JPH0369954A - Photosensitive material for forming color image - Google Patents

Abstract

PURPOSE:To form an image having superior color balance immediately after formation and after the lapse of time by specifying the amts. of pigments contained in capsules and the amts. of the three-color capsules. CONSTITUTION:When three kinds of microcapsules separately contg. yellow, magenta and cyan pigments besides a polymerizable compd., silver halide and a reducing agent are applied to obtain a photosensitive material for forming a color image, the ratio of the magenta pigment content of the microcapsules to the yellow pigment content and the ratio of the cyan pigment content to the yellow pigment content are regulated to 0.8-1.2 each. The ratio of the amt. of the magenta pigment-contg. microcapsules to the amt. of the yellow pigment- contg. microcapsules and the ratio of the amt. of the cyan pigment-contg. microcapsules to the amt. of the yellow pigment-contg. microcapsules are also regulated to 0.5-1.5 each. A full-color image having superior color balance not only immediately after formation but also after the lapse of time can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a photosensitive material capable of forming full-color images.

``Prior Art'' A photosensitive material in which a capsule containing a polymerizable compound, silver halide, a reducing agent, and a leuco dye is coated on a support is known. , coated with three types of microcapsules each containing three types of leuco dyes: yellow, magenta, and cyan.
A photosensitive material for full color image formation is disclosed. Furthermore, Japanese Patent Application Laid-Open No. 187346/1987 discloses a photosensitive material containing a cyan pigment, but does not disclose a photosensitive material for forming full-color images.

"Problems to be Solved by the Invention" The photosensitive material described in JP-A No. 61-275742 is an excellent material that allows full-color images to be obtained using a simple device, but it uses a leuco dye. As a result, the images obtained were unstable and tended to gradually fade under indoor lighting. Especially in full-color images, the fading speed of the three colors is different, so first
Even if the balance was adjusted, the hue could change to something undesirable over time.

An object of the present invention is to provide a photosensitive material that can form full-color images with excellent color balance not only immediately after image formation but also after time.

"Means for Solving the Problems" The photosensitive material of the present invention comprises microcapsules containing a polymerizable compound, silver halide, a reducing agent, and a yellow pigment on a support; , a microcapsule containing a magenta pigment; and a microcapsule containing a polymerizable compound, a silver halide, a reducing agent, and a cyan pigment. The ratio of the magenta pigment content to the yellow pigment content and the cyan III pigment content are each in the range of 0.8 to 1.2, and further contains a yellow pigment. The ratio of the amount of microcapsules containing magenta pigment to the amount of microcapsules and the ratio of the amount of microcapsules containing cyan pigment to the amount of microcapsules are each 0. This is a photosensitive material for color image formation, characterized in that it has a molecular weight in the range of 5 to 1.5.

In the present invention, a pigment is used as an image forming substance, and by keeping the amount contained in the capsule and the amount of the three color capsules within a certain range, the color balance can be maintained immediately after image formation and after time. This provides an excellent photosensitive material.

Generally, when obtaining a full-color image using a photosensitive material in which three types of microcapsules containing three color image-forming substances are coated on a support, the extinction coefficient of the coloring material must be adjusted to match the color balance. There are four ways to adjust the amount of three-color imaging material contained within the capsule, to adjust the amount of the three types of capsules, and to adjust the particle size/wall thickness of the capsule. Since it is not easy to adjust only the extinction coefficient while maintaining a desirable hue, the second, third, and fourth methods are usually used in combination as long as graininess is not impaired. Particularly easy is the combination of the second method and the third method. However, when pigments are used as color image-forming substances as in this case, the effective adjustment range has not been previously known, and in particular, the amount of pigment contained in the capsule must be relatively well-balanced for the three colors. I realized this for the first time. This is due to the amount of pigment,
When the amount of the polymerizable compound exceeds 10%, which is an important area for practical use, the viscosity inside the capsule changes significantly in response to changes in the amount of pigment. This is presumed to be due to a large change in

The amount of three pigments contained in each capsule and 3
By keeping the amount of color capsule within the range of the present invention,
Full-color images with good color balance can be obtained without impairing graininess.

In addition, since the full-color image obtained using the photosensitive material of the present invention is formed from pigments, the image stability is very good, and the color balance hardly changes even if stored for a long time under indoor light. .

The silver halide, reducing agent, polymerizable compound, pigment, microcapsules, other additives, and support that constitute the light-sensitive material of the present invention will be explained below.

Light-sensitive materials contain silver chloride, silver bromide, silver halide,
Any grains of silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be as fine as about 0.01 micron or less, or as large as a projected area diameter of up to 10 microns, or as a polydisperse emulsion, as described in U.S. Pat.
Monodisperse emulsions such as those described in British Patent No. 74.628, British Patent No. 3.655.394, and British Patent No. 1.413,748 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 by Cutoff, Photography, Inc. Science and Engineering.
ence and Engineering), No. 14
Volume 248-257 (1970); U.S. Patent No. 4,4
34゜226, 4,414,310, 4,43
It can be easily prepared by the methods described in British Patent No. 3.048, British Patent No. 4,439,520 and British Patent No. 2.112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It is also possible to bond with a compound other than silver halide, such as silver rhodan or lead oxide, or to use two or more types of silver halide grains with different halogen compositions, crystal habits, grain sizes, etc. You can also do that.

The halogenated photographic emulsion that can be used in the present invention is, for example, published by Research Disclosure (RDlkt17643 (
December 1978), pp. 22-23, 11, Emulsion Production (
Emulsion preparation andt
ypes)” and N118716 (November 1979), p. 648.

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 Magnetics 17.
643 and Kaimagne 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Taruokuku Arashi RD17643 RD1871
6 Chemical sensitizers Page 23 Page 648 Right column Sensitivity enhancers Same as above Spectral sensitizers 23~
Page 24 Page 648 Right column - Super sensitizer
Page 649 Right column Anti-fog agent Pages 24-25 64
Page 9, right column ~ and stabilizer The above-mentioned silver halide grains include Japanese Patent Application Laid-Open No. 63-6
It is preferable to use silver halide grains having a relatively low capri value, such as the photosensitive material described in Japanese Patent No. 8830.

A reducing agent that can be used in a light-sensitive material has a function of reducing silver halide and/or a function of promoting (or inhibiting) 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, amylreductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidophenols, 2
．． 4-disulfonamidophenols, 2.4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4-
Sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α
- Sulfonamide ketones, hydrazines, etc. By adjusting the type, amount, etc. of the reducing agent, it is possible to polymerize the polymerizable compound in either the area where the silver halide latent image is formed or the area where no latent image is formed. In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, 1-phenyl-3-pyrazolidones, hydroquinones, and sulfonamidophenols are particularly preferred as reducing agents.

Regarding various reducing agents having the above functions, please refer to JP-A-61-183640, JP-A No. 61-188535, and JP-A-61-188535.
Publications No. 1-228441 and JP-A-62-7
No. 0836, No. 62-86354, No. 62-8635
No. 5, No. 62-206540, No. 62-264041
No. 62-109437, No. 63-254442, Japanese Patent Application No. 63-97379, No. 63-296774, No. 63-296775, Japanese Patent Application No. 1-27175,
1-54101, 1-91162, 1-90
No. 087 and other publications and specifications (including those described as developing agents or hydrazine derivatives), and the above reducing agents are described in "The Theo" by T. JaIles.
ry of the Photographic Pr
ocess 4th edition, pp. 291-334 (1977) Research Disclosure Vol. 170. 1
No. 17029 (pages 9-15) of June 1978, and Vol. 176 of the same magazine, No. 17643 of December 1978.
No. (pages 22-31). Also, JP-A-62
As in the photosensitive material described in Publication No. 210446, a reducing agent precursor capable of releasing a reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. For photosensitive materials, the above publications,
Reducing agents and reducing agent precursors described in the specification and literature can be effectively used. Therefore, "reducing agent" in this specification
includes the reducing agents and reducing agent precursors described in the above-mentioned publications, specifications, and literature.

Among these reducing agents, those having basicity that form salts with acids can be used in the form of salts with appropriate acids.

These reducing agents may be used alone, but as described in the above specifications, two or more reducing agents may be used in combination, or two or more reducing agents may be used. When used in combination, the interaction of reducing agents is, firstly, due to so-called superadditivity, silver halide (and/or
Second, to promote the reduction of silver halide (silver salt).
and/or an oxidized form of the first reducing agent produced by the reduction of the organic silver salt) causes the polymerization of the polymerizable compound (or suppresses the polymerization) through a redox reaction with other reducing agents coexisting. ), etc. are possible. 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.

(4) (5) H (2) H Hs CHtsu (6) 11 (3) OC+Jss (7) OH (9) Hs The amount of reducing agent added can vary widely, but in general O , 1-1500 mol%, preferably 10-1500 mol%
It is 300 mol%.

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 with 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, methacrylamides, and maleic anhydride. Examples include acids, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

Specific examples of polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, Tricyclodecanyloxyacrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, phythanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylolpropane triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylated bisphenol A diacrylate, 2-(2-hydroxy-1,1-dimethylethyl)-5-hydroxylmethyl-5- Ethyl-1,3-dioxane diacrylate, 2
-(2-hydroxy-1,1-dimethylethyl)-5,
Examples include 5-dihydroxymethyl-1-3-dioxane triacrylate, triacrylate of a propylene oxide adduct of trimethylolpropane, 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, pentaerythritol tetramethacrylate, Methacrylate and dimethacrylate of polyoxyalkylenated bisphenol A can be mentioned.

The above-mentioned polymerizable compounds may be used alone or in combination of two or more types. A photosensitive material using a combination of two or more types of polymerizable compounds is described in JP-A-62-210445. 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. Of course, the use of a substance that serves both as a reducing agent and a polymerizable compound as described above is also included in type B of the photosensitive material.

Pigments that can be used in photosensitive materials include commercially available pigments,
Known materials described in various documents can be used.

Regarding literature, please refer to Color Index (C, 1,) Handbook,
“Latest Pigment Handbook” Japan Pigment Technology Association Kan (published in 1977)
, “Latest Pigment Application Technology J CMC Publishing (published in 1986)
, "Printing Ink Technology J" (CMC Publishing, published in 1984), etc.

By color, the types of pigments include white pigments, black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and others.
Included are polymer-bound 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. For 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 a surface treatment. Surface treatment methods include surface coating with resin or wax;
Possible methods include attaching a surfactant and bonding a reactive substance (for example, a silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, which are 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 0.05 mm after being dispersed in the polymerizable compound. 01μ～10
It is preferably in the μ range, and more preferably in the 0.05 to 1 μ range.

The amount of pigment is 5 to 120 parts by weight per 100 parts by weight of the polymerizable compound.
It is preferably used in a proportion of 10 to 60 parts by weight, more preferably 10 to 60 parts by weight.

As a method for dispersing the pigment into the polymerizable compound, known dispersion techniques used in ink production, toner production, etc. can be used. Dispersing machines include sand mills, attritors, pearl mills, super mills, ball mills, impellers, desparzer-1KD mills, colloid mills, and Eiger mills.
Examples include motor mills, guinatrons, three-roll mills, and pressurized niegoo mills. For details, see "Latest Pigment Application Technology"
(CMC Publishing, 1986).

In the light-sensitive material of the present invention, the polymerizable compound, silver halide, reducing agent, and pigment are contained in microcapsules. 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. For details, please refer to JP-A No. 6
Publication No. 2-209450 and JP-A-63-28784
There is a description in Publication No. 4.

Regarding microcapsules, various known techniques can be applied without particular limitation. Examples include methods using coacervation of hydrophilic wall-forming materials in US Pat. No. 2,800,457 and US Pat. No. 2,800,458; US Pat. 38-1957
4, 42-446, and 42-771; methods by precipitation of polymers as described in U.S. Pat. No. 3,418,250 and 3,660,304; Method using isocyanate-polyol wall materials; Method using isocyanate wall materials described in U.S. Pat. No. 3,914,511; U.S. Pat. Nos. 4,001,140 and 4
A method using a urea-formaldehyde-based or urea-formaldehyde resyl cimur-based wall forming material described in each specification of US Pat. No. 087376 and US Pat. No. 4,089,802; Method using a wall-forming material; 1 nsitu method by polymerization of monomers as described in Japanese Patent Publication Nos. 36-9168 and 51-9079; polymerization described in British Patent Nos. 927807 and 965074 Distributed cooling method;
US Patent No. 3,111,407 and British Patent No. 9304
Examples include the spray drying method described in the specification described in No. 22. The method for microencapsulating oil droplets of a polymerizable compound is not limited to the above, but a method in which a core material is emulsified and then a polymer film is formed as a microcapsule wall is particularly preferred. For photosensitive materials using microcapsules having an outer shell made of polyester resin, see Japanese Patent Application Laid-Open No. 622.
Regarding photosensitive materials using microcapsules having outer shells made of polyurea resin and/or polyurethane resin, JP-A-62-209438 discloses the use of microcapsules having outer shells made of amino aldehyde resin. Regarding the light-sensitive materials that were
No. 2-209439 describes a photosensitive material using microcapsules having an outer shell made of gelatin.
2-209440 describes a photosensitive material using microcapsules having an outer shell made of epoxy resin, and JP-A-62-209441 discloses microcapsules having a composite resin outer shell containing polyamide resin and polyurea resin. Regarding the photosensitive material used, see JP-A-62-209.
No. 447 describes a photosensitive material using a microcapsule having a composite resin shell containing a polyurethane resin and a polyester resin, and JP-A-62-209442 discloses a photosensitive material using a microcapsule having a composite resin shell containing a polyurethane resin and a polyester resin.

It is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsule. Regarding photosensitive materials containing silver halide in the wall material of microcapsules, JP-A No. 6
There is a description in Publication No. 2-169147.

In addition, Japanese Patent Application No. 1-37782 discloses that in order to obtain capsules with particularly excellent wall density, a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group is used. A microcapsule is disclosed in which a polymer wall of a high molecular compound is provided around a membrane.
It is preferably used in the present invention.

The light-sensitive material of the present invention may further contain a base or a base precursor as an image formation accelerator.

As the base and base precursor that can be used in the photographic material of the present invention, inorganic bases and organic bases, or their base precursors (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used.

Preferred base precursors include JP-A-59-18
No. 0549, No. 59-180537, No. 59-195
No. 237, No. 61-32844, No. 6136743, No. 61-51140, No. 61-52638, No. 6
No. 1-52639, No. 61-53631, No. 61-5
No. 3634, No. 61-53635, No. 61-5363
No. 6, No. 61-53637, No. 61-53638,
No. 61-53639, No. 61-53640, No. 61
-55644, 61-55645, 61-55
No. 646, No. 61-84640, No. 61-10724
No. 0, No. 61-219950, No. 61-251840
No. 61-252544, No. 61-313431, No. 63-316740, No. 64-68746, and Japanese Patent Application No. 62-209138, which describe organic acids and bases that are decarboxylated by heating. Salt, also JP-A No. 59-157637, JP-A No. 59-166943, JP-A No. 6
Examples include compounds that eliminate bases upon heating as described in Publication No. 3-96159.

The base precursor of the present invention is 50°C to 20°C.
It is preferable to release the base at 0°C, and between 80°C and 18°C.
It is more preferable to release at 0°C.

When using a base or base precursor in a photosensitive material,
A base or base precursor may be present outside the microcapsule.

Methods for incorporating bases or base precursors outside microcapsules include JP-A-62-209521 and JP-A-62-209521;
No. 2-209522, No. 62-209526, No. 63
-65437, 63-97943, 62-20
No. 9523, No. 62-253140, No. 63-654
It is described in each publication No. 3.

Further, a method of releasing a base using a reaction is described in Japanese Patent Application Laid-Open No. 63-25208 and Japanese Patent Application No. 187803-1983. Furthermore, a method of generating a base by electrolysis is described in JP-A-61-232451.

The base or base precursor can be used in the photosensitive material in a wide range of amounts. The base or base precursor is suitably used in an amount of 100% by weight or less, more preferably 0.1% by weight of the coating film of the photosensitive layer.
In the present invention, the base and/or base precursor may be used alone or as a mixture of two or more.

Furthermore, a base or a base precursor may be accommodated in a photosensitive microcapsule, and a method for incorporating a base precursor into a capsule is disclosed in Japanese Patent Application Laid-open No. 64-32251.
It may be introduced in the form of direct solid dispersion in a polymerizable compound as described in Japanese Patent Application No. 63-218964 and Japanese Patent Application No. 1989 by the present applicant.
As stated in the specification of the patent application 1ti (A) entitled "Photosensitive material" filed on August 22nd, a base precursor is dispersed in water and emulsified in a polymerizable metal compound. It may also be introduced in the form of

Specific examples of these bases and base precursors are shown below, but the invention is not limited to these.

(1) (3) (4) (6) (7) (9) Although there are no particular limitations on the support for the photosensitive material of the present invention,
It is preferable to use a material that can withstand the processing temperature during development.

Materials that can be used for the support include glass, paper, high quality paper, baryta paper, coated paper, cast coated paper,
Synthetic paper, metals and their analogues, polyester, polyethylene, polypropylene acetyl cellulose, cellulose ester, polyvinyl acecool, polystyrene, polycarbonate, polyethylene terephthalate polyester
Examples include films such as carbon fiber, and paper laminated with resin materials and polymers such as polyethylene.

In addition, when using a porous support such as paper, JP-A-62-
No. 209529, No. 63-38934, No. 63-81
No. 339, No. 63-81340, No. 63-97941
Supports described in various publications such as No., No. 64-88543, and No. 64-88544 can be used.

The photosensitive material of the present invention is used to form an image according to the usage method described below, and an image-receiving material is generally used. The image receiving material will be explained below.

The image-receiving material may be a support only, or an image-receiving layer may be provided 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, metals and their analogues, and polyester can be used. , polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polyethylene, polycarbonate,
Mention may be made of films such as polyethylene terephthalate, and papers coated with resin materials or polymers such as polyethylene. Note that when a porous material such as paper is used as the support for the image-receiving material, it is preferable that the support has a certain level of smoothness as in the image-receiving material described in JP-A-62-209530. Furthermore, regarding image-receiving materials using transparent supports, Japanese Patent Application Laid-Open No. 62-20
There is a description in Publication No. 9531.

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 image receptivity of the polymerizable compound.

Examples of white pigments 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, magnesium carbonate, and barium carbonate. , alkaline earth metal salts such as calcium carbonate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, etc., as well as aluminum ξ silicate, aluminum hydroxide, zinc sulfide, various clays, talc, kaolin, Examples include zeolite, acid clay, activated clay, and glass.

As organic white pigments, polyethylene, polystyrene,
Examples include benzoguanamine resin, urea-formalin resin, melamine-formalin resin, and polyamide resin.

These white pigments may be used alone or in combination, but those with high oil absorption for polymerizable compounds are preferred.

Furthermore, as the binder used in the image-receiving layer of the present invention, water-soluble polymers, polymer latexes, polymers soluble in organic solvents, and the like can be used. As a water-soluble polymer,
For example, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, and methylcellulose, proteins such as gelatin, phthalated gelatin, casein, and ovalbumin, starches such as dextrin and etherified starch, polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly-N- vinylpyrrolidone,
Polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole,
Examples include synthetic polymers such as polystyrene sulfonic acid, locust bean gum, pullulan, gum arabic, and sodium alginate.

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

Examples of polymers soluble in organic solvents include polyester resins, polyurethane resins, polyvinyl chloride resins, polyacrylonitrile resins, and the like.

As for how to use the above-mentioned binders, two or more types can be used in combination, and furthermore, the two types of binders can also be used in combination in such a ratio that phase separation occurs. An example of such usage is described in Japanese Patent Application No. 313483/1983.

The average particle size of the white pigment is 0.1~20μ, preferably 0.1~1Oμ, and the coating amount is 0゜1g~60g.
, preferably in the range of 0.5g to 30g. The weight ratio of the white pigment to the binder is 0.1 of the binder to 1 of the pigment.
The range is preferably from 0.01 to 0.4, and more preferably from 0.03 to 0.3.

The method of using the photosensitive material will be described below.

The photosensitive material can be used simultaneously with imagewise exposure or after imagewise exposure.
Perform development processing and use.

Although various exposure means can be used as the above-mentioned exposure method, a latent image of silver halide is generally obtained by imagewise exposure to radiation including visible light. The type of light source and amount of exposure
Sensitive wavelength of silver halide (if dye sensitization is performed,
It can be selected depending on the sensitized wavelength) and sensitivity. Further, the original image may be a black and white image or a color image.

The photosensitive material is developed at the same time as the imagewise exposure or after the imagewise exposure. The photosensitive material was published under the Special Publication Act in 1977-111.
Development processing using a developer described in Japanese Patent No. 49 or the like may be performed. As mentioned above, the method described in Japanese Patent Application Laid-Open No. 61-69062 which performs heat development treatment is a dry treatment, and therefore has the advantage of being simple to operate and capable of processing in a short time. Therefore, the development process for photosensitive materials is as follows:
The latter is especially good.

As the heating method in the above heat development treatment, various conventionally known methods can be used. In addition, like the photosensitive material described in JP-A No. 61-294434,
A heat generating layer may be provided on the photosensitive material and used as a heating means. Further, as in the image forming method described in JP-A-62-210461, heat development may be performed while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 50°C to 200°C, preferably 60°C to 150°C.
It is ℃. The heating time is generally 1 second or more, preferably 1 second to 5 minutes, and more preferably 1 second to 1 minute.

Furthermore, as in the image forming method described in Japanese Patent Application No. 1-3282, the development is carried out in a state in which the photosensitive layer contains a liquid in the range of 10 to 400% by weight of the polymerizable compound.
In addition, the heat treatment may be performed at a temperature of 50° C. or higher.

The photosensitive material can be thermally developed as described above to polymerize the polymerizable compound in the area where the silver halide latent image is formed or the area where the silver halide latent image is not formed.

In this way, by pressing the photosensitive material and the image-receiving material, which have obtained a polymer image on the photosensitive layer, in a superimposed state,
The unpolymerized polymerizable compound can be transferred to an image-receiving material to obtain a color image on the 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, pressure may be applied while conveying using a pressure roller such as a nip roll, or the pressure may be applied intermittently using a dot impact device or the like.

Alternatively, highly pressurized air can be blown with an air gun or the like, or the pressure can be applied with an ultrasonic generator, a piezoelectric element, or the like.

Photosensitive materials include color photography and printing photosensitive materials, printing photosensitive materials, computer graphic hard copy photosensitive materials,
It has many uses, such as photosensitive materials for copying machines.

"Examples" The present invention will be explained in more detail with the following Examples, but the present invention is not limited thereto.

Examples of the present invention and comparative examples will be described below.

Example-1 16 g of gelatin and 0.5 g of sodium chloride were added to an aqueous gelatin solution of halogen i (EB-1) (1,500 Mi of water, and purified with 1N sulfuric acid.
H3.2 and kept at 50°C>, an aqueous solution containing 1 g of potassium bromide and a silver nitrate aqueous solution
(100 g of silver nitrate dissolved in 300 g of water) was simultaneously added at an equal flow rate over 50 minutes. One minute after this addition was completed, 430 μ of sensitizing dye (SB-1) was added, and 15 minutes after addition, 2.9 g of potassium iodide was added.
An aqueous solution containing 100- and a silver nitrate aqueous solution (100-
3 g of silver nitrate dissolved in the solution) was added at an equal flow rate over 5 minutes. To this emulsion, 1.2 g of poly(isobutylene-monosodium co-maleate) was added and precipitated, washed with water and desalted, 4 g of gelatin was added and dissolved, and 0.5 μm of sodium thiosulfate was added.・5
Chemical sensitization was performed at 0°C for 15 minutes, and the average particle size was 0.2.
460 g of a monodispersed tetradecahedral silver iodobromide emulsion (EB-1) having a diameter of 2 μm and a coefficient of variation of 20% was prepared.

Add 20 g of gelatin and 0.5 g of sodium chloride to a gelatin aqueous solution of halogen (EC-1) (1,600 ml of water, and pH it with IN sulfuric acid.
3.2 and kept at 42°C), an aqueous solution containing 71 g of potassium bromide and a silver nitrate aqueous solution (
(211,100 g of nitric acid dissolved in 200 g of water)
were simultaneously added at equal flow rates over 30 minutes. One minute after this addition was completed, 480 μg of sensitizing dye (SG-1) was added.
was added, and 10 minutes after the addition of the sensitizing dye, an aqueous solution 100- containing 2.9 g of potassium iodide and an aqueous silver nitrate solution (3 g of sI nitric acid dissolved in 100+d of water) were simultaneously added over a period of 5 minutes. 1.2 g of poly(isobutylene-monosodium co-maleate) was added to this emulsion, and after sedimentation, washing with water and desalting, 4.5 g of gelatin was added.
Add and dissolve 0.7 g of sodium thiosulfate.
In addition, chemical sensitization was carried out at 60'C for 15 minutes to prepare 460 g of a monodispersed tetradecahedral silver iodobromide emulsion (EG-1) having an average grain size of 0.times.12 .mu.m and a coefficient of variation of 21%.

Aqueous gelatin solution of halogen (ER-1) (20g gelatin in 1600WIi water)
Add 0.5 g of sodium chloride and adjust the pH to 3 with IN sulfuric acid.
, 5 and kept warm at 45°C), 200 - of an aqueous solution containing 71 g of potassium bromide and an aqueous silver nitrate solution (1 l of silver nitrate in 200 w 1 l of water).

(dissolved Og) was simultaneously added at an equal flow rate over 30 minutes. One minute after this addition is complete,
Add the sensitizing dye (SR-1), and after adding the sensitizing dye 1
Aqueous solution containing 3.65 g of potassium iodide from 5 minutes 10
(lNi and silver nitrate aqueous solution (water 10 (silver nitrate 0.0 in ld)
22 g (dissolved)) were added at equal flow rates over 5 minutes. Add 1.2 g of poly(isobutylene-monosodium co-maleate) to this emulsion and let it settle.
After washing with water and desalting, 3.5 g of gelatin was added and dissolved, and then 0.45 μ of sodium thiosulfate was added and heated to 55°C.
Chemical sensitization was carried out for 20 minutes with an average particle size of 0.13.
Monodispersed tetradecahedral silver iodobromide emulsion (E
R-1) 460g was prepared.

Sensitizing dye (SB-1) ((:Hz) #5ot0 (CHz) 4SO3H・N (CJs) Sensitizing dye (SR-1) 3% aqueous solution of gelatin in a 300-mm dispersion container 16
0 g, 40 g of base precursor (BG-1) and 200 glass beads with a diameter of 0.5 to 0.75 mm were added,
A solid dispersion with a particle size of 1.011 m or less (KB-1
) was obtained.

\, -ノ/' I Preparation of (GY-1) -+1 To 270 g of the polymerizable compound (MN-1), add 30 g of Microlith Yellow 4GA (trade name, manufactured by Ciba Geigy), and mix it with an Eiger motor mill ( A dispersion (GY-1) was obtained by stirring for 1 hour at 5000 revolutions per minute.

270 g of the polymerizable compound (MN-1) of (GM-1) was mixed with 30 g of Microrethread 177A (trade name, manufactured by Ciba Geigy), and the mixture was heated every minute using an Eiger motor mill (manufactured by Eiger Engineering). The mixture was stirred at 5000 rpm for 1 hour to obtain a dispersion (GM-1).

270 g of polymerizable compound #yJ (MN-1) of (GC-1) was mixed with 30 g of Microlith Blue 4GA (trade name, manufactured by Ciba Geigy) using an Eiger motor mill (manufactured by Eiger Engineering). The mixture was stirred at 5000 revolutions per minute for 1 hour to obtain a dispersion (GC-1).

Copolymer (IP-1) was added to 45 g of pigment dispersion (GY-1) of (PB-1).
) of (SV-1) 20% (wt%) solution, 9 g, (RD
-1) 2.3g, (RD-2) 3.1g, (FF-3)
0.006g was added and dissolved to prepare an oily solution.

10 g of silver halide emulsion (EB-1) and 35 g of solid dispersion (KB-1) were added to this solution, and while keeping the temperature at 60°C, the mixture was heated at 15,000 revolutions per minute using a homogenizer.
The photosensitive composition of W/Q emulsion (PB
-1) was obtained.

Copolymer (I P-
(SV 1) 20% (weight%) of 1)? Yoon night 9
g, (RD-1) 2. 3 g,
3.1 g of (RD-2) and 0.006 g of (FF-3) were added and dissolved to prepare an oily solution.

4 g of silver halide emulsion (EG-1) and 35 g of solid dispersion (KB-1) were added to this solution, and stirred for 5 minutes at 15,000 rpm using a homogenizer while keeping the temperature at 60°C. Q emulsion grass photosensitive composition (PC-
1) was obtained.

Copolymer (IP-1) was added to 45 g of pigment dispersion (GC-1) of (PR-1).
1) (7) (SV-1) 9 g of 20% (wt%) solution, (RD-1) 2.3 g, (RD-2) 3.1 g,
(FF-3) 0.005g was added and dissolved to prepare an oily solution.

7 g of silver halide emulsion (ER-1) and 35 g of solid dispersion (KB-1) were added to this solution, and stirred for 5 minutes at 15,000 rpm using a homogenizer while keeping the temperature at 60°C. Photosensitive composition of Q emulsion'# (PR
-1) was obtained.

Polymerizable compound (MN-1>H3 Trade name: Kayarad R604 (Nippon Kayaku Special) Copolymer (IP 1) (FF 2) CI.

C8° (SV-1) CHz C1l CI (zOcHtH (RD-2) 0■ 126 g of a 10% aqueous solution of the polymer (2P-2) was added to 5.6 g of a 15% aqueous solution of the transparent polymer (2P-1).

Furthermore, 8.5 g of water was added and mixed to adjust the pH to 5.0. The above-mentioned photosensitive composition (PB-1) was added to this mixed solution, and the photosensitive composition (PB-1) was added to the mixture, and the photosensitive composition (PB-1) was heated at 60°C and 5,000 revolutions per minute for 2 seconds using Daysilver.
The mixture was stirred for 0 minutes to obtain an emulsion in the form of a W/Q/W emulsion.

Separately, 20 g of a 37% formaldehyde aqueous solution and 76.3 g of water were added to 14.8 g of melamine, heated to 60° C., and stirred for 40 minutes to obtain a transparent aqueous solution of melamine/formaldehyde initial condensate.

40 g of this initial jtJl condensate was added to 193.5 g of the above W/Q/W emulsion, and the pT was adjusted to 5.0 using a 10% aqueous solution of sulfuric acid. Then, this was heated to 60°C and stirred for 60 minutes. Add 1 liter of a 40% aqueous solution of urea to this.
Add 1g, adjust the pH to 3.5, and incubate for an additional 40 minutes at 60°C.
Stir at ℃. After cooling, the pH was adjusted to 6.5 using a 10% aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB-1) having capsule walls made of melamine formaldehyde resin.

In the preparation of star-shaped photosensitive microcapsule dispersion (CB-1) of microcapsules (CG-1), photosensitive composition (PG-1) was used instead of photosensitive composition (PB-1). A photosensitive microcapsule dispersion (CC;-1) was prepared in the same manner except that the same procedure was used.

In the preparation of the star-shaped photosensitive microcapsule dispersion (CB-1) of the microcapsule dispersion (CR-1), the photosensitive composition (PR-1) was used instead of the photosensitive composition (PB-1). A photosensitive microcapsule dispersion (CR1) was prepared in the same manner except for the following.

Polymer (2P-1) Potassium polyvinylbenzenesulfinate polymer (2
P-2) Polyvinylpyrrolidone, -90 (manufactured by Wako Pure Chemical Industries, Ltd. G Kiku), 1 meter grinder, 20 parts of LBSP and LBKP80 were beaten to 293 cc of Canadian freeness (C3F) using a refinery, and alkyl ketene was added as a neutral sizing agent. 0.3 parts of dimer (Acopel 12, manufactured by Daiso Hercules), polyamide borium chlorohydrin (as a fixing agent)
Kaimen 557, Deinoku Hercules Company! ! 8ri0.
and 0.5 parts of cation-modified polyacrylamide (trade name: Polystron 705, manufactured by Arayo Kagaku ■) as a tenacity enhancer were added in a bulb bone dry weight ratio.

Next, the above paper stock was weighed at 960 g/c using a Fourdrinier paper machine.
d. Paper was made into a base paper with a thickness of 66 μm.

A coating liquid for forming a moisture-proof layer made of polyvinylidene chloride resin was applied to the surface (felt surface) of the base paper produced as described above, 100 parts of SBR latex (product name: 5N304, manufactured by Sumitomo Nogatatsuta), and sodium polyacrylate (product (Product name: Nearon T40, manufactured by Toagosei Kagaku Kogyo ■) 1 part, Clay (Product name: UW-90, manufactured by Engelhard) 2
Coating liquids for forming a moisture-proof layer were prepared, each having a composition of 0.00 parts and 100 parts of a petroleum resin (trade name: Carbo Mule R, manufactured by Daifuku Hercules Co., Ltd.). 16g/m, 5
A paper support was prepared by coating at a coating amount of g/rd.

Photosensitive microcapsule dispersion i (CB-1) 5g,
(CG-1)4. 8g, (cR-1)4. 5g
To the mixture was added 3 g of a 10% aqueous solution of PVA205 (manufactured by Kuraray), and the mixture was coated on the paper support using a #60 roller and dried to prepare a photosensitive material.

Calcium carbonate (PC700, manufactured by Shiraishi Kogyo Sumifun) 77.
1g, surfactant (BOYS 520, manufactured by Kao Koku) 1.6g
, and water 221.4- and polytron dispersion 1
(PTl 0/35 type, manufactured by Kinemachi Chikara Co., Ltd.) for 20 minutes at 2000 revolutions per minute. 71 g of this dispersion and 34.5 g of an 8% polyvinyl alcohol (PVA-117, manufactured by Kuraray) were mixed, and then 28.5 g of water was mixed.
d was added to prepare a coating solution for forming an image-receiving layer.

This coating solution was applied to a paper support (JIS-
A paper support using a base paper having a fiber length distribution defined by P-8207 such that the sum of the weight percent of the 24 mesh residue and the weight percent of the 42 mesh residue is 30 to 60%. [Refer to Japanese Unexamined Patent Publication No. 186239/1983]) to a uniform weight of 102 g/d, and dried at 60° C. to prepare an image receiving material (R3-2).

After exposing the photosensitive material using a tungsten light bulb through a step wedge to a color temperature of 4800, 20001ux, and 1 second exposure, the photosensitive material was placed on a hot plate heated to 135°C. Place the photosensitive layer in close contact with each other for 10 minutes.
Developed by heating for seconds.

Next, the photosensitive material was overlapped with the image-receiving material (R3-2), and in that state was passed through a pressure roller of 500 kg/cJ.

The image-receiving material was then peeled off from the photosensitive material to obtain a positive image on the image-receiving material. The density of the obtained image was measured using a Macbeth reflection densitometer. The ratio of magenta density to yellow density (M/Y) was 1.01, and the ratio of cyan density to yellow density (C/Y) was 1.02, indicating excellent balance. Furthermore, there was virtually no problem with the graininess of this image.

Example 2 In preparing the pigment dispersion in Example 1, the pigment concentration was varied from 5% to 20% to prepare various dispersions.

Other than this, various photosensitive microcapsule dispersions having different pigment concentrations were prepared in exactly the same manner.

Example 1 was prepared by using these photosensitive microcapsule dispersion branches and varying the ratio of the three color capsules from 0 to 2.
A photosensitive material was prepared in the same manner as above.

When these were evaluated in the same manner as in Example 1, the results shown in FIG. 1 were obtained. The area indicated by A in Figure 1 is an area where the ratio of pigment concentrations within the capsule (magenta to yellow and cyan to yellow) is less than 0°8 and more than 1.2, and in this area, the amount of capsules used is Color balance that is preferable even if changed (0,9<M/Y, C/
This means that Y, M/c<1.1) was not obtained.

Furthermore, the area indicated by B in Figure 1 is an area where the ratio of the amounts of capsules used in the three colors (magenta to yellow and cyan to yellow) is less than 0.5 and more than 1. This means that graininess is noticeable in the image.

From the above results, in order to obtain an image with a preferable color balance without impairing graininess, the ratio of pigment concentrations in the capsule should be set between 0.8 and 1. 2, and the ratio of the amount of capsules used can be set to a region C of 0.5 to 1.5.

Furthermore, the sample with excellent color balance and good graininess obtained as described above was exposed to a fluorescent lamp for 3 months, and then stored for 1 month at 40°C and 80% high temperature and high humidity. I tested it and the color balance did not change at all.

[Brief explanation of drawings]

FIG. 1 shows the relationship between pigment ratio, capsule ratio and color balance. The shaded area represents A, the horizontal line represents B, and the unlined area represents C.
indicates excellent color balance.

Claims (1)

[Claims] microcapsules containing a polymerizable compound, silver halide, a reducing agent, and a yellow pigment on a support; microcapsules containing a polymerizable compound, a silver halide, a reducing agent, and a magenta pigment; and a polymerizable compound; In a color image-forming photosensitive material coated with three types of microcapsules: microcapsules containing silver halide, a reducing agent, and a cyan pigment, the content of magenta pigment is higher than the content of yellow pigment in the capsules. The ratio of the content of cyan pigment and the content of cyan pigment are in the range of 0.8 to 1.2, respectively, and the ratio of the amount of microcapsules containing magenta pigment to the amount of microcapsules containing yellow pigment is in the range of 0.8 to 1.2. The ratio of the amount of microcapsules containing cyan pigment is 0.5 to 1.5, respectively.
A photosensitive material for color image formation, characterized in that the material is in the range of .