JPH04235556A - Manufacture of photosensitive microcapsule and photosensitive material using it - Google Patents

Abstract

PURPOSE:To obtain photosensitive microcapsules each having a polymeric compound as its core material whose holding property is good. CONSTITUTION:A core material composed of a polymeric compound of density more than 1.0 is emulsified and dispersed in a water medium and a capsule wall made from amino aldehyde resin is formed around the oil drop of the core material. Capsules generated are sunk into the water medium and a part or the whole of the supernatant is removed and the capsules are dispersed again in the water medium. Next, a capsule wall made from amino aldehyde resin is further formed around the capsules.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing photosensitive microcapsules and a photosensitive material using the same.

0002

[Prior Art] (1) A photosensitive material in which silver halide, a reducing agent, a color image-forming substance, and a polymerizable compound are housed in microcapsules (photosensitive microcapsules) has been disclosed in JP-A No. 61-275742 and 61-278849
It is stated in the No. (2) A photosensitive material in which a photopolymerization initiator, a color image forming substance, and a polymerizable compound are housed in microcapsules,
It is described in JP-A-57-179836, JP-A-57-197538, JP-A-62-60694, and JP-A-62-94843.

[0003] As an image forming method using a photosensitive material having the structure (1) above, the photosensitive material is first imagewise exposed to form a latent image, and then this is thermally developed to form a latent image. polymerize the polymerizable compound in the portion that has been treated, further overlap the photosensitive material with an image-receiving material having an image-receiving layer, pressurize in this state, and transfer the unpolymerized polymerizable compound to the image-receiving material,
A commonly used method is to obtain a transferred image on an image-receiving material. On the other hand, regarding the method of polymerizing the polymerizable compound in the area where the latent image was not formed, JP-A No. 62-
No. 70836, No. 62-81635, JP-A-2-14
No. 1756, No. 2-141757, No. 2-20725
No. 4, No. 2-262662, and other publications and specifications.

[0004] Various wall materials for microcapsules used in these photosensitive materials and image forming methods are known.
JP 64-91131, JP 1-154140, JP 2-89680, JP 62-209438, JP 6
No. 3-269146, No. 62-209440, No. 62
-209437, No. 62-209441, etc. Among these, JP-A-62-209439
The microcapsules whose wall material is made of amino aldehyde resin, as described in the above publication, are particularly excellent in retaining core substances. In addition to the amino aldehyde resin wall microcapsules mentioned above, microcapsule manufacturing methods include emulsifying and dispersing oil droplets as a core material in an aqueous medium, and then forming a polymer resin wall around the oil droplets. is common.

[0005]

Problem to be Solved by the Invention: After emulsifying and dispersing an oily liquid containing a polymerizable compound in an aqueous medium, urea and
When a capsule wall made of formalin/resorcinol or melamine/formalin resin is formed, the resulting microcapsules may not necessarily have good core substance retention properties depending on the conditions. In particular, JP-A-64-32
No. 251, JP-A No. 1-263641, JP-A No. 2-14
6041 and Japanese Patent Application No. 1-160148, this tendency was stronger when a base precursor was included in the microcapsules in order to speed up the development reaction. As a result, photosensitive materials with photosensitive layers containing these microcapsules exhibit stickiness, which is thought to be due to seepage of the core substance, and when images are formed using them, Dmin (lowest density area) The problem arose of rising prices.

[0006]

[Means for solving the problem] Through the research of the present inventor,
The above-mentioned problem is to emulsify and disperse an oil-based liquid containing at least a color image-forming substance and a polymerizable compound and (1) a silver halide and a reducing agent or (2) a photopolymerization initiator and having a density of more than 1.0 in an aqueous medium. After forming a microcapsule wall made of amino aldehyde resin around the oil droplets, the resulting capsules are allowed to settle, some or all of the supernatant is removed, the capsules are redispersed in an aqueous medium, and then the capsules are This was achieved by further forming a capsule wall made of amino aldehyde resin around the .

[0007] A method for sedimentation of capsules once formed is described in Japanese Patent Application No. 136267/1999, and
By removing transfer inhibitors such as microcapsules and amorphous objects, Dmax (highest density area) has been improved compared to conventional photosensitive materials, but Dmin and core substance retention of microcapsules still remain. There wasn't. Therefore, the present inventor found that by re-encapsulating the above-mentioned microcapsules and microcapsules from which irregularly shaped objects were removed, Dmin was improved and a sufficient capsule wall with excellent core substance retention was formed. This has led to the present invention.

In the two-time encapsulation of the present invention, an amino aldehyde resin is used as the wall material in both the first and second encapsulations, and the method is described, for example, in US Pat. 40873
No. 76, No. 4089802 and No. 402545
No. 5, JP-A-62-209439, JP-A-64-91
No. 131, Japanese Patent Application Publication No. 1-154140 and Japanese Patent Application No. 1983
It is described in JP-241635. After the first encapsulation, the resulting capsules are sedimented, some or all of the supernatant is removed, water or an aqueous liquid containing a water-soluble polymer is added, and the capsules are redispersed in the aqueous medium, followed by the first encapsulation. The microcapsules according to the present invention can be manufactured by following the same process as encapsulation and again forming a capsule wall made of amino aldehyde resin.

[0009] Capsules may be sedimented by natural sedimentation by standing still, or by centrifugation. A precipitating agent may be used, but it is necessary that it can be redispersed in a later step. Examples of the amino aldehyde resin used as the capsule wall material of the present invention include urea-formaldehyde resin, urea-formaldehyde resin,
Examples include formaldehyde-resorcinol resin, melamine-formaldehyde resin, acetoguanamine-formaldehyde resin, and benzoguanamine-formaldehyde resin. In the present invention, the first and second
It is particularly preferable to use melamine-formaldehyde resin for both rounds of encapsulation because capsules with high core substance retention can be obtained.

[0010] Furthermore, in order to obtain capsules with particularly excellent wall density, JP-A-2-216151 discloses that in the first encapsulation, a water-soluble polymer having a sulfinic acid group and a polymer having an ethylenically unsaturated group are used. Microcapsules have been disclosed in which a polymer wall of a high molecular compound such as melamine/formaldehyde resin is provided around a membrane made of a reaction product with a chemical compound, which is preferable for the present invention.

[0011] The average particle size of the microcapsules formed by the method of the present invention is preferably 5 to 25 μm. The particle size distribution of microcapsules was determined by Japanese Patent Application Laid-open No. 6
As in the photosensitive material described in Publication No. 3-5334, it is preferable that the distribution is uniform over a certain value. Further, the film thickness of the microcapsules is preferably within a certain value range with respect to the particle diameter, as in the photosensitive material described in JP-A-63-81336. In addition, in order to accommodate silver halide in microcapsules, the average particle size of silver halide grains, which will be described later, is preferably one-fifth or less, and one-tenth or less, of the average size of microcapsules. It is even more preferable. The average grain size of silver halide grains is 5% of the average size of microcapsules.
A uniform and smooth image can be obtained by reducing the amount to 1/1 or less.

When silver halide is contained in microcapsules, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules. A photosensitive material containing silver halide in the wall material of microcapsules is described in JP-A-62-169147. The photosensitive microcapsules of the present invention contain (
1) A silver halide, a reducing agent, a color image-forming substance, and a polymerizable compound; or (2) a photopolymerization initiator, a color image-forming substance, and a polymerizable compound. In the case of (1), the polymerizable compound can be polymerized by developing after exposure. In the case of (2), the polymerizable compound can be polymerized only by exposure. Polymerization can be accelerated by further applying heat.

The present invention will be mainly explained with reference to (1), but as will be described later, the photopolymerization initiator that can be used in (1) can also be used in (2). In the production of photosensitive microcapsules according to the above (1) of the present invention, when dispersing an oily liquid containing at least silver halide, a reducing agent, a color image forming substance, and a polymerizable compound in an aqueous medium, preferably contains a nonionic water-soluble polymer and an anionic water-soluble polymer. In this case, the oily liquid containing the polymerizable compound is preferably 10 to 120% by weight based on the aqueous medium,
More preferably 20 to 90% by weight.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy Examples include propylcellulose and methylcellulose. Examples of anionic water-soluble polymers include polystyrene sulfinic acid, styrene sulfinate copolymers, polystyrene sulfonates, styrene sulfonic acid copolymers, polyvinyl sulfate ester salts, polyvinyl sulfonates, and maleic anhydride. - Styrene copolymers, maleic anhydride/isobutylene copolymers, etc. can be mentioned. In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably in the range of 0.01 to 5% by weight, more preferably in the range of 0.1 to 2% by weight.

In the above case, it is particularly preferable to use a nonionic water-soluble polymer and a water-soluble polymer having a small amount of sulfinic acid groups in combination. Further, when the capsules are sedimented and the aqueous liquid added to the sedimented capsules after removing the upper layer contains a water-soluble polymer, it is preferable to use the above-mentioned nonionic and anionic polymers. In addition, like the photosensitive material described in JP-A No. 63-32535,
It is preferable to keep the amount of residual aldehyde in the microcapsules below a certain value.

The silver halide, reducing agent, color image forming substance, polymerizable compound, and
and the support will be explained in detail. In the light-sensitive material of the present invention, any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide may be used as silver halide. be able to. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, dodecahedrons, and dodecahedrons, those with irregular crystal systems such as spherical and plate shapes, It may be one having crystal defects such as twin planes, or a composite form thereof.

The grain size of the silver halide can be as fine as about 0.01 microns or less, or as large as up to about 10 microns in projected area diameter, and can be used in polydisperse emulsions as described in US Pat. No. 3,574,628. No. 3,655,394
Monodisperse emulsions such as those described in No. 1, British Patent No. 1,413,748 and the like may also be used. Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
Tographic Science and En
gineering), Vol. 14, pp. 248-257 (
1970); U.S. Patent No. 4,434,226;
, No. 414,310, No. 4,433,048, No. 4,
439,520 and British Patent No. 2,112,157
It can be easily prepared by the method described in No.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it 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 rhodan or lead oxide. In addition, halogen composition,
Two or more types of silver halide grains having different crystal habits, grain sizes, etc. can also be used together.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation
ion and types)”, and the same No.
18716 (November 1979), p. 648, etc. The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17
643 and the same No. 18716,
The relevant sections 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 descriptions are shown in the table below. Additive type RD17
643RD18716
Chemical sensitizer page 23
Page 648 right column
Sensitivity enhancer
Same as above
Spectral sensitizer pages 23-24
Page 648 right column~
supersensitizer
Page 649 right column
Antifogging agent pages 24-25
Page 649 right column~
and stabilizer As the silver halide grains, it is preferable to use silver halide grains having a relatively low fog value, such as the light-sensitive material described in JP-A-63-68830.

In order to uniformly contain silver halide in the microcapsules, it is preferable that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit be dissolved in the polymerizable compound. The details are described in JP-A-62-209450, JP-A-63-287844, and JP-A-2-216151.

The reducing agent that can be used in the photographic material of the present invention has a function of reducing silver halide and/or a function of promoting (or suppressing) polymerization of a polymerizable compound. There are various types of reducing agents having the above functions. The reducing agents 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-sulfonamide indanones, 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α- These include sulfonamide ketones and hydrazines.

[0023] Regarding various reducing agents having the above-mentioned functions, please refer to JP-A-61-183640 and JP-A-61-1885.
35, 61-228441, and JP-A-62-70836, 62-86354, and 6
No. 2-86355, No. 62-206540, No. 62-
No. 264041, No. 62-109437, No. 63-2
No. 54442, Japanese Patent Application No. 63-97379, No. 63-2
No. 96774, No. 63-296775, JP-A-2-2
No. 07254, No. 1-54101, No. 1-91162
No. 1-90087 and other publications and specifications. (Including those described as developing agents or hydrazine derivatives) Also, regarding the above-mentioned reducing agents, T. Jmam
“The Theory of the P” by es
photographic Process” 4th edition, pp. 291-334 (1977) Research Disclosure Vol. 170, June 1978 No. 17
No. 029 (pages 9-15), and Vol. 176,
There is also a description in No. 17643 (pages 22-31) of December 1978.

Furthermore, as in the photosensitive material described in JP-A No. 62-210446, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base is used instead of the reducing agent. May be used. The reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature can also be effectively used in the photosensitive material used in this specification. Therefore, the "reducing agent" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications and literature. Among these reducing agents, those having basicity that form salts with acids can also be used in the form of salts with appropriate acids.

These reducing agents may be used alone, or as described in the above specifications, two or more reducing agents may be used in combination. When two or more types of reducing agents are used together, the interaction of the reducing agents is, first, to promote the reduction of silver halide (and/or organic silver salt) through so-called superadditivity; , causing polymerization of the polymerizable compound via a redox reaction with other reducing agents coexisting with an oxidized form of the first reducing agent generated by reduction of silver halide (and/or organic silver salt); (or suppressing polymerization), etc. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring. Specific examples of the above reducing agent are shown below.

[0026]

[Chemical formula 1]

[0027]

[Case 2]

[0028]

[Chemical formula 3]

[0029]

[C4]

The amount of the reducing agent added can vary widely, but is generally 0.1 to 1500 mol %, preferably 10 to 300 mol %, based on the silver salt. There are no particular restrictions on the color image-forming substance that can be used in the photosensitive material of the present invention, and various types can be used. In other words, substances that themselves are colored (dyes and pigments), and substances that are colorless or light in color but are exposed to external energy (heating, pressure, light irradiation, etc.) or other components (color developers). Color image-forming substances also include substances that develop color upon contact with (color formers).

As the color image-forming substance of the present invention, dyes and pigments which have excellent image stability and are themselves colored are preferred, as described in JP-A-62-187346. As the dyes and pigments used in the present invention, in addition to commercially available dyes and pigments, known dyes and pigments described in various literatures can be used. Regarding literature, please refer to the color index (
C. I. ) Handbook, “Latest Pigment Handbook” edited by Japan Pigment Technology Association (published in 1977), “Latest Pigment Application Technology” CMC Publishing (
(published in 1986), “Printing Ink Technology” (CMC Publishing, 1
(published in 1984).

The types of pigments are white pigments, black pigments, yellow pigments, orange pigments, brown pigments, red pigments, violet pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other heavy pigments. Included are coalescing dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, and isoindolinone pigments. , quinophthalone pigments, dyeing lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, etc. can be used.

The pigment that can be used in the present invention may be the above-mentioned naked pigment, or may be a pigment that has been subjected to surface treatment. Surface treatment methods include methods of surface coating with resin or wax, methods of attaching surfactants, methods of bonding reactive substances (for example, silane coupling agents, epoxy compounds, polyisocyanates, etc.) to the pigment surface, etc. is considered and described in the following documents.

Properties and Applications of Metallic Soaps (Saiwai Shobo) Printing Ink Technology (CMC Publishing, 1984) Latest Pigment Application Technology (CMC Publishing, 1986) The particle size of the pigment that can be used in the present invention is So, 0.01μ~1
It is preferably in the range of 0μ, more preferably in the range of 0.05 to 1μ. The pigment is preferably used in an amount of 5 to 60 parts by weight based on 100 parts by weight of the polymerizable compound.

[0035] As a method for dispersing the pigment into the polymerizable compound, known dispersion techniques used in ink production, toner production, etc. can be used. Examples of the dispersing machine include a sand mill, attritor, pearl mill, super mill, ball mill, impeller, desperser, KD mill, colloid mill, Dynatron, three-roll mill, and pressure kneader. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986). Polymerizable compounds used in photosensitive materials generally have addition polymerizability or ring-opening polymerizability. Examples of the compound having addition polymerizability include compounds having an ethylenically unsaturated group, and compounds having ring-opening polymerizability include compounds having an epoxy group, and compounds having an ethylenically unsaturated group are particularly preferred.

Compounds having ethylenically unsaturated groups that can be used in photosensitive materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, and methacrylamides. , maleic anhydride, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

Specific examples of preferred polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxyethyl esters. Acrylate, tricyclodecanyloxyacrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylolpropane triacrylate acrylate, pentaerythritol tetraacrylate,

Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylated bisphenol A diacrylate,
2-(2-hydroxy-1,1-dimethylethyl)-5
-Hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, 2-(2-hydroxy-1,1-dimethylethyl)-5,5-dihydroxymethyl-1,3-
Examples include dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, hexaacrylate of caprolactone adduct of dipentaerythritol, polyacrylate of hydroxypolyether, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Examples include pentaerythritol tetramethacrylate and polyoxyalkylenated bisphenol A dimethacrylate. The above polymerizable compounds may be used alone or in combination of two or more. For photosensitive materials containing two or more types of polymerizable compounds, JP-A-62
There is a description in Publication No.-210445. In addition, a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned reducing agent can also be used as a polymerizable compound.

As the support for the photosensitive material of the present invention, it is preferable to use a material with good thermal conductivity. Materials that can be used for the support include glass, paper, high-quality paper,
Films such as baryta paper, coated paper, cast coated paper, synthetic paper, metals and their analogs, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, polyimide, and resin materials. Examples include paper laminated with a polymer such as polyethylene.

Among these, the preferred support of the present invention is a polymer film, and from the above-mentioned thermal conductivity, a polymer film with a thickness of 50 μm or less is particularly preferred. That is, the image forming method of the present invention requires at least a series of steps such as imagewise exposure, heating, and pressing, and it is more efficient to use the photosensitive material in the form of a continuous strip. Particularly preferred. Therefore, photosensitive materials are transported, heated, pressurized, and
Since it is subjected to operations such as winding and rolling, it is necessary to have mechanical properties or thermal properties that can withstand such operations. From this point of view, the support is preferably a polymer film from the viewpoint of mechanical properties (tensile strength, modulus of elasticity, stiffness, etc.), and among these, one with good thermal conductivity and a thickness of 50 μm or less is particularly preferred. If the thickness exceeds 50 μm, the thermal conductivity is poor and it is difficult to shorten the heat development time. Moreover, those having a thickness of 10 μm or less have problems in transportability in terms of mechanical strength.

Furthermore, in order to coat the photosensitive layer on the support,
It is preferable to provide an undercoat layer as described in JP-A-61-113058 on the polymer film, or to provide a metal vapor deposited film such as aluminum on the polymer film. Therefore, as a support for a photosensitive material for carrying out the image forming method of the present invention, a polymer film having a thickness of 50 μm or less and having an aluminum vapor-deposited film is particularly preferable. Other components that can be used in the photosensitive material of the present invention will be explained below. In the present invention, it is preferable to use a base precursor in order to cause the heat development reaction to proceed rapidly. Examples of base precursors that can be used in the photosensitive material of the present invention include base precursors of inorganic bases and organic bases (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.)
can be used.

Preferred base precursors include JP-A-59-180549, JP-A-59-180537, JP-A-59-195237, JP-A-61-32844, and JP-A-61.
-36743, 61-51140, 61-52
No. 638, No. 61-52639, No. 61-53631
No. 61-53634, No. 61-53635, No. 61-53636, No. 61-53637, No. 61-
No. 53638, No. 61-53639, No. 61-536
No. 40, No. 61-55644, No. 61-55645, No. 61-55646, No. 61-84640, No. 6
No. 1-107240, No. 61-219950, No. 61
-251840, 61-252544, 61-
No. 313431, No. 63-316740, No. 64-6
8746 and Japanese Patent Application No. 62-209138, salts of organic acids and bases that are decarboxylated by heating, and JP-A Nos. 59-157637 and 59-166.
Examples include compounds that eliminate bases upon heating as described in Japanese Patent No. 943 and No. 63-96159.

The base precursor of the present invention is 50
It is preferable to release the base at a temperature between 80°C and 200°C.
It is more preferable to release at a temperature of 180°C to 180°C. In the present invention, in order to make the heat development reaction proceed more rapidly, it is preferable to accommodate the base precursor in microcapsules. In that case, the following base precursor consisting of a salt of a carboxylic acid and an organic base having a solubility in water and a polymerizable compound at 25° C. of 1% or less is preferred. (a) The base precursor consists of a salt of a carboxylic acid and an organic base, and the organic base has a partial structure corresponding to an atomic group obtained by removing one or two hydrogen atoms from an amidine represented by the following formula (1). It is a diacid to tetraacid base consisting of four structural groups and the structural group of the partial structure.

[0045]

[C5]

[In the above formula (1), R11, R1
2, R13 and R14 each represent a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic residue (each group may have one or more substituents), and R11, R12
, R13 and R14 may be bonded to each other to form a five- or six-membered nitrogen-containing heterocycle] (b) The base precursor is a salt of a carboxylic acid and an organic base. and the organic base has the following formula (2
) is a diacid to tetraacid base consisting of two to four partial structures corresponding to an atomic group obtained by removing one or two hydrogen atoms from guanidine, and a linking group of the partial structures.

[0047]

[C6]

[In the above formula (2), R21, R2
2, R23, R24 and R25 each represent a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic residue ( each group may have one or more substituents), and R21
, R22, R23, R24, and R25 may be bonded to each other to form a five- or six-membered nitrogen-containing heterocycle] In addition, the above (a) and (b) The base precursors are described in detail in JP-A-63-31670 and JP-A-64-68746, respectively. Specific examples of these base precursors are shown below, but are not limited thereto.

[0049]

[C7]

[0050]

[Chemical formula 8]

[0051]

[Chemical formula 9]

[0052]

[Chemical formula 10]

[0053]

[Chemical formula 11]

[0054]

[Chemical formula 12]

In the present invention, when the base precursor is accommodated in microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used. Kaihei 1-2
63641), it is particularly preferable to use a photosensitive composition in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (Unexamined Japanese Patent Publication No. 63-21
No. 8964, Japanese Patent Application No. 1-182245, Japanese Patent Application No. 1-1
60148 and the specification) Here, when dispersing the base precursor in water, it is preferable to use a nonionic or amphoteric water-soluble polymer.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy Examples include propylcellulose and methylcellulose. Moreover, gelatin can be mentioned as an amphoteric water-soluble polymer.

The above water-soluble polymer is preferably contained in a proportion of 0.1 to 100% by weight, more preferably 1 to 50% by weight, based on the base precursor. Further, the base precursor is preferably contained in an amount of 5 to 60% by weight, more preferably 10 to 50% by weight, based on the dispersion. In addition, the base precursor is 2 for polymerizable compounds.
It is preferably contained in a proportion of ~50% by weight, and 50% by weight.
More preferably, it is contained in a proportion of 30% by weight.

In addition, in order to reduce the solubility of the base precursor in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexyl urea, octyl alcohol, dodecyl alcohol, stearyl alcohol, stearamide, etc. are added to the polymerizable compound. -OH,
-SO2 NH2 , -CONH2 , -NHCONH
A compound having a hydrophilic group such as 2 can also be added.

The binders that can be used in the photosensitive material can be contained in the photosensitive layer alone or in combination. It is preferable to use a mainly hydrophilic binder. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. synthetic polymeric materials such as water-soluble polyvinyl compounds. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others. Incidentally, a photosensitive material using a binder is described in JP-A-61-69062. Furthermore, a photosensitive material using a binder together with microcapsules is described in JP-A-62-209525.

In the present invention, an organic metal salt can be used together with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the organic silver salt oxidizing agents described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 626, columns 52-53. Also, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A No. 13235, and JP-A No. 6
Acetylene silver described in the publications No. 1-249044 and No. 64-57256 is also useful. Two or more types of organic silver salts may be used in combination. The above organic silver salts can be used together in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is 1mg in terms of silver.
A suitable amount is between 10 g/m2 and 10 g/m2.

The anti-smudge agent used in the photosensitive material is preferably a particulate material that is solid at room temperature. As a specific example,
Starch particles described in UK Patent No. 1,232,347, polymer fine powders described in US Pat. No. 3,625,736, etc., microcapsule particles containing no coloring agent described in UK Patent No. 1,235,991, etc., US Pat. No. 271
Inorganic particles such as cellulose fine powder described in No. 1375, talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina can be mentioned. The average particle size of the particles is preferably in the range of 3 to 50 μm, more preferably in the range of 5 to 40 μm in volume average diameter. As mentioned above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective if the particles are larger than the microcapsules.

Various image formation accelerators can be used in the photosensitive material. Image formation accelerators have functions such as ■ promoting the movement of bases or base precursors, promoting the reaction between reducing agents and silver salts, and promoting immobilization of dye-donating substances through polymerization. are classified into the aforementioned bases or base precursors, nucleophilic compounds, oils, heat solvents, surfactants, compounds that interact with silver or silver salts, compounds that have an oxygen scavenging function, and the like. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details, see U.S. Pat. No. 4,678,739, columns 38-40;
It is described in publications and specifications such as JP-A-62-209443.

In the light-sensitive material, in a system in which a polymerizable compound is polymerized in an area where a silver halide latent image is not formed,
A thermal or photopolymerization initiator can be used to initiate polymerization or to polymerize unpolymerized polymerizable compounds after image transfer. Examples of thermal polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, sulfinic acids, and the like. For details, please refer to the Society of Polymer Science, Edited by the Editorial Committee for Experimental Polymer Science.
Addition Polymerization/Ring-Opening Polymerization” (1983, Kyoritsu Shuppan) No. 6
It is described on pages 1 to 18, etc.

Examples of photopolymerization initiators include benzophenones, acetophenones, benzoins, and thioxanthone. Details of these are described in "Ultraviolet Curing System" (1989, General Technology Center), pages 63 to 147. Various surfactants can be used in photosensitive materials for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, promoting development, and the like. Specific examples of surfactants are given in JP-A-62-1734.
No. 63, No. 62-183457, etc.

An antistatic agent can be used in the photosensitive material for the purpose of preventing static electricity. It is described as an antistatic agent in Research Disclosure, 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. JP-A-63-29748 regarding photosensitive material with white pigment added to photosensitive layer
There is a description in the bulletin.

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

When a solvent for a polymerizable compound is used in a photographic material, it is preferable to encapsulate it in a microcapsule separate from the microcapsule containing the polymerizable compound. Regarding photosensitive materials using organic solvents that are miscible with polymerizable compounds encapsulated in microcapsules, Japanese Patent Laid-Open No. 6
There is a description in Publication No. 2-209524. A water-soluble vinyl polymer may be adsorbed onto the silver halide grains described above. A photosensitive material using a water-soluble vinyl polymer as described above is described in JP-A-63-91652.

In addition to those mentioned above, examples of optional components that can be included in the photosensitive layer and their usage can be found in the application specifications related to the above-mentioned series of photosensitive materials and in Research Disclosure Magazine Vol. 170, 19
It is described in No. 17029, June 1978 (pages 9-15). Layers that can be optionally provided on photosensitive materials include:
Image receiving layer, heating layer, antistatic layer, anticurl layer, peeling layer, cover sheet or protective layer, antihalation layer (
colored layer), etc.

[0069] Regarding the photosensitive material using a heat generating layer, see JP-A No. 61-294434, and about the photosensitive material provided with a cover sheet or protective layer, see JP-A No. 62-2.
No. 10447 discloses a photosensitive material provided with a colored layer as an antihalation layer, and Japanese Patent Application Laid-Open No. 63-101842.
They are described in the respective publications. Furthermore, examples of other auxiliary layers and their usage are also described in the applications relating to the above-mentioned series of light-sensitive materials.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include azoles and azaindenes described in RD17643 (1978) pages 24-25, and JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 2, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957, etc. are used. .

Various development stoppers can be used in the photosensitive material in order to always obtain a constant image regardless of the processing temperature and processing time during development. The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples thereof include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction of coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof. For more details, see JP-A-6
No. 2-253159 (31)-(32), Patent Application No. 1-
It is described in No. 72479, No. 1-3471, etc.

After the image forming method of the present invention, an image receiving material is generally used together with the photosensitive material. The image-receiving material used in the image forming method using the photosensitive material of the present invention will be described below. The image-receiving material may be only a support, but it is preferable to provide an image-receiving layer on the support. Supports for image-receiving materials are not particularly limited, but like the supports for photosensitive materials, glass, paper, high-quality paper, baryta paper, coated paper, cast-coated paper, synthetic paper, cloth, metal, and their analogs can be used. Examples include films of polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, etc., and papers laminated with resin materials and polymers such as polyethylene.

In addition, when using a porous material such as paper as a support for the image-receiving material, Japanese Patent Laid-Open No. 62-20953
It is preferable that the image-receiving material has a certain level of smoothness like the image-receiving material described in Japanese Patent No. 0. 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 the voids between the particles of the white pigment increase the receptivity of the polymerizable compound.

Examples of the white pigment used in the image-receiving layer include inorganic white pigments such as oxides such as silicon oxide, titanium oxide, zinc oxide, magnesium oxide, and aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate, and magnesium carbonate. , barium carbonate, calcium carbonate,
Alkaline earth metal salts such as calcium silicate, magnesium hydroxide, magnesium phosphate, and magnesium hydrogen phosphate, as well as aluminum silicate, aluminum hydroxide, zinc sulfide, various clays, talc, kaolin, zeolite, acid clay, and activated clay. Examples include white clay and glass. Examples of organic white pigments include polyethylene, polystyrene, benzoguanamine resin, urea-formalin resin, melamine-formalin resin, polyamide resin, and the like. These white pigments may be used alone or in combination, but
Those with high oil absorption for polymerizable compounds are preferred.

Further, as the binder used in the image-receiving layer of the present invention, water-soluble polymers, polymer latexes, polymers soluble in organic solvents, etc. can be used. Examples of water-soluble polymers include cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, proteins such as gelatin, phthalated gelatin, casein, and ovalbumin, starches such as dextrin and etherified starch, polyvinyl alcohol, and polyvinyl alcohol moieties. Synthetic polymers such as acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, polystyrene sulfonic acid,
Other examples include locust bean gum, pullulan, gum arabic, and sodium alginate.

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

Examples of polymers soluble in organic solvents include polyester resins, polyurethane resins, polyvinyl chloride resins, and polyacrylonitrile resins. The above-mentioned binders can be used in combination of two or more types, and can also be used in combination in such a ratio that the two types of binders cause phase separation. An example of such usage is described in Japanese Patent Laid-Open No. 1-154789.

[0078] 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 to 10 μ.
It ranges from 1 g to 60 g, preferably from 0.5 g to 30 g. The weight ratio of the white pigment to the binder is preferably in the range of 0.01 to 0.4 of the binder to 1 of the pigment, and is 0.0
The range of 3 to 0.3 is more preferable.

In addition to the binder and the white pigment, the image-receiving layer can contain various additives as described below. For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Typical color developers include phenols, organic acids or their salts, or esters, but when leuco dyes are used as color image forming substances,
Zinc salts of derivatives of salicylic acid are preferred, especially 3,
Zinc 5-di-α-methylbenzylsalicylate is preferred. The color developer is preferably contained in the image-receiving layer in a coating amount ranging from 0.1 to 50 g/m<2>. More preferably, it is in the range of 0.5 to 20 g/m2.

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 constituted as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above structure has the advantage that it is easy to form a transferred image, and that a glossy image can be obtained by heating after image formation. The above thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastic resins (plastics), waxes, and the like. 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 an image-receiving layer containing thermoplastic compound fine particles as described above,
It is described in No. 2-280071 and No. 62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In forming images using image-receiving materials, color image-forming substances are transferred along with unpolymerized polymerizable compounds. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding with the curing process (fixing process) of the unpolymerized polymerizable compound. Further, regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see JP-A-62-161149, and regarding an image-receiving material having an image-receiving layer containing a thermal polymerization initiator, see JP-A-62-210444, respectively. There is a description.

In the image forming method using the photosensitive material of the present invention, the photosensitive material is transferred to a support not coated with a photosensitive layer during the imagewise exposure step, simultaneously with the imagewise exposure, or after the imagewise exposure. A series of steps will be described, including a step of heating from the surface of the photosensitive material, and a step of overlapping and pressing the surface of the photosensitive material coated with the photosensitive layer with the image receiving material. Although various exposure means can be used as the exposure method in the imagewise exposure step, a latent image of silver halide is generally obtained by imagewise exposure to radiation including visible light. The type of light source and the amount of exposure can be selected depending on the wavelength at which the silver halide is sensitive (in the case of dye sensitization, the sensitized wavelength) and sensitivity.

Typical light sources include natural light, ultraviolet light, visible light, infrared light, fluorescent light, tungsten lamp, mercury lamp, halogen lamp, xenon flash lamp, laser light source (gas laser,
solid state lasers, chemical lasers, semiconductor lasers, etc.)
Examples include light emitting diodes, plasma arc tubes, FOTs, and the like. In special cases, high-energy ray sources such as X-rays, γ-rays, and electron beams can also be used.

The photosensitive material of the present invention, especially in the case of a full-color photosensitive material, is composed of microcapsules that are sensitive to multiple spectral regions, and therefore requires image exposure using multiple corresponding spectral lines. It is. Therefore, one type of the light source may be used or a combination of two or more types may be used. When choosing a light source,
In addition to choosing a light source that is suitable for the sensitive wavelength of the photosensitive material, the choice can also be made by taking into consideration whether image information is transmitted via electrical signals, the processing speed of the entire system, compactness, power consumption, etc.

[0085] When image information does not go through electrical signals, for example, direct photography of landscapes or people, direct copying of original images,
In the case of exposure through a positive such as a reversal film, a camera, an exposure device for printing such as a printer or an enlarger, an exposure device of a copying machine, etc. can be used. In this case, the two-dimensional image can be exposed simultaneously in so-called one shot, or can be scanned and exposed through a slit or the like. You can also enlarge 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 multiple monochromatic light sources is usually used.

When image information is recorded via electrical signals, the image exposure device may be a combination of light emitting diodes and various lasers depending on the color sensitivity of the heat-developable color photosensitive material; Various devices known as image display devices (CRT, liquid crystal display, electroluminescent display, electrochromic display, plasma display, etc.) can also be used. In this case, the image information includes an image signal obtained from a video camera or an electronic still camera, a television signal typified by the Nippon Television Signal Standard (NTSC),
Image signals obtained by dividing an original image into many pixels using a scanner or the like, or image signals stored on recording materials such as magnetic tapes or disks can be used.

When exposing a color image, a combination of LEDs, lasers, fluorescent tubes, etc. is used depending on the color sensitivity of the photosensitive material, but it is also possible to use multiple combinations of the same type of LED, or to use a combination of different types. It's okay. In the photographic field, the color sensitivity of photosensitive materials is R (red), G (green), and B (blue).
Usually, they are photosensitive, but in recent years they are often used in combination with UV, IR, etc., and the range of use of light sources is expanding. For example, the color sensitivity of a photosensitive material is (G, R, IR)
or (R, IR (short wave), IR (long wave)), (
UV (short wave), UV (medium wave), UV (long wave)), (UV
, B, G) etc. are utilized. The light source may also be a combination of different types, such as a combination of two-color LED and a laser. The above-mentioned arc tube or element may be used for scanning exposure using a single tube or element for each color, or an array may be used to increase the exposure speed. Arrays that can be used include LED arrays, liquid crystal shutter arrays, magneto-optic shutter arrays, and the like.

The above-mentioned image display device is a CRT.
There are color displays and monochrome displays, as shown in Figure 2. However, a method of combining a monochrome display with a filter and performing several exposures may be adopted. Existing two-dimensional image display devices may be used in a one-dimensional manner like FOT, or one screen may be divided into several parts and used in combination with scanning.

The imagewise exposure step described above produces a latent image on the silver halide contained in the microcapsules. The image forming method using the photosensitive material of the present invention includes a step of heating in order to thermally develop the photosensitive material simultaneously with or after the imagewise exposure. Preferably, thermal development is carried out by heating the surface of the support on which the photosensitive layer of the photosensitive material is not coated.

This heating means is disclosed in Japanese Patent Application Laid-Open No. 61-29
As in the photosensitive material described in Japanese Patent No. 4434, a heating layer may be provided on the surface of the support on which the photosensitive layer of the photosensitive material is not coated and heated. Furthermore, as described in JP-A-61-147244, a hot plate, an iron, or a heated roller is used, or as described in JP-A-62-144166, a photosensitive material is sandwiched between a heated roller and a belt. A heating method may also be used.

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 the entire surface of the photosensitive material may be heated simultaneously (heating plate, heat plate, etc.) with a smaller surface area.
The entire surface may be heated over time by scanning with a heated roller, heated drum, etc.). In addition to the above heating method in which the heating element and the photosensitive material are brought into direct contact, it is also possible to heat the photosensitive material in a non-contact manner by applying electromagnetic waves, infrared rays, hot air, etc. to the photosensitive material.

In the image forming method using the photosensitive material of the present invention, thermal development is performed by heating the surface of the photosensitive material on the support on which the photosensitive layer is not coated. The surface coated with the layer may be in direct contact with the air, but it may also be covered with a heat insulating material to prevent heat from escaping. In this case, it is preferable not to apply strong pressure (10 kg/cm2 or more) to the photosensitive layer so as not to destroy the microcapsules contained in the photosensitive layer. Thermal development by heating may be carried out simultaneously with or after the imagewise exposure, but it is preferable to carry out heating after 0.1 seconds or more has elapsed after the imagewise exposure. Heating temperature is generally 60°C to 250°C, preferably 80°C
to 180° C., and the heating time is between 0.1 and 5 seconds.

The photosensitive material can be thermally developed as described above to polymerize the polymerizable compound in the areas where the silver halide latent image is formed or the areas where the silver halide latent image is not formed. In addition, if a polymerization inhibitor is generated in the area where a latent image of silver halide is formed by reaction with a reducing agent, the polymerization inhibitor may be added to the photosensitive layer in advance, preferably in microcapsules, to initiate thermal or photopolymerization. It is also possible to decompose the agent by heating or irradiating it with light, uniformly generating radicals, and polymerizing the polymerizable compound in the portion where the silver halide latent image is not formed. In this case, in addition to the imagewise exposure step and heat development step described above, a step of heating or exposing the entire surface is required if necessary, but the method is the same as the imagewise exposure step or the heat development step.

[0094] According to the image forming method using the photosensitive material of the present invention, the unpolymerized polymerizable compound is transferred to the image-receiving material by pressing the photo-sensitive material and the image-receiving material in a superimposed state, on which a polymer image is formed on the photosensitive layer. can be transferred to obtain a color image on an image-receiving material. As the above-mentioned pressurizing method, a conventionally known method can be used. 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 conveying using a pressure roller such as a nip roll. Pressure may be applied intermittently using a dot impact device or the like.

[0095] It is also possible to blow high-pressure air with an air gun or the like, or pressurize with an ultrasonic generator, piezoelectric element, or the like. The pressure required for pressurization is 500k
g/cm2 or more, preferably 800 kg/cm2 or more. However, if heating is also used at 40° to 120° C. during pressurization, the pressure may be 300 kg/cm 2 or less. The photosensitive material of the present invention is a photosensitive material for color photography and printing,
It has many uses such as printing photosensitive materials, computer graphics hard copy photosensitive materials, photocopying machine photosensitive materials, etc., and the image forming method of the present invention can create compact and inexpensive image forming systems such as photocopiers, printers, and simple printing machines. I can do things.

[0096]

[Example] Example 1 Preparation of silver halide emulsion (EB-1) 24 g of lime-treated inert gelatin was added to distilled water,
After dissolving at 0° C. for 1 hour, 3 g of NaCl was added, and the pH was adjusted to 3.2 by adding 1N sulfuric acid. Add this liquid to I
The solution and the solution II were simultaneously added at 60° C. using a controlled double jet method over a period of 45 minutes while maintaining pAg=8.5 until the solution I was used up. After addition, p
Adjust H to 6.0 with 1N NaOH and further (ATR
-1) Add 4.8 mg and (SB-1) 480 mg, and then add 4.1 g of KI over 20 minutes to 3 minutes after addition.
100 g of an aqueous solution containing was added at an equal flow rate.

To this emulsion, 1.1 g of (CK-1) was added and precipitated, washed with water and desalted, 6 g of lime-treated gelatin was added and dissolved, and a 72% aqueous solution of (ATR-1) 3
cc was added to adjust the pH to 6.2. Average particle size 0
．． 550 g of a monodispersed tetradecahedral silver iodobromide emulsion (EB-1) having a diameter of 24 μm and a coefficient of variation of 20% was prepared.

I Liquid AgNO3 120g Distilled water
550ccII Liquid KBr 85g Distilled water 550cc

0099
Preparation of silver halide emulsion (EG-1) Same as silver halide emulsion (EG-1) except that the addition time of solutions I and II was changed to 15 minutes, and (SB-1) was replaced with (SG-1).
1) 450 mg was added. Average particle size 0.18μ
m, monodispersed silver iodobromide emulsion (EG-1) with a coefficient of variation of 22%
550g was prepared.

Preparation of silver halide emulsion (ER-1) Same as silver halide emulsion (EG-1) except (SG-1)
450 mg of (SR-1) and (SR-3) instead of
100 mg was added. Average particle size 0.18 μm,
Monodispersed silver iodobromide emulsion (ER-1) 55 with a coefficient of variation of 22%
0g was prepared.

[0101]

[Chemical formula 13]

[0102]

[Chemical formula 14]

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

Preparation of solid dispersion (KB-1) 300ml
110 g of a 5.4% aqueous solution of lime-processed gelatin, polyethylene glycol (average molecular weight 200
0), 20 g of a 5% aqueous solution of base precursor (BG-1
)70g and diameter O. Add 200 ml of glass beads of 5 to 0.75 mm, and stir at 3000 r. using a Dyno Mill.
p. m. Disperse for 30 minutes and adjust the pH to 6.5 with 2N sulfuric acid.
Base precursor (B) with a particle size of 1.0 μm or less
A solid dispersion (KB-1) of G-1) was obtained.

[0105]

[Chemical formula 15]

Preparation of pigment dispersion (GY-1) Microlith Yellow 4GA was added to 255 g of the polymerizable compound (MN-2).
(trade name, manufactured by Ciba Geigy) and stirred for 1 hour at 5000 revolutions per minute using an Eiger motor mill (manufactured by Eiger Engineering).
Y-1) was obtained.

Preparation of pigment dispersion (GM-1) 255 g of polymerizable compound (MN-2) was added with Microrethread 3RA.
(trade name, manufactured by Ciba Geigy) and stirred for 1 hour at 5000 revolutions per minute using an Eiger motor mill (manufactured by Eiger Engineering).
M-1) was obtained.

Preparation of pigment dispersion (GC-1) Copper phthalocyanine (CI) was added to 255 g of the polymerizable compound (MN-1).
Pigment 15) 45g, Solsperse 500
0 (manufactured by ICI) 1.13g, Solsperse 24000
(manufactured by ICI) and stirred for 1 hour at 5000 revolutions per minute using an Eiger motor mill (manufactured by Eiger Engineering) to obtain a dispersion (GC-1).

Preparation of photosensitive composition (PB-1) Copolymer (1P-1) (S
V-1) 9 g of 20% (wt%) solution, (RD-1) 2
．． (SV of 3g, (RD-3) 6.2g, (FF-3)
-1) 1 g of 0.5% (wt%) solution and (ST-1
) was added and dissolved to prepare an oily solution. Add 3.8 g of silver halide emulsion (EB-1) and 24 g of solid dispersion (KB-1) to this solution, and stir at 10,000 revolutions per minute using a 40φ dissolver for 5 minutes while keeping the temperature at 60°C. A W/O emulsion photosensitive composition (P
B-1) was obtained.

Preparation of photosensitive composition (PG-1) Copolymer (1P-1) (S
V-1) 9 g of 20% (wt%) solution, (RD-1) 2
．． (SV of 3g, (RD-2) 3.1g, (FF-3)
-1) 1 g of 0.5% (wt%) solution and (ST-1
) was added and dissolved to prepare an oily solution. 3.8 g of silver halide emulsion (EG-1) and 24 g of solid dispersion (KB-1) were added to this solution, and while keeping it at 60°C, it was rotated at 10,000 revolutions per minute using a 40φ dissolver.
The photosensitive composition of W/O emulsion (PG
-1) was obtained.

Preparation of photosensitive composition (PR-1) To 45 g of pigment dispersion (GC-1) was added copolymer (1P-1) (
SV-1) 9 g of 20% (wt%) solution, (RD-1)
2.3g, (RD-3) 6.2g, (FF-3) (S
V-1) 1 g of 0.5% (wt%) solution and (ST-
1) 5g was added and dissolved to prepare an oily solution. 3.8 g of silver halide emulsion (ER-1) and 24 g of solid dispersion (KB-1) were added to this solution, and the mixture was stirred at 10,000 revolutions per minute using a 40φ dissolver for 5 minutes while keeping the temperature at 50°C. , W/O emulsion photosensitive composition (P
R-1) was obtained.

[0112]

[Chemical formula 16]

[0113]

[Chemical formula 17]

[0114]

[Chemical formula 18]

Photosensitive microcapsule dispersion (CB-1
) Preparation 36 g of water was added to 4 g of a 15% aqueous solution of polymer (2P-1), and the mixed liquid was adjusted to pH 5.0 with 2N sulfuric acid. 60 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid and mixed at 60°C for 30 minutes. This mixed solution was added to the photosensitive composition (PB-1) and stirred for 20 minutes at 60° C. and 7000 revolutions per minute using a 40φ dissolver to obtain an emulsion in the form of a W/O/W emulsion. Separately, 52.2 g of a 37% formaldehyde aqueous solution and 170.3 g of water were added to 31.5 g of melamine, and the mixture was heated at 60°C.
and stirred for 30 minutes to obtain a transparent aqueous solution of melamine/formaldehyde initial condensate.

25 g of this initial condensate was added to the W/O/W emulsion cooled to 25° C., and the pH was adjusted to 5.0 using 2N sulfuric acid while stirring at 1200 rpm with a propeller blade. Next, the temperature of this liquid was raised to 70° C. over 30 minutes, and the mixture was further stirred for 30 minutes. To this was added 10.3 g of a 40% aqueous solution of urea, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring was continued at 70° C. for an additional 40 minutes. After cooling this liquid to 25° C., the pH was adjusted to 6.5 using a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion having capsule walls made of melamine formaldehyde resin.

Further, the same amount of distilled water was added to 120 g of this photosensitive microcapsule dispersion, and the mixture was centrifuged at a speed of 500 rpm. 200 g of the supernatant was removed, and 80 g of distilled water was added to the remaining microcapsule-containing liquid to redisperse it to prepare a photosensitive microcapsule redispersion liquid (CCB-1). In addition, 6 of polymer (2P-2) was added to this dispersion.
% aqueous solution was added thereto, and to this was added 25 g of the aqueous solution of the above-mentioned melamine/formaldehyde initial condensate, and the pH was adjusted to 5.0 using 2N sulfuric acid while stirring at 1200 rpm with a propeller blade.

[0118] Next, the temperature of this liquid was raised to 70°C over 30 minutes, and the mixture was further stirred for 30 minutes. Add to this 40% of urea.
% aqueous solution was added, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring was continued at 70°C for an additional 40 minutes. After cooling this liquid to 25° C., the pH was adjusted to 6.5 using a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB-1) having capsule walls made of melamine formaldehyde resin.

Photosensitive microcapsule dispersion (CG-1
) Preparation Add 16 g of water to 4 g of a 15% aqueous solution of polymer (2P-1).
The pH of the mixed solution was adjusted to 5.0 with 2N sulfuric acid. 80 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid and mixed at 60°C for 30 minutes. The above photosensitive composition (PG-1) was added to this mixed solution, stirred at 60°C for 20 minutes at 4000 revolutions per minute using a 40φ dissolver, and
An emulsion in the form of a /O/W emulsion was obtained. Then (
In the same manner as in the preparation of CB-1), melamine/formaldehyde initial condensate was added and encapsulated, followed by sedimentation and redispersion to obtain a photosensitive microcapsule dispersion (CCG-1).
was prepared and encapsulated again to prepare a photosensitive microcapsule dispersion (CG-1).

Photosensitive microcapsule dispersion (CR-1
) Preparation Add 36 g of water to 4 g of a 15% aqueous solution of polymer (2P-1).
The pH of the mixed solution was adjusted to 5.0 with 2N sulfuric acid. 80 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid 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 for 20 minutes at 5000 rpm at 50°C using a 40φ dissolver.
An emulsion in the form of a /O/W emulsion was obtained.

[0121] Then, in the same manner as in the preparation of (CB-1),
A photosensitive microcapsule dispersion (CCR-1) is prepared by adding a melamine/formaldehyde initial condensate, encapsulating it, settling it, and redispersing it, and then encapsulating it again.
-1) was adjusted. Polymer (2P-1) Potassium polyvinylbenzenesulfinate polymer (2
P-2) Polyvinylpyrrolidone K-90

Preparation of photosensitive material 101 22.5 g of photosensitive microcapsules (CB-1), (C
G-1) 22.5g, (CR-1) 22.5g mixed solution, surfactant (WW-1) 0.3g, surfactant (WW-2) 10% aqueous solution 1.5g, PVA KL
7.4 g of a 20% aqueous solution of 318 (manufactured by Kuraray, carboxy-modified PVA) was added and mixed at 40°C. This coating solution was applied to the aluminum-deposited surface of a support made of a 25μ thick polyethylene terephthalate film with aluminum deposited on it.
Application amount: 114cc/m2 by extrusion method
After drying at 60℃, 25℃, 65%
It was rolled up under the following conditions so that the coated side was on the inside. This photosensitive material was sealed in a moisture-proof bag laminated with aluminum under conditions of 25° C. and 55%.

[0123]

[Chemical formula 19]

Preparation of image receiving material (RS-1) 240 g of calcium carbonate (PC700, manufactured by Shiraishi Kogyo Co., Ltd.), 5.6 g of surfactant (Poise 520, manufactured by Kao Corporation), and 354.4 ml of water were stirred. After mixing, the mixture was dispersed for 3 minutes at 8000 revolutions per minute using a dispersing machine (trade name: Ultra Disperser (LK-41 model), manufactured by Yamato Scientific). 52g of this dispersion and 10% polyvinyl alcohol (
A coating solution for forming an image-receiving layer was prepared by mixing 52 g of an aqueous solution of PVA-17 (manufactured by Kuraray Co., Ltd.) and adding 4 ml of a 1% aqueous solution of the following surfactant and 22 ml of water.

[0125] This coating solution was applied to a paper support weighing 80 g/m2 (as the fiber length distribution specified by JIS-P-8207, the sum of the weight % of the 24 mesh residue and the weight % of the 42 mesh residue was 30 to Paper support using base paper having a fiber length distribution of 60% [JP-A-63-18623
No. 9]) was coated uniformly at 65 g/m 2 and dried at 60° C. to prepare an image-receiving material (RS-1).

[0126]

[C20]

Image Formation The following experiments were carried out at 25°C and 50%. Using a halogen lamp whose color temperature was adjusted to 3100K, the photosensitive material 101 taken out from the moisture-proof bag was heated to continuously change color temperature from 0 to
It was exposed to light at 20000 lux for 1 second through a wedge having a transmission density of 4.0, an ND filter having a density of 1.0, and yellow and magenta CC filters (manufactured by Fuji Film) so as to match the gray balance. After 5 seconds of exposure, heat development was carried out for 2 seconds using a heat developing machine heated to 150° C. from the side opposite to the coated side of the photosensitive material.

[0128] After 10 seconds of heating, the image receiving material (RS-1)
The photosensitive material with its coated surfaces overlapped was passed through a pressure roller having a diameter of 3 cm and a pressure of 1200 kg/cm 2 at a speed of 2 cm/sec. When the image-receiving material was peeled off from the photosensitive material immediately after passing, a clear positive image was obtained on the image-receiving material. When the density of this image was measured using X-Rite 310, the maximum density was 1.20 and the minimum density was 0.08.

Comparative Example 1 Preparation of Photosensitive Microcapsules (CB-2) In preparing the photosensitive microcapsule dispersion (CB-1) of Example 1, 150 g of W/O/W emulsion was used, and melamine/formaldehyde initial condensation was carried out. The pH was adjusted to 5.0 using 2N sulfuric acid while stirring at 1200 rpm with a propeller blade. Next, the temperature of this liquid was raised to 70° C. over 30 minutes, and the mixture was further stirred for 30 minutes. Add 10.3g of 40% aqueous solution of urea to this, and purge with 2N sulfuric acid.
The H was adjusted to 3.5 and stirring continued at 70° C. for an additional 40 minutes. After cooling this liquid to 25°C, the pH was adjusted to 6.5 using a 2N aqueous sodium hydroxide solution, and melamine.
A photosensitive microcapsule dispersion (CB-2) having formaldehyde resin as the capsule wall was prepared.

Preparation of photosensitive microcapsules (CG-2) Photosensitive microcapsule dispersion (CG-1) of Example 1
In the preparation of (CB-2), 150g of W/O/W emulsion was used, and then melamine and
By adding 50 g of formaldehyde initial condensate and encapsulating, a photosensitive microcapsule dispersion (CG
-2) was adjusted.

Preparation of photosensitive microcapsules (CR-2) Photosensitive microcapsule dispersion (CR-1) of Example 1
In the preparation of (CB-2), 150g of W/O/W emulsion was used, and then melamine and
By adding 50 g of formaldehyde initial condensate and encapsulating, a photosensitive microcapsule dispersion (CR
-2) was adjusted.

Preparation of photosensitive material 102 15 g of photosensitive material microcapsules (CB-2) (CG-
2) Add 0.5 g of surfactant (WW-1) and 1 part of surfactant (WW-2) to a mixture of 15 g (CR-2) and 16 g.
0.8 g of a 0% aqueous solution and 15.6 g of a 10% aqueous solution of PVA KL318 (manufactured by Kuraray, carboxy-modified PVA) were added and mixed at 40°C. This coating solution was applied to a 25μ thick polyethylene terephthalate film with aluminum deposited on the aluminum support surface using an extrusion method to a coating amount of 75cc/m2, and after drying at 60°C, 25°C. It was wound up under conditions of 65% so that the coated surface was on the inside. This photosensitive material was heated at 25°C and 55°C.
% in a moisture-proof bag laminated with aluminum.

An image was formed using the image-forming photosensitive material 102 in the same manner as in Example 1. The image density is the highest density of 1.03 and the lowest density of 0.08, and compared to the photosensitive material 101 of the present invention, the lowest density is almost the same level, but due to transfer inhibition by undeposited melamine/formaldehyde resin. However, a decrease in the maximum concentration was observed.

Comparative Example 2 Preparation of Photosensitive Material 103 When preparing the photosensitive material 101 in Example 1, microcapsule redispersion liquids (CB-1), (CG-1), (CR-1) were used.
) instead of microcapsule dispersion (CC
B-1), (CCG-1), (CCR-1),
Photosensitive microcapsule (CCB-1) 16g, (CC
G-1) 16g, (CCR-1) 16g mixed solution, surfactant (WW-1) 0.5g, surfactant (WW
-2) 1.3g of 10% aqueous solution, PVA KL318
(manufactured by Kuraray, carboxy-modified PVA) 10% aqueous solution 2
5g was added and mixed at 40°C.

[0135] This coating solution was applied to the aluminum vapor-deposited surface of a polyethylene terephthalate film having a thickness of 25 μm using an aluminum vapor-deposited film, using an extrusion method, in a coating amount of 90 cc/m2, and after drying at 60°C, It was wound up at 25° C. and 65% so that the coated surface was on the inside. This photosensitive material was sealed in a moisture-proof bag laminated with aluminum under conditions of 25° C. and 55%.

An image was formed using the image-forming photosensitive material 103 in the same manner as in Example 1. The image density was a maximum density of 1.21 and a minimum density of 0.20, which was higher than that of the light-sensitive material of the present invention. In addition, in the lowest density part of the image, linear unevenness due to the destruction of the microcapsules due to scratches and stickiness due to seepage of the core substance on the surface of the photosensitive material were observed, and compared to the microcapsules of the present invention, the capsules It was found that the wall formation was insufficient.

Test for core substance retention on microcapsule walls Photosensitive materials 101, 102, and 103 were each 2.6 cm thick.
The pieces were cut into 10 cm x 10 cm pieces, each placed in 10 ml of toluene, and then left to stand for 10 minutes. When these liquids were analyzed by liquid chromatography after filtration, monomers were detected in 101 at 3% or less of the applied amount, whereas in 102, monomers were detected at 10% of the applied amount and 103.
30% of the cases were detected. Therefore, the photosensitive material 101 of the present invention is a photosensitive material that provides a high maximum density and a low minimum density, and has excellent core substance retention.

Claims (4)

[Claims] Claim 1: An oily liquid containing at least silver halide, a reducing agent, a color image-forming substance, and a polymerizable compound and having a density of more than 1.0 is emulsified and dispersed in an aqueous medium, and the emulsion is dispersed around the oil droplets. After forming a capsule wall made of amino aldehyde resin, the resulting capsules are allowed to settle, some or all of the supernatant is removed, the capsules are redispersed in an aqueous medium, and then additional amino aldehyde resin is applied around the capsules. A method for producing photosensitive microcapsules, the method comprising forming a capsule wall consisting of: 2. A photosensitive material comprising a support and a photosensitive layer comprising at least the photosensitive microcapsules produced by the method according to claim 1 and a binder. 3. An aqueous medium containing at least a photopolymerization initiator, a color image forming substance, and a polymerizable compound, the density of which is 1.
．． After emulsifying and dispersing an oily liquid with a size larger than 0 and forming a capsule wall made of amino aldehyde resin around the oil droplets, the resulting capsules are sedimented and a part or all of the supernatant is removed to form the capsules. A method for producing photosensitive microcapsules, which comprises redispersing them in an aqueous medium and then forming a capsule wall made of an amino aldehyde resin around the capsules. 4. A photosensitive material comprising a support and a photosensitive layer comprising at least the photosensitive microcapsules produced by the method according to claim 3 and a binder.