light-sensitive layer containing microcapsules.

General formula [I]

[Chemical 2]

In the general formula [I], R ₁ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group,
It represents an acylamino group, a sulfonylamino group, a ureido group, and an amino group, and n represents 0 or an integer of 1 to 5. (When n is an integer of 2 or more, R _{1 s} may be the same or different and may be linked to each other to form a condensed ring.) R ₂ is an alkyl group or a cycloalkyl group , Aralkyl group,
Represents an aryl group and a heterocyclic group.

The compound of the present invention will be described in detail below. In the general formula [I], R ₁ is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 30 or less carbon atoms (which may be substituted. For example, a methyl group, Ethyl group, n-butyl group,
2-ethylhexyl group, 2-methoxyethyl group, 2-chloroethyl group and the like), cycloalkyl group (which may be substituted. For example, cyclopentyl group, cyclohexyl group and the like), aralkyl group (which may be substituted. ,
Diphenylmethyl group, benzyl group, 1-phenylethyl group, etc., aryl group (may be substituted.
Phenyl group, tolyl group, 4-methoxyphenyl group, 2-
Methoxy-4-methylphenyl group, etc.), alkoxy group (which may be substituted, for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, 2-ethylhexyloxy group, methoxyethoxy group, etc.), aryl Oxy group (which may be substituted. For example, phenoxy group, 4-cyanophenoxy group, 3,5-dichlorophenoxy group, 4-methylphenoxy group, etc.), acylamino group (which may be substituted. For example, acetyl Amino group,
n-propionylamino group, benzoylamino group, etc., 3
-Chlorobenzoylamino group and the like), sulfonylamino group (which may be substituted. For example, methanesulfonylamino group, ethanesulfonylamino group, p-toluenesulfonylamino group and the like), and ureido group (which may be substituted. , A methylaminocarbonylamino group, a phenylaminocarbonylamino group, etc.) and an amino group (which may be substituted. Further, the substituent may form a ring. For example, N-methylamino group, N, N-diethylamino group. ,
N, N-dioctylamino group, morpholino group, piperidyl group, etc.), and n represents 0 or an integer of 1 to 5. (When n is an integer of 2 or more, the R _{1 s} may be the same or different and may be linked to each other to form a ring.

R ₂ is an alkyl group having 30 or less carbon atoms (which may be substituted. For example, methyl group, ethyl group, isopropyl group, 2-ethylhexyl group, n-octyl group,
2-methoxyethyl group, etc.), cycloalkyl group (which may be substituted, for example, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (which may be substituted, for example, diphenylmethyl group, benzyl group, 1-phenylethyl Group, etc.), aryl group (which may be substituted. For example, phenyl group, p-toluyl group, p-methoxyphenyl group, 3- (pentanecarbonylamino) phenyl group, 3
-(Octanesulfonylamino) phenyl group, 2-chlorophenyl group, etc., and heterocyclic group (which may be substituted. For example, unsaturated heterocyclic group such as pyridyl group, cenyl group, furyl group, or tetrahydrofuran, sulfolane , 2,2,6,6-tetramethylpiperidine).

The hydrazine derivative of the present invention is disclosed in JP-A-62-62.
It can be synthesized by the method described in -180361, 62-275247 and the like. Specific examples of the hydrazine derivative represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

In the present invention, the hydrazine derivative is preferably used in the range of 1 to 500 mol%, more preferably 10 to 200 mol%, based on the total amount of silver. Two or more kinds of these hydrazine derivatives can be used in combination. Further, other types of reducing agents can be used in combination.

As the reducing agent which can be used in combination with the hydrazine derivative of the present invention, hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles,
4-amino-5-pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines,
Reductones, amino reductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acyl Aminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamido ketones , Hydrazines, etc. Regarding the above-mentioned various reducing agents,
"Public Technology No. 5" (Aztec Co., Ltd., issued March 22, 1991), pages 18 to 35, for details. The addition amount of the reducing agent which can be used in combination with the hydrazine derivative of the present invention can be widely varied, but is generally 0.1 to 1500 mol%, preferably 10 to 10 mol% with respect to the silver salt.
It is 300 mol%. )

The silver halide, the polymerizable compound, the color image-forming substance, the base precursor, the microcapsules containing the above components, and the support, which are used in the photothermographic material of the present invention (hereinafter simply referred to as photosensitive material), are described below. explain.

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

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

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

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

The 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 1.
It is described on page 7. 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 polymerizable compound that can be used in the light-sensitive material of the present invention is not particularly limited, and known polymerizable compounds can be used. It is preferable to use a polymerizable compound having a high boiling point (for example, a boiling point of 80 ° C. or higher) that is less likely to volatilize during heating because it is subjected to heat development treatment. Further, since the present invention is intended to immobilize the color image forming substance by polymerizing and curing the polymerizable compound, the polymerizable compound is preferably a crosslinkable compound having a plurality of functional groups in the molecule. The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group, but a compound having an ethylenically unsaturated group is particularly preferable. Examples of compounds having an ethylenically unsaturated group include acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydrides, maleic acid esters, and itacone. There are acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives. The above-mentioned various polymerizable compounds are described in detail in "Public Technology No. 5", pages 51 to 55 and Japanese Patent Application No. 3-116667.

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

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

As the base precursor 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 64-5.
4452, salts of organic acids and bases which are decarboxylated by heating as described in JP-A Nos. 4452 and 59-157637.
Nos. 59-166943 and 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 Nos. 2-146041, and 3-2.
No. 5444, each publication) Here, in dispersing the base precursor in water, a nonionic or amphoteric water-soluble polymer described in “Public Technology No. 5”, pages 128 to 135 can be used. ..

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

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

When aminoaldehyde 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 uniform over a certain value, as in the photosensitive material described in JP-A-63-5334.
Further, the film thickness of the photosensitive microcapsules is not shown in
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 silver halide grains to be one fifth or less of the average size of 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. -Styrene copolymers, maleic anhydride / inbutylene copolymers and the like can be mentioned. In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight. In the above case, it is particularly preferable to use the nonionic water-soluble polymer in combination with the water-soluble polymer having a small amount of sulfinic acid groups. Further, in order to reduce the solubility of the base precursor in the polymerizable compound, in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexylurea, octyl alcohol, dodecyl alcohol, stearyl alcohol, -OH such as stearamide,-. SO ₂ NH ₂ , −
CONH _2, it is also possible to add a compound having a hydrophilic group such as -NHCONH _2.

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

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

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

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

The image forming accelerator has a function of promoting transfer of a base or a 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.

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

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

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

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

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

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction of a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More details are described in JP-A-62-253159, pages (31) to (32), and the above-mentioned "Known technology No. 5", pages 98 to 107.

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

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

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

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

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

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

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

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

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

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

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

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

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

When the image information does not pass through an electric signal, for example, direct 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, and scanning exposure can also be performed through a slit or the like. You can also stretch or reduce the original image. In this case, the light source is not a monochromatic light source such as a laser but a light source such as a tungsten lamp or a fluorescent lamp, or a combination of a plurality of monochromatic light sources.

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

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

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

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

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

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

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

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

In the image forming method of the present invention, the unpolymerized polymerizable compound is transferred to the image receiving material by the step of applying pressure in the state where the 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 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 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.

[0081]

【Example】

Example 1 Preparation of Silver Halide Emulsion (EB-1) 24 g of lime-processed inert gelatin was added to 900 ml of distilled water, dissolved at 40 ° C. over 1 hour, 3 g of NaCl was added, and 1N sulfuric acid was added thereto to pH 3.2. Adjusted to.

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

To this emulsion, 1.1 g of (CK-1) was added, precipitated, washed with water, desalted, and then added with 6 g of lime-processed gelatin to dissolve, 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 0.24 μm and a coefficient of variation of 20% was prepared.

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

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

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

[0087]

[Chemical 9]

[0088]

[Chemical 10]

(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.

[0091]

[Chemical 11]

Preparation of Pigment Dispersion (GY-1) To 255 g of the polymerizable compound (MN-1), 45 g of Seika Fast Yellow 5900 (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 270 g of the polymerizable compound (MN-1), microlith was added.
Magenta 2BA (trade name, manufactured by Ciba Geigy) 30g
Were mixed and stirred using an Eiger motor mill (manufactured by Eiger Engineering Co., Ltd.) at 5000 rpm for 1 hour to obtain a dispersion (GM-1).

Preparation of Pigment Dispersion (GC-1) To 255 g of the polymerizable compound (MN-1), 45 g of copper phthalocyanine (CI Pigment 15) and Disperbik-161.
Mix 15g, Eiger Motor Mill (Eiger
(Manufactured by Engineering Co., Ltd.) was stirred at 5000 rpm for 1 hour to obtain a dispersion (GC-1).

Preparation of Photosensitive Composition (PB-1) 45 g of pigment dispersion (GY-1) was added with (SV of (1P-1)
-1) 9 g of 10% (wt%) solution, (RD-1) 2.
3 g, compound (RE-3) 2.0 g of the present invention, (FF-
2 g of (SV-1) 0.5% (wt%) solution of 3) and 0.5 g of (ST-1) were added and dissolved to prepare an oily solution. 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., stirring was carried out at 10,000 rpm for 5 minutes using a 40φ dissolver to obtain a photosensitive composition (PB-1) as a W / O emulsion.

Preparation of Photosensitive Composition (PG-1) 49 g of pigment dispersion (GM-1) was added to (1P-1) of (SV
-1) 9 g of 10% (wt%) solution, (RD-1) 2.
0 g, 1.8 g of the compound (RE-3) of the present invention, (FF-
2 g of 0.5% (wt%) solution of (SV-1) of 3) and 0.5 g of (ST-2) were added and dissolved to prepare an oily solution. Add silver halide emulsion (EG-1) 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 (PG-1) as a W / O emulsion.

Preparation of Photosensitive Composition (PR-1) 45 g of the pigment dispersion (GC-1) was added with (S) of (1P-1).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.0 g, 1.8 g of the compound (RE-3) of the present invention, (F
2 g of (SV-1) 0.5% (wt%) solution of F-3)
And (ST-1) 0.5 g were added and dissolved to prepare an oily solution.

A silver halide emulsion (ER-1) was added to this solution.
7.6 g and 24 g of solid dispersion (KB-1) were added, and 5
While maintaining the temperature at 0 ° C., a 40φ dissolver was used to stir at 10000 rpm for 5 minutes to obtain a W / O emulsion photosensitive composition (PR-1).

[0099]

[Chemical 12]

[0100]

[Chemical 13]

Photosensitive microcapsule dispersion (CB-
Preparation of 1) 46 g of water was added to 4 g of a 15% aqueous solution of polymer (2P-1).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
To this solution, 50 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. This mixed solution was added to the above-mentioned photosensitive composition (PB-1) and stirred at 60 ° C. for 20 minutes at 8000 rpm using a 40φ dissolver, and
An emulsion in the form of a / O / W emulsion was obtained. Separately, 5% of 37% aqueous formaldehyde solution was added to 31.5 g of melamine.
2.2 g and 170.3 g of water were added, the mixture was heated to 60 ° C. and stirred for 30 minutes to obtain a transparent aqueous solution of the melamine-formaldehyde initial condensate.

25 g of this initial condensate was added to the emulsion in the state of 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. Then add this liquid to 30
The temperature was raised to 70 ° C. per minute, and the mixture was further stirred for 30 minutes. To this, add 10.3 g of 40% aqueous solution of urea and add 2N
The pH was adjusted to 3.5 with sulfuric acid and stirring was continued at 70 ° C. for a further 40 minutes. This solution was cooled to 40 ° C., 9 g of a 3% aqueous solution of κ-carrageenan was added, the mixture was stirred for 10 minutes, and the pH was adjusted to 6.5 with a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB- 1) was prepared. Polymer (2P-1) Polyvinylbenzenesulfinic acid potassium-co-acrylamide Polymer (2P-2) Polyvinylpyrrolidone K-90

Photosensitive microcapsule dispersion (CG-
1) and Preparation of (CB-1) 36 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-1).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
To this solution, 60 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. The photosensitive composition (PG-1) was added to this mixed solution, and the mixture was stirred at 60 ° C. for 20 minutes at 6000 rpm using a 40φ dissolver, and was then mixed with W.
An emulsion in the form of a / O / W emulsion was obtained.

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

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

Then, in the preparation of (CB-1), (P
(PR-1) was used in place of B-1) and the dissolver was stirred at a rate of 10000 min.
A photosensitive microcapsule dispersion (CR-1) was prepared in the same manner except that the rotation was continued for 20 minutes.

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

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

[0109]

[Chemical 14]

This coating solution was applied on the aluminum vapor-deposited surface of a support obtained by vapor-depositing aluminum on a polyethylene terephthalate film having a thickness of 25 μm by an extrusion method so that the coating amount was 109 cc / m ^2, and dried at 60 ° C. The photosensitive material 101 was prepared by winding the coated surface inside at 25 ° C. and 60%. 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).

[0112]

[Chemical 15]

Example 2 In Example 1, the photosensitive compositions (PB-1), (PG-
1) and (PR-1) are prepared, the compound of the present invention (RE-
Instead of (3), (RE-7) was added in an amount of 1.8 g and 1.
A light-sensitive material 102 was prepared in the same manner as in Example 1 except that 2 g and 1.2 g were used.

Example 3 In Example 1, the photosensitive compositions (PB-1) and (PG-
1) and (PR-1) are prepared, the compound of the present invention (RE-
Instead of 3), two types of compounds (RE-6) and (RE-9) (1.2 g, 0.6 g) and (1.0
g, 0.4 g) and (1.0 g, 0.5 g) were used to prepare a photosensitive material 103 in the same manner as in Example 1.

Example 4 In Example 1, the photosensitive compositions (PB-1) and (PG-
1) and (PR-1) are prepared, the compound of the present invention (RE-
Instead of 3), (RE-12) 1.8g, (RE-2
4) A light-sensitive material 103 was prepared in the same manner as in Example 1 except that 1.0 g and (RE-30) 1.5 g were used.

Comparative Example 1 The photosensitive compositions (PB-1) and (PG-
1) and (PR-1) were prepared, the compound of the present invention (RE-
In place of 3), (RD-2) shown below is prepared as 1.
A light-sensitive material 105 for comparison was prepared in the same manner as in Example 1 except that 2 g was added.

[0117]

[Chemical 16]

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 30 seconds, the image receiving material (RS-
1) and the coated surfaces are overlaid at a speed of 2 cm / sec, a pressure roller (diameter 3 cm, pressure 400 kg / cm ² ) (surface temperature 7
The image receiving material was peeled off from the light-sensitive material immediately after passing through it. The maximum and minimum densities of the obtained image are X-Ri
It was measured by te310, and D value = minimum density / maximum density was used as a criterion of discrimination. (The smaller the D value, the better the discrimination.) Regarding the hue of the obtained image, cyan filter SP-5 (manufactured by FUJIFILM) and ND were used without using wedges.
After adjusting the exposure amount using a filter and after obtaining a sample of the cyan density part by the same image forming method as above,
Cyan density and yellow density were measured by X-Rite 310 to obtain Y value = yellow density / cyan density. The Y value was compared 10 seconds after the image formation and 30 minutes after the image formation.
(The smaller the difference in Y value between 30 seconds after image formation and 30 minutes after image formation, the smaller the change in hue.)

[0119]

[Table 1]

From the above results, it can be seen that an image with good discrimination can be obtained with the light-sensitive material of the present invention. In the light-sensitive material of the present invention, the change in hue immediately after image formation was very small.

Claims (1)

[Claims] 1. A photosensitive material having a photosensitive layer containing microcapsules containing at least a silver halide, a hydrazine derivative, a polymerizable compound, a color image-forming substance and a base precursor on a support, and the hydrazine derivative is generally A photosensitive material represented by the formula [I]. General formula [I] In the general formula [I], R ₁ is a hydrogen atom, a halogen atom,
It represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonylamino group, a ureido group, and an amino group, and n represents 0 or an integer of 1 to 5. (N is 2
In the case of the above integers, R _{1 s} may be the same or different, and may be linked to each other to form a condensed ring. ) R ₂ represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group.