JPH04175752A - Photosensitive material - Google Patents

Abstract

PURPOSE:To resolve the defect that the transfer concentration is low and the reduction of sensitivity is large by concurrently containing a color pigment and a colorless dye in a color image forming material used for a photosensitive material. CONSTITUTION:A photosensitive layer containing a micro-capsule storing at least silver halogenide, a reducing agent, a polymerized compound and a color image forming material is formed on a base. A color pigment and a coupler which is a colorless dye soluble in the polymerized compound are concurrently used for the color image forming material among components stored in the photosensitive micro-capsule. An image having high transfer concentration, excellent storage stability and little aging reduction of image concentration can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a photosensitive material in which a polymerizable compound can be polymerized by utilizing the photosensitivity of silver halide.

``Prior Art'' A photosensitive material has a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support. A latent image is formed on the silver halide, and a polymerizable compound is polymerized in response to the latent image. It can be used in image forming methods.

An example of this image forming method is published in Japanese Patent Publication No. 45-1 i i49.
No. 47-20741, No. 49-10697, JP-A No. 57-138632, No. 57-142638,
No. 57-176033, No. 5'l-211146,
It is described in distribution publications No. 58-107529, No. 58-121031, and No. 58-169143. In these methods, when exposed silver halide is developed using a developer, coexisting polymerizable compounds (e.g. vinyl compounds) are removed.
By polymerizing, a polymer compound is formed in an image-like manner. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, JP-A-61-69062, JP-A-61-73145, JP-A-61-183640, JP-A-61
-188535, 61-228441 Publications K1
A method is described in which the formation of macromolecular compounds can be carried out in a dry process.

The above method uses a recording material (photosensitive material) in which a support carries a photosensitive layer consisting of a photosensitive silver salt (silver halide), a reducing agent, a crosslinking compound (polymerizable compound), and a binder. be.

The image-forming power method described above is a method of polymerizing a heavy compound in a portion where a latent image of silver halide is formed.

Furthermore, there is a method of polymerizing a polymerizable compound in a portion of silver halide where a latent image is not formed.
No. 1, No. 61260241, No. 62-70836,
No. 62-81635, Japanese Patent Application No. 6:L-296774, No. 63-296775, Japanese Patent Application No. 1-27175,
It is described in Publication No. 1-54101.

One embodiment of a photosensitive material that can be used in the image forming method described above is a photosensitive material in which constituent components of the light layer, such as silver halide and polymerizable compounds, are contained in microcapsules. It is described in JP-275742. 1) Microcapsules (as described above) (hereinafter referred to as
The Iε optical material of the embodiment using photosensitive microcapsules has the advantage of providing clear images, particularly those with excellent sharpness.On the other hand, the development and polymerization reactions in the above image forming method are carried out using alkaline Proceeds smoothly under certain conditions. For this reason, it is preferable to include a base or a base precursor as an image formation accelerator in the photosensitive material. Regarding photosensitive materials characterized by having a photosensitive layer or a salt or base precursor, see JP-A-1986:2-
It is described in the specification of No. 26/1041.

When a base or a base precursor is added to a photosensitive material using the photosensitive microcapsules described above, the base or base precursor may be contained in a photosensitive microcapsule, or the image formation promoting function of the base or base precursor may be This is preferable in this respect.

JP-A-64-32251, JP-A-1-26:36
□Specification No. 11 describes the use of photosensitive microcapsules characterized by containing a base or a salt ant precursor6. Colorless dyes such as leuco dyes are used as color image-forming substances.1 On the other hand, there are photosensitive materials that use colored pigments, which have better image stability than dyes such as leuco dyes, as color image-forming substances. 62-
No. 187346 does not mention it. .

[Problem to be solved by the invention, - According to research by the present inventors, photosensitive materials containing colored pigments in photosensitive microcapsules are colorless dyes that can develop color such as leuco dyes (hereinafter simply referred to as colorless dyes). Compared to light-sensitive materials that contain
It turns out that the drawback is that there is a large decrease in sensitivity.

In particular, in the case of colored pigments, if the a degree of the pigment in the photosensitive capsule is increased in order to increase the transfer density, the viscosity increases rapidly at 10 to 20% or more of the conjugate compound, rather than the transfer density. It was on a downward trend. This tendency is particularly severe when the base precursor is incorporated into the capsule.

From the above, in the conventional technique in which a colored pigment or a colorless dye is used alone as a color image forming substance in a photosensitive microcapsule, it is difficult to reduce the transfer density of an image by -L.
It has become clear that it is difficult to achieve both storage stability (reduction or small reflection density when an image is stored under light irradiation)3. ``Means to solve the problem'' This problem is A photosensitive material having a photosensitive layer containing microcapsules containing at least silver halide, a reducing agent, a polymerizable compound, and a color image forming substance on a support,
This problem could be solved by simultaneously using a colored pigment and a colorless dye as the color image forming substance.

[Effects of the Invention] Among the components contained in photosensitive microcapsules, the present inventors simultaneously combined a coloring pigment and a colorless dye (coloring agent) soluble in a polymerizable compound as a color image forming substance. By using this method, it has become possible to obtain images with higher transfer density than before and with excellent storage stability (less decrease in image density over time). Also, until now, only coloring type 1 was used,
Attempts were made to lower the transfer density by -1 by increasing the pigment concentration, but encapsulation was difficult due to increased viscosity, etc., and the sensitivity was significantly lowered, making it impossible to put it to practical use.

This problem can now be avoided by using colorless dyes in combination with colored pigments.

"Detailed Description of the Invention" The color image-forming substance used in the light-sensitive material of the present invention is characterized in that it simultaneously contains a colored pigment (which may partially contain a colored dye) and a colorless dye. Here, various types of colored pigments and colorless dyes can be used.

First, coloring pigments that can be used in the present invention are described in Japanese Patent Application Laid-Open No. 187346/1987, Japanese Patent Application No. 205879/1999, Japanese Patent Application No. 205883/1999, and the like. Other commercially available products and various documents, such as Color Index (C, 1,) Handbook, "Latest Pigment Handbook" edited by Japan Pigment Technology Association (published in 1977), [Latest Pigment Application Technology J.
CMC Publishing (1986), “Printing Ink Technology,”
CMC Publishing, 1984) etc. can be used.

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. For surface treatment methods, see Properties and Applications of Metal Soaps (Saiwai Shobo)
, Printing Ink Technology (CMC Publishing, 1984), Latest Pigment Application Technology (CMC Publishing, 1986), etc.

These pigments are preferably used in a finely dispersed state in the polymerizable compound, and known dispersion techniques can be used as a method for dispersing them. Details of the dispersion technology are described in "Latest Pigment Application Technology J" (CMC Publishing, 1986).

On the other hand, examples of colorless dyes or color-forming substances that develop color when they come into contact with another component include those that develop color due to acid-base reactions, redox reactions, coupling reactions, chelate-forming reactions, etc. between two or more components. A variety of systems are included. For example, pressure-sensitive copying paper (29-58
page), azography (pages 87-95), heat-sensitive coloring by chemical change (pages 118-120), and other known coloring systems, or seminars sponsored by the Kinki Chemical Industry Association - Latest dye chemistry - Attractive functional dyes. It is possible to use the coloring system described in the Proceedings of Utilization and New Developments-1, pp. 26-32 (June 19, 1980). Specifically, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran, which is used in pressure-sensitive paper, and an acidic substance (coloring agent) such as acid clay or phenols: an aromatic diazonium salt or Systems using azo coupling reactions of diazotate, diazosulfonates, naphthols, anilines, active methylenes, etc., reactions of hexamethylenetetramine with ferric ions and gallic acid, and reactions of phenolphthalein-complexanes. Chelate-forming reactions such as reactions with alkaline earth metal ions; redox reactions such as reactions between ferric stearate and pyrogallol and reactions between silver behenate and 4-methoxy-1-naphthol can be used.

Regarding the present invention, the pressure-sensitive paper used in this paper is
A system comprising a coloring agent having a partial structure such as lactone, lactam, or spiropyran and an acidic substance (color developer) such as acid clay or phenols, that is, a system using a leuco dye is preferable.

Specifically, leuco dyes include triphenylmethane-phthalide series, fluoran series, phenothiazine series, indolylphthalide series, leuco auramine series, spiropyran series,
Rhodamine lactam type, triphenylmethane type, azaphthalide type, chromenoindole type, etc. can be used.

Regarding photosensitive materials using these leuco dyes, see JP-A-62-2 O9436, JP-A No. 62-288827, JP-A No. 62-288828, JP-A No. 63-112190,
No. 63-251278, No. 63-251279, No. 61-251280, No. 64. -42275 No. 6
No. 153542, No. 63-1.13446, No. 63-
It is described in various publications such as No. 129338 and No. 6111.2188.

In addition, examples of substances that develop color using some kind of energy such as heating, pressure, or light irradiation include thermochromic compounds, piezochromic compounds, photochromic compounds, and leukochromic compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. The body is known.

All of these compounds develop color upon heating, pressurization, light irradiation, or air oxidation, and these compounds can also be used as color image-forming substances in the light-sensitive materials of the present invention. It is preferably used in a proportion of 0.5 to 60 parts by weight per 100 parts by weight of the polymerizable compound,
More preferably, it is used in a proportion of 2 to 50 parts by weight. The mixing ratio of the colored pigment and the colorless dye is not particularly limited, but the weight ratio is preferably from 5.1 to 1:5, and from 21 to 1.
．． 2 is more preferred.

Below, other substances used in the photosensitive material of the present invention, namely:
Silver halide, reducing agent, polymerizable compound, base or base precursor, microcapsule, etc. will be explained in order.

The light-sensitive material of the present invention includes silver chloride, silver chloride,
Any grains of silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used.

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

The grain size of the silver halide can be as fine as about 0.01 micron or less, or as large as up to about 10 microns in projected area diameter (also in polydisperse emulsions, as described in U.S. Pat.
Monodisperse emulsions such as those described in British Patent No. 574,628, 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 Gutoff, Photographic Science and Engineering.
er+ce and Er+gineering)
, Vol. 14, pp. 248-257 (1970); U.S. Pat. It can be easily prepared by the method described in Japanese Patent No. 2.11.2,157.

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 may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Furthermore, two or more types of silver halide grains having different halogen compositions, 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) Nα17643
(December 1978), pp. 22-23.

``I, emulsion production (EI[+ulsiori preparation
ration and types)”, and
(L18716 (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 subject to Research Disclosure Nα1
7643 and Nα18716, 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 two Research Disclosures in Section L, and the relevant descriptions are shown in the table below.

Additive type RD 1.7643 RD 1.
8716 Chemical sensitizers Page 23 Page 648 Right column Sensitivity enhancers Same as above Photosensitizers
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 Right Column Anti-Friction Agent 24
~Page 25 Page 649 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 fog value, such as the light-sensitive material described in Japanese Patent No. 8830.

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 copolymer used in the present invention is preferably a copolymer represented by general formula (7).

-+A+-. B→-3(7) B In the above general formula (7), A is a repeating unit derived from a hydrophilic monomer, B is a repeating unit derived from a hydrophobic monomer, and 0 and p means a numerical value indicating the mole % of A and B in the total repeating unit constituting the above polymer, and 5≦0≦95.5≦p≦95, and o+p=100.

In the present invention, it is more preferable that the hydrophilic monomer has a nonionic, anionic, or amphoteric hydrophilic group as a hydrophilic group, and examples of these hydrophilic groups include a hydroxyl group, a hydroxyphenyl group, -CO
OHl-COCH.

group, a group having an ether bond, a sulfonic acid group, and the like. Details of these polymers are described in JP-A-62-209450, JP-A-63-287844, and other publications.

Specific examples of copolymers that can be used in the present invention are described below, but the invention is not limited thereto.

CH, CH3 substitute CH, -C force, iCH2-C] 71
[CO□C)lzcH”c)12CO2HCH,CH.

-fCH2-C-5-m, -fCH,-C1
-,.

C02CH, CHtOHCO□C,H.

The reducing agent that can be used in the light-sensitive material of the present invention has a function of reducing silver halide and/or a function of promoting (or suppressing) polymerization of a polymerizable compound. There are various types of reducing agents having the above functions.

The above reducing agents include hydroquinones, catechols, p
-aminophenols, p-phenylenediamines, 3
-Pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4゜5
-dihydroxy-6-amitubirimidines, diductones, amylreductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2,4-disulfonamidophenols, 2.
4-disulfonamide naphthols, 0- or p-acylaminophenols, 2-sulfonamide indanones, 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, Examples include sulfonamide pyrazolotriazoles, α-sulfodiamide ketones, and hydrazines. 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-mentioned functions, please refer to JP-A-61-183640, JP-A No. 61-1.88535, JP-A No. 61-2284.41, and JP-A No. 61-18364.
-70836, 61-86354, 62-86
No. 355, No. 62-206540, No. 62-264.
04] No. 62-109437, No. 63-254
No. 4.42, Patent Application No. 63-97379, No. 63-29
No. 6774, No. 63-296775, Patent Application No. 1-27
No. 175, No. 1-54101, No. 1-911.62, No. 1-911.62, No. 1-54101, No. 1-911.62, Same! , -90087 and other publications and specifications (
The above reducing agents (including those described as developing agents or hydrazine derivatives) are also described in "T.
he theory of the photography
phic Process” 4th edition, pp. 291-334 (1977) Research Disclosure Magazine 197
No. 17029 (Pages 9-15), June 1978, and No. 17643 (Pages 22-31) of the same magazine, December 1978.
It is also mentioned. 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 may be used in place of the reducing agent. good. 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, "1 reducing agent" in this specification includes the above-mentioned publications,
Included are reducing agents and reducing agent precursors as described in the specification 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, but as described in each of the above specifications, two or more types of 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; , silver halide (
The oxidized form of the first reducing agent produced by the reduction of the first reducing agent (and/or 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.

2/ /′ / 2/ /″′ ,/ /′ ・、7.・Pa >ingredient ／　　＼、 ′　　　＼ / / / / /// /″ /′ (1)　　　　).

OH C, He(t) OC,,H,.

t9) CH.

The amount of reducing agent added can be varied over a wide range, but is generally 0. 1 to 1500 mol%, preferably 10
~300 mol%.

The polymerizable compound used in the photosensitive material of the present invention is generally a compound having 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, benyl acrylate, furfuryl acrylate, ethos, etc. Kinetquin ethyl acrylate, tricyclodecanyloxyacrylate, nonylph 2yloxyedyl acrylate, 143-dioxolane acrylic L/-1-, hexanediol diacl, J
L==t, buta/diol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylolpropane triacrylate, pentaerythritol detraacrylate/-1, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate, polyoxyethylated bisphenol A diacrylate,
! -(2-hydroxy-1,1-dimethylethyl) -
,,5-hydroquinemethyl-5-ethyl-1,,3-
Shiokizun diacrylate, 2. (2-hydroquine-river, ■ -dimethylethyl)-5,5-cypidroquine methyl-1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, polyacrylate of hydroquine polyether, polyester acrylate and polyurethane acrylate-1.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate,
Ethyl/glycol dimethacrylate, butaneol dimethacrylate, neopendel glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and polyoxyalkylenated bisphenol A dimethacrylate, etc. can.

The above polymerizable compounds may be used alone or in combination of two or more F. A photosensitive material using a combination of two or more types of polymerizable compounds is described in JP-A-62-2104-15. Note that a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of a reducing agent can also be used as a polymerizable compound.

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.

For details on inorganic bases or organic bases, see JP-A-6
No. 2-209448, No. 62-170954, No. 63
It is described in various publications such as No. -316760 and No. 64-68746. In the present invention, bases with a pKa of 7 or more are particularly preferred.

Details of base precursors are described in the following publications.

JP-A No. 59-1.8054.9, No. 59-18053
No. 7, No. 59-195237, No. 61-32844, No. 61-3.6743, No. 61-51140, No. 61. -52638, 61-52639, 61
No. 53631, No. 61-53634, No. 61-536
No. 35, No. 61-53636, No. 61-53637, No. 61-53638, No. 61-53639, No. 6
No. 1-53640, No. 61-55644, No. 61. −
No. 55645, No. 61-55646, No. 61-846
No. 40, No. 61-107240, No. 61-21095
No. 0, No. 61-251840, No. 61-252544
No. 61-313431, No. 61316740,
No. 64-68746 and patent application No. 62-209138
Salts of organic salts and bases that are decarboxylated by heating described in each publication, as well as JP-A-59-157637 and JP-A-59-157637;
9-1 No. 66943, No. 63-961.59, a compound that releases a base by heating, and a method of releasing a base using a reaction is disclosed in JP-A-63-252.
No. 08 and Japanese Patent Application No. 61187803. Furthermore, a method of generating a base by electrolysis is described in JP-A-61-232451.

Among these base precursors, in the present invention, compounds that release a base upon heating are preferred. In order to release the base, the required temperature is preferably 50°C to 200°C, and 80°C to 200°C.
More preferably, the temperature is between 180°C and 180°C.

Specific examples of these bases and base precursors are shown below, but are not limited thereto.

HH HN NH CH2CH.

The base or base precursor is suitably used in an amount of not more than 100% by weight of the coated film of the photosensitive layer, and more preferably in a range of 0.1% to 40% by weight. In the present invention, the base and the base precursor may be used alone or in a mixture of two or more.

In the present invention, when a base or a base precursor is added to a photosensitive material using photosensitive microcapsules, it can be added to various locations of the photosensitive material, but the base or base precursor is accommodated in the photosensitive microcapsule. In particular, it is necessary from the viewpoint of the image formation promoting function of the base or base precursor. As a method for incorporating the base precursor into the capsule, it may be introduced directly into a polymerizable compound in the form of solid dispersion as described in JP-A-64-32251 and JP-A-63-92686; 1
In the specifications of No. 263641 and Japanese Patent Application No. 1-160148, l:! As described in , the base binder/curser may be dispersed in water and then introduced into the polymerizable compound in the form of emulsification.

In the present invention, the aforementioned silver halo) fluoride, a reducing agent, a polymerizable compound, a color image forming substance, a base or a base precursor are contained in microcapsules.

For these microcapsules, various known techniques can be applied without any particular limitations. Examples of 11 examples include the method described in U.S. Pat. No. 2,800,457 and U.S. Pat. method, described in US Patent No. 32871.54 and British Patent No. 990443 distribution specification, and Japanese Patent Publication No. 3
No. 8-19574, No. 41-446 and No. 42-7
Interfacial polymerization method described in 71 Partition Specification, US Patent No. 3418
No. 250 and No. 3,660,304; method by precipitation of distributed polymer; method using isocyanate-polyol wall material described in U.S. Pat. No. 3,796,669; method using isocyanate-ol wall material described in U.S. Pat. No. 1,391,4511 Method, U.S. Patent No. 400114 ([No. 4087376 and U.S. Pat. No. 4089802] Method using a urea-formaldehyde-based or urea-formaldehyde resin runnol-based wall forming material, U.S. Pat. No. 402545
Method using wall-forming materials such as melamine-formaldehyde resin and hydroxypropyl cellulose described in No. 5 specification: Japanese Patent Publication No. 36-9168 and Japanese Patent Application Laid-Open No. 51-907
ir+ 5ij by polymerization of monomers described in each publication No. 9
U Law, UK Patent Nos. 927807 and 965
No. 074 Polymerization dispersion cooling method described in each specification, U.S. Patent No. 3
Examples include the spray drying method described in No. 11.1407 and British Patent No. 9304229.

Although the method for microencapsulating oil droplets of a polymerizable compound is not limited to the following methods, a method in which a core substance is emulsified and then a polymer film is formed as a microcapsule wall is particularly preferred. Regarding photosensitive materials using microcapsules having outer shells made of polyamide resin and polyester resin, Japanese Patent Application Laid-Open No. 62-20943
7, and JP-A-61-209438 describes a photosensitive material using microcapsules having an outer shell made of polyurea resin, *' or polyurethane resin.
Regarding a photosensitive material using microcapsules having an outer shell made of amino aldehyde resin, Japanese Patent Application Laid-Open No. 62-2094
No. 39 describes a photosensitive material using a microcapsule having an outer shell made of ceratin, as described in Japanese Patent Application Laid-Open No. 62-209.
No. 440 describes a photosensitive material using microcapsules having an outer shell made of epoxo resin, and the degree of temperature is disclosed in Japanese Patent Application Laid-Open No. 62.
Regarding photosensitive materials using microcapsules having a composite resin outer shell containing polyamide resin and polyurea resin, Japanese Patent Application Laid-open No. 1982-209447 describes microcapsules having a composite resin outer shell containing polyurethane resin and polyester resin. Photosensitive materials using capsules are described in JP-A-61209442.

It is preferable that the 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
2-, No. 16914.7.

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 support for the photosensitive material of the present invention is not particularly limited, but 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, wood-free paper, coated paper, cast coated paper, synthetic paper, metals and their analogs, plastic sheets with metal deposited on one or both sides, polyester, acetyl cellulose,
Examples include films of cellulose ester, polyvinyl acecool, polystyrene, polycarbonate, polyethylene terephthalate polyamide, etc., and papers 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=38'934, No. 63-8
No. 1339, No. 63-81340, No. 6:3-979
Supports described in publications such as No. 41, No. 64-88543, and No. 64-88544 can be used.

Hereinafter, arbitrary components that can be included in the photosensitive layer, auxiliary layers that can be arbitrarily provided on the photosensitive material, etc. will be sequentially explained.

Optional components that can be included in the photosensitive layer of the photosensitive material include organic silver salts, various image formation accelerators, thermal polymerization inhibitors, polymerization initiators, development stoppers, fluorescent whitening agents, antifading agents, Harenyon or anti-irradiation dyes or pigments, pigments that can be decolored by heating or light irradiation, matting agents, anti-smudge agents, plasticizers, water-releasing agents,
Examples include binders, hardeners, coating aids, antistatic agents, solvents for polymerizable compounds, and water-soluble vinyl polymers.

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 agent described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Furthermore, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235, and JP-A-61-24904
Acetylene silver described in the publications No. 4 and No. 64-57256 is also useful. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 1 to 10 g/rr in terms of silver.
r is appropriate.

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 above-mentioned bases or base precursor 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 on these see US Pat.
, No. 678, 739, columns 38-40, JP-A-62-20
It is described in publications such as No. 9443 and specifications.

In light-sensitive materials, the purpose is to initiate polymerization in a system that polymerizes polymerizable compounds in areas where latent silver halide images are not formed, or to polymerize unpolymerized polymerizable compounds after image transfer. A thermal or photopolymerization initiator can be used as the initiator.

Examples of thermal polymerization initiators include azo compounds, organic peroxides,
Examples include inorganic peroxides and sulfinic acids. For details on these, please refer to the Society of Polymer Science and Technology, Edited by the Editorial Committee of Polymer Experiments (q-weighting platform/ring-opening polymerization) (1983).
Imori Publishing), pages 6 to 18, etc.

Examples of photopolymerization initiators include benzophenones, acetophenones, benzoins, thioxansones, and the like. These details are described in ``Ultraviolet Curing System J'' (1989, General Technology Center), pp. 63-147.

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 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. Specifically, an acid precursor that releases an acid when heated, a V electrophile compound that causes a substitution reaction of coexisting chlorine when heated, or a nitrogen-containing hete[] ring cyclized mercapto compound and its precursor. etc. can be mentioned.

For more details, see JP-A No. 62-253159 (31) - (
32), Japanese Patent Application No. 1-72479, Japanese Patent Application No. 1-3471, etc.

Dyes or pigments may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halogenation or irradiation. JP-A-63-29748 describes a photosensitive material in which a white pigment is added to the photosensitive layer.

When the above-mentioned microcapsules are used as the photosensitive layer of the photosensitive material, a dye having the property of being decolored by heating or light irradiation may be included in the microcapsules. The dye having the property of being decolored by heating or light irradiation corresponds to a yellow filter in a conventional silver salt photographic system, and can be made to function as -C.

Regarding photosensitive materials using dyes that have the property of decolorizing by heating or light irradiation, as described in JP-A-63-
As an anti-smudge agent for use in photosensitive materials as described in Japanese Patent No. 97940, it is preferable to use particulate materials that are solid at room temperature. Specific examples include starch particles described in British Patent No. 1,232,347, polymer fine powders described in U.S. Pat. No. 3,625,736, etc., and microcapsule particles containing no coloring agent described in British Patent No. 1,235,991, etc. , cellulose fine powder described in US Pat. No. 2,711,375, inorganic particles such as talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina. The average particle size of the above particles is preferably a volume average diameter in the range of 3 to 50 μm (<,
A range of 5 to 40 μm is more preferred. For the above particles, a larger force is effective than for microcapsules.

Binders that can be used in photosensitive materials can be contained in the photosensitive layer alone or in combination. It is preferable to use a mainly hydrophilic binder. Transparent or translucent hydrophilic binders are typical examples of hydrophilic binders, such as natural substances such as gelatin, seratin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyhinylpyrrolidone, acrylamide polymers, etc. Contains synthetic polymeric materials such as water-soluble polyvinyl compounds.

Other synthetic polymeric substances include dispersed vinyl compounds, which increase the stability of photographic materials, especially in the form of latexes. Regarding photosensitive materials using binders,
There is a description in JP-A No. 61-69062. Further, a photosensitive material using a binder together with microcapsules is described in JP-A-62-209525.

When using latin as a binder for photosensitive materials, various hardening agents can be used.

Specific examples include aldehyde hardeners, anridine hardeners, epoxy hardeners, vinylsulfone hardeners, N-medylol hardeners, and polymer hardeners.

For more information on these, see U.S. Patent No. 4,678,73.
No. 9, column 41, JP-A-59-116655, JP-A No. 62-
No. 245261, No. 61-18942, No. 62-23
There are descriptions in various publications such as No. 4157.

For photosensitive materials, coating aids, peelability improvements, slipperiness improvements,
Various surfactants can be used for purposes such as preventing static electricity and promoting development. Specific examples of surfactants are given in JP-A-62
-173463, No. 62-183457, etc. An antistatic agent can be used in the photosensitive material for the purpose of preventing static electricity. As an antistatic agent, it is described in Research Disclosure magazine, November 1978, No. 17643 (page 27).

When a solvent for a polymerizable compound is used in a photosensitive 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 Application Laid-Open No. 62-2095
There is a description in Publication No. 24. 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 the above-mentioned materials, examples of optional components that can be included in the photosensitive layer and how they are used can be found in the application specifications for the series of photosensitive materials mentioned above, and in Research Disclosure Vol. 1.170, 1978, 6. It is described in Monthly issue No. 17029 (pages 9-15).

Layers that can be optionally provided on the photosensitive material include an image-receiving layer, a heating layer, an antistatic layer, an anti-curl layer, a peeling layer,
Examples include a cover sheet or protective layer, a layer containing a base or a base precursor, a base barrier layer, an antihalation layer (colored layer), and the like.

Instead of using the image-receiving material described below as a method of using the photosensitive material, the above image-receiving layer may be provided on the photosensitive material and an image may be formed on this layer. The image-receiving layer provided on the photosensitive material can have the same structure as the image-receiving layer provided on the image-receiving material. Details of the image receiving layer will be described later.

Regarding photosensitive materials using a heat generating layer, Japanese Patent Application Laid-open No. 1983
For photosensitive materials provided with a cover sheet or a protective layer, see JP-A No. 62-210447, and for photosensitive materials provided with a layer containing a base or base precursor, see JP-A No. 62-253140. A photosensitive material provided with a colored layer as an antihalation layer is described in JP-A-63-101842. Further, a photosensitive material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application Laid-Open No. 61-253140. 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.

Further, the pH of the photosensitive layer of the present invention is preferably 7 or less, and when the base or base precursor is contained in microcapsules, it is preferable that the pH of the photosensitive layer does not increase even when heated.

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.

Next, the image receiving material will be explained. Image-receiving materials generally have an image-receiving layer provided on a support. As a support for image-receiving material,
Although there are no particular limitations, glass, paper, high quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, metals and their analogues, polyester,
polyethylene, polypropylene, acetylcellulose,
Examples include films of cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, etc., and papers laminated with resin materials and 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. 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 contains a white pigment, a binder, a color developer,
It is thought that the polymerizable compound is received by the white pigment, the color developer itself, the white pigment, and the spaces between the particles of the color developer.

Examples of the white pigment used in the image-receiving layer include silicon oxide and tita oxide.

Oxides such as zinc oxide, magnesium oxide, aluminum oxide, etc., magnesium sulfate, barium sulfate, calcium sulfate, magnesium carbonate, barium carbonate, calcium carbonate, carunium silicate, magnesylano 1 hydroxide, magnesium phosphate, magnesium hydrogen phosphate, etc. alkaline earth metal salts, as well as aluminum silicate, aluminum hydroxide, zinc sulfide, sugar clays, talc, kaolin,
Examples include theolite, acid clay, activated clay, and glass.

Examples of the organic white pigment 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, and those having a high oil absorption with respect to 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.
For example, cellulose derivatives such as carboquinomethylcellulose, hydroquine ethylcellulose, and methylcellulose, proteins such as ceratin, phthalated ceratin, casein, and ovalbumin, starches such as dextrin, and etherified detritin, polyhinyl alcohol, and polyhinyl alcohol. Synthetic polymers such as vinyl alcohol partial acetal, polyN-H:ruvirolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, polystyrene sulfonic acid, etc., low-strength stoxin cam, pullulan, gum arabic , sodium alginate, and the like.

Examples of the polymer latex include styrene/butadiene copolymer latex, methyl methacrylate/butadiene copolymer latex, polymer of acrylic ester and/or methacrylic ester, or copolymer latex/ethy-1-non/vinyl acetate. Examples include copolymer latex.

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

The above-mentioned binder can be used in combination with two types of binders, and furthermore, in a ratio such that the two types of binders cause phase separation3. Examples of such usage include The average particle size of the white pigment described in JP-A-1-154789 is 0. 1-20μ.

Preferably it is 0.1 to 10μ, and the coating amount is 0.1g.
~60g8 Preferably, it is in the range of 0.5g to 30g. The weight ratio of the white pigment to the binder is preferably in the range of 0.01 to 0.4, preferably 0.03 to 1 of the pigment.
A range of ˜0°3 is more preferable.

In addition, the image-receiving layer includes a color developer for coloring the colorless color former transferred from the photosensitive material side. Typical color developers include phenols, organic acids, their salts, or esters, and when leuco dyes are used as color image forming substances, zinc salts of salicylic acid derivatives are preferred. Among these, zinc 3,5-cα-methylpentylsalicylate is preferred.

The color developer is preferably contained in the image-receiving layer in an amount ranging from 0.1 to 50 g/-.

More preferably, it is in the range of 0.5 to 20 g/m.

In addition to the above-mentioned additives, the image-receiving layer can optionally contain various additives as described below. For example, the image-receiving layer may contain a thermoplastic compound.

When the image-receiving layer contains a thermal 6J plastic compound, the image-receiving layer itself is preferably composed of aggregates of fine particles of the thermoplastic compound (4). Moreover, it has the advantage that a glossy image cannot be obtained by heating after image formation.The thermo-8J plastic compound is not particularly limited, and can be arbitrarily selected from known plastic resins (plastics), waxes, etc. It can be used selectively.However, it is preferable that the glass transition point of the thermoplastic resin and the melting point of the wax are 200°C or lower.For an image receiving material having an image receiving layer containing thermoplastic compound fine particles as described above, , JP-A-61-280071 and JP-A-62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material,
The color image-forming material is transferred along with the unpolymerized polymerizable compound. 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. 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-62-2.
Each of these is described in Publication No. 10444.

A dye or pigment can be included in the image-receiving layer for the purpose of writing characters, symbols, frames, etc. on the image-receiving layer, or for the purpose of making the background of an image a specific color. Further, a dye or a pigment may be included in the image-receiving layer for the purpose of making it easier to distinguish between the front and back sides of the image-receiving material. As the dye or pigment, various known substances including dyes or pigments that can be used in image formation can be used, but there is a risk that the dye or pigment may damage the image formed in the image-receiving layer. In some cases, it is preferable to lower the dyeing density of the dye or pigment (for example, make the reflection density 1 or less), or to use a dye or pigment that has the property of being decolored by heating or light irradiation.

An image-receiving material having an image-receiving layer containing a dye or pigment that has the property of being decolored by heating or light irradiation is described in JP-A-62-251741.

When the dye or pigment described above is contained in the image-receiving layer, it may be contained uniformly or unevenly distributed in a portion. For example, when the support is made of a light-transmitting material, a portion of the reflected image becomes a projected image due to the white pigment contained in the image-receiving layer. By doing so, image information that is unnecessary in the projected image can also be written as a reflected image in the image-receiving layer portion containing the white pigment.

The image-receiving layer may be configured as layers on two sides depending on the functions described above. Further, the layer thickness of the image-receiving layer is 5 to 5.
00 μm, preferably in the range of 10 to 200 μm.
More preferably, it is in the μm range.

Note that a protective layer may be further provided on the image-receiving layer. Furthermore, a layer made of aggregates of fine particles of a thermoplastic compound may be further provided on the image-receiving layer. An image-receiving material in which a layer made of aggregates of fine particles of a thermoplastic compound is further provided on the image-receiving layer is described in JP-A-62-210460.

Furthermore, a pressure-sensitive adhesive or a layer containing an adhesive and a release paper may be laminated in this order on the surface of the support opposite to the surface on which the image-receiving layer is provided. The sticker-like image receiving material having the above structure is disclosed in Japanese Patent Application Laid-open No. 63-24647 by the present applicant.
There is a description in the bulletin.

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.

As the exposure method, various exposure means may be used, and a latent image of the 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, the heat development treatment may be carried out while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 50°C to 200°C, preferably 80°C to 180°C.
It is ℃. The heating time is generally 0.1 seconds or more, preferably 0.1 seconds or more. 5 seconds to 10 seconds, more preferably 0.
5 seconds to 5''.

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 and the color image-forming substance can be transferred to an image-receiving material to obtain a color image on the image-receiving material.

A conventionally known method can be used for the pressurization method described in ``2''.

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.

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.

Furthermore, when pressing the photosensitive material and the image-receiving material in a superimposed state, they may be heated at the same time. The heating temperature at this time is 35°
C to 120°C, preferably 408C to 80°C.

The photosensitive material of the present invention is a photosensitive material for black and white or color photography and printing, a printing photosensitive material, a printing plate, an X-ray photosensitive material, a medical photosensitive material (for example, an ultrasonic diagnostic CRT photosensitive material), a computer graphic hard copy. It has many uses such as photosensitive materials and photosensitive materials for copying machines.

Example J The present invention will be explained in more detail with the following examples. However, the present invention is not limited thereto.

Example 1 [Preparation of photosensitive material] Preparation of silver halide emulsion (A-1) (sensitivity) 16 g of seratin and 0.5 g of sodium chloride were added to an aqueous gelatin solution (water tsooWl, and the solution was adjusted to pH 3.2 with IN sulfuric acid. 71% of potassium bromide (adjusted to
300 mI of an aqueous solution containing g! and silver nitrate aqueous solution (water 3
0.59 mol of silver nitrate dissolved in 0.00 ml) was simultaneously added in a trickle stream over a period of 50 minutes. One minute after this addition was completed, 43 mA' of a 1% methanol solution of the following sensitizing dye (1) was added, and then 1 minute after the addition of the sensitizing dye (1) was added.
Aqueous solution containing 2.9 g of potassium iodide from 5 minutes 100
mA' and silver nitrate aqueous solution (silver nitrate 0.018 in 100 - water
mol) was added at equal flow rates over 5 minutes. To this emulsion, 10 cc of a 10% alkaline aqueous solution of isobutylene maleic anhydride copolymer was added to precipitate the emulsion, washed with water and desalted, then 12 g of seratin was added and dissolved, and 0.0 cc of sodium thiosulfate was added. 5 ■Additionally 60°C
Chemical sensitization was carried out for 15 minutes with an average particle size of 0°22μ.
m monodispersed 14-hedral silver iodobromide emulsion (A-1) 1000
g was prepared.

Sensitizing dye (1) The following polymerizable compound - Kawa (trade name, Kayarad R-6
84, Nippon Kayaku (manufactured by Kiki) 210g1m, yellow pigment (trade name, Microlith Yellow 4GA, manufactured by Ciba Kaigyi)
45 g and 4.5 g of the following leuco yellow dye were mixed and stirred at 70°C for 12 hours to form an ink composition (A-1).
was created.

(Polymerizable compound)-1 (Leuco yellow dye) Preparation of base precursor solid dispersion [X] 70 g of the base precursor represented by the following formula (1) and 130 g of a 5% seratin aqueous solution were mixed, and using a Dyno Mill dispersion machine, 3000
rpm for 1 hour to prepare a solid dispersion [X] of a base precursor consisting of particles with an average size of 0.5 μm.

[■] Add 20% methylpropylene glycol of the copolymer shown below to 45 g of the ink composition (A-1) prepared above.
9 g of solution and 2.3 g of reducing agent (RD-1), reducing agent (
3.1 g of RD-2), mercapto compound (FF-1)
Add 0.006g of methylene chloride to 60
The mixture was stirred at °C for 1 hour to prepare an oily liquid.

copolymer CH, CH.

6 CH2-C de 100 years old CHt C 廿 CO, C
H2CH=CH2CO□H F-1 Add which silver halide emulsion (A-1) 5 to this oily liquid.
g and 24 g of the above solid dispersion of base precursor (X)
Add the mixed solution and stir at 15,000 r, p, m for 5 minutes using a homogenizer while keeping the temperature at 60 ° C.
0 emulsion photosensitive composition (A, -1) was prepared.

Preparation of photosensitive microcapsule liquid (A-1) 8 g of 15% aqueous solution of potassium polyvinylbenzenesulfinate
A mixture of 130 g of a 7.1% aqueous solution of polyvinylpyrrolidone (trade name: Ni-90, manufactured by Wako Pure Chemical Industries (Kiku)) was adjusted to pH 5.
, adjusted to 0. Add the above photosensitive composition (A-
Add 1) and use Daysilver at 60℃ for 20 minutes.
The mixture was stirred at 5000 r, p, m to obtain a W/○/W emulsion.

Separately, 20.0 g of a 37% formaldehyde aqueous solution and 76.3 g of distilled 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 an aqueous solution of this initial condensate was added to the W, O.W.
Stir for a minute.

Furthermore, in order to remove formaldehyde remaining in the capsule dispersion, 16 g of an aqueous solution of urea 409 was added, the pH was adjusted to 35 using a 20% aqueous solution of phosphoric acid, and stirring was continued for 40 minutes. After the reaction was completed, the capsule liquid was adjusted to pH 6.5 using a 10% aqueous sodium hydroxide solution and cooled.

As described above, the photosensitive microcapsule dispersion (A
-1) was adjusted.

Style of photosensitive material (A-, 1) 45% of the above photosensitive microcapsule dispersion (A-kawa)
g, 0.2 g of a surfactant (trade name: Emmalex NP-8, manufactured by Nippon Emulsion (manufactured by Kiki), and 10 g of a 5% aqueous solution of polyvinyl alcohol (trade name: PVA, -205, manufactured by Kuraray), and further water were added. A coating solution for forming a photosensitive layer was prepared with a total amount of 74 g.

48 g of this coating solution was applied to a 1-note film L of aluminum-deposited polyethylene terephthalate with a length of 2,571 m.
, 'm' coating amount and dried at about 408C to prepare a photosensitive material (A-1).To prepare 125g of water per side of the image receiving material, 11g of sulfur and lithium 409hexamethyleneate aqueous solution was added. Further, 34 g of zinc 3,5-di-α-methylpentylsalicylate and 82 g of 55% calcium carbonate slurry were mixed with this and coarsely dispersed using a mixer. Disperse the liquid with a Dynamyl dispersion machine, and 2 of the obtained liquid
00g, 8% polyvinyl alcohol aqueous solution 112
g was added and mixed uniformly. Add 70% water to this mixture.
g was added to prepare a coating solution for forming an image-receiving layer. And weigh this coating liquid at 55g/rr? paper support (JIS-P-
, 8207) (paper support using a base paper having a fiber length distribution such that the sum of the weight % of the 24 mesh residue and the weight % of the 42 mesh residue is 30 to 60%) The film was uniformly coated on the surface at a coating weight of 58 g/m, and then dried at 60° C. to prepare an image-receiving material.

Example-2 Preparation of silver halide emulsion (A-2) (green-sensitive) 20 g of seratin and 0.5 g of sodium chloride were added to an aqueous gelatin solution (1600 mβ of water, and the solution was adjusted to pH 3 with IN sulfuric acid.
2 and kept at 42°C), an aqueous solution containing 71 g of potassium bromide at 200 mA! and silver nitrate aqueous solution (
(0.59 mol of silver nitrate dissolved in 200 ml of water)
were simultaneously added at equal flow rates over 30 minutes. One minute after this addition was completed, 48 m (!) of a 1% methanol solution of the following sensitizing dye (2) was added.
0ml! and silver nitrate aqueous solution (0.0 silver nitrate in 100 ml of water)
18 mol dissolved) was added at equal flow rates over 5 minutes. To this added emulsion, 10 ee of a 10% alkaline aqueous solution of isobutylene maleic anhydride copolymer was added to precipitate it, washed with water to desalt it, and then 18 g of seratin was added and dissolved, followed by 0.7 μl of sodium 100 sulfate. Add
Chemical sensitization was performed at 60°C for 15 minutes, and the average particle size was 0.
．． 12 μm monodispersed tetradecahedral silver iodobromide emulsion (A −=2
) 1000g was prepared.

Sensitizing dye (2) Red pigment (trade name: Microlith Red 3R-A, manufactured by Ciba Geigy) was added to 21.0 g of polymerizable compound-1.
45 g of the following leuco macenta dye (trade name: Barka Script 1.6B, manufactured by Ciba Geigy) were mixed and stirred at 70°C for 12 hours to form an ink composition (A-2).
was created.

In the preparation of the photosensitive composition (A-1) of leuco macenta dye Example-1,
Instead of the ink composition (A-1) used, the same amount of the above ink composition (A-2) was used, and the silver halide emulsion (
The above silver halide emulsion (A-2) was used instead of A-1,).
A photosensitive composition (A-2) was prepared in exactly the same manner except that the same amounts of , ) were used.

Preparation of photosensitive microcapsule dispersion (A-2) (green sensitive) Photosensitive microcapsule dispersion (A-1) of Example-1
In the preparation of, instead of the photosensitive composition (A-1),
A photosensitive microcapsule dispersion (A-2) was prepared in the same manner except that the above photosensitive composition (A-2) was used.

Preparation of Photosensitive Material (1-2) In preparing the photosensitive material (A-1) of Example-1, the above photosensitive microcapsule dispersion was used instead of the photosensitive microcapsule dispersion (A-1). A photosensitive material (A-2) was prepared in exactly the same manner except that the same amount of (8-2) was used.

Example-3 Preparation of silver halide emulsion (A-3) (sensitivity) Ceratin aqueous solution (20 g of gelatin and 0.5 g of sodium chloride were added to 1,600 ml of water, adjusted to pH 3.5 with IN sulfuric acid, and heated at 45°C. 71g of potassium bromide
200 ml of an aqueous solution containing silver nitrate (200 ml of water)
0.59 mol of silver nitrate dissolved in .rrl) was simultaneously added at an equal flow rate over 30 minutes. One minute after this addition was completed, 48ml of a 0.5% methanol solution of the following sensitizing dye (3) was added! and after addition of the sensitizing dye, 1
Aqueous solution containing 3.65 g of potassium iodide from 5 minutes 10
0ml and silver nitrate aqueous solution (silver nitrate 0.22 in 1°OmA of water)
g (dissolved)) was added at equal flow rates over 5 minutes. To this emulsion, 10 cc of a 10% alkaline aqueous solution of isobutylene maleic anhydride copolymer was added, sedimented, washed with water, and desalted. 10 g of gelatin was added and dissolved, and further 0.45 μl of sodium thiosulfate was added. 55℃
Chemical sensitization was carried out for 20 minutes with an average particle size of 0.13.
μm monodisperse 14-hedral silver iodobromide emulsion (A-3) 1000
g was prepared.

Sensitizing dye (3) To 210 g of polymerizable compound-1, add 45 blue pigments (trade name, Microlis Blue 4G-A, manufactured by Ciba Geigy).
g and 45 g of the following leuco-based dye, and heated at 70℃.
The mixture was stirred for 2 hours to prepare an ink composition (A-3).

In the preparation of the photosensitive composition (A-1) of Example-1,
Instead of the ink composition (A-1) used, the same amount of the above ink composition (A-3) and the silver halide emulsion (A-3) were used.
-1), the above silver halide emulsion (A-3)
The photosensitive composition (
A-3) was prepared.

Preparation of photosensitive microcapsule dispersion (A-3) (red sensitivity) Photosensitive microcapsule dispersion (A-1) of Example-1
In the preparation of, instead of the photosensitive composition (A-1),
A photosensitive microcapsule dispersion (A-3) was prepared in the same manner except that the above photosensitive material (A-3) was used.

Photosensitive material (made by Nnee U-9-1) In the preparation of the photosensitive material (A-4) of Example-I, the above photosensitive material was used instead of the photosensitive microcapsule dispersion (A-1). The photosensitive material (A-3) was prepared in exactly the same manner except that the same amount of the microcapsule dispersion (A-3) was used.
It was created.

The evaluation method and results of the photosensitive materials are shown in the last table.

Comparative Example I In the production of the photosensitive material of Example 1, the ink composition (A
Photosensitive materials (A, -1, P) were produced in exactly the same manner except that the leuco yellow dye in -1) was removed.

Comparative Example 2 In the production of the photosensitive material of Example 2, the ink composition (A
A photosensitive material (A-2P) was prepared in exactly the same manner except that the leuco macenta dye in -2) was removed. , Comparative Example 3 In the production of the photosensitive material of Example 3, the ink composition (A
A photosensitive material (A-3P) was produced in exactly the same manner except that the leuco cyan dye in -3) was removed.

Comparative Example 4 In the production of the photosensitive material of Example 1, the ink composition (A
A photosensitive material (A-ID) was produced in exactly the same manner except that the yellow pigment in -1) was removed.

Comparative Example 5 In the production of the photosensitive material of Example 2, the ink composition (,
A-2) In exactly the same manner except for removing the red pigment,
A photosensitive material (A-2D) was prepared.

Comparative Example 6 Example: In the production of a photosensitive material of (, an ink composition of (
A = 3) except for the blue pigment in the same manner,
A photosensitive material (A-3D) was produced.

Comparative Example 7 In the production of the photosensitive material of Example 2, the ink composition (A
A photosensitive material (A-4D) was prepared in exactly the same manner except that the red pigment in 2) was removed and the amount of leuco macenta dye (same as in Example 2) was increased from 45 g to 90 g.

Comparative Example 8 In the production of the photosensitive material of Example 2, the ink composition (,
An attempt was made to produce photosensitive microcapsules in exactly the same manner except that the leuco macenta dye in A,-2) was removed and the red pigment (same as in Example-2) was increased from 45g to 90g. However, the capsule particle size was 100 μm or more, and good capsules could not be obtained. In addition, the transferred image was unclear.

The evaluation results of the photosensitive materials produced in Comparative Examples 1 to 7 in 1-1-1 are summarized in the table on the next page together with Examples.

The photosensitive materials obtained in the above actual examples and comparative examples were
Cl11, each cut into 2.6ca+ width. This photosensitive material was overlapped with the coated surface of the image-receiving material produced in Example-1 without being exposed to light, and in that state, the weight was 800 kg/c.
n! was passed through a pressure roller. The image-receiving material on which the transferred image was obtained was heated using a xenon lamp (85,000 Iux, UV
For about 3 weeks (50°C1) under irradiation conditions (with filter)
After aging at 40% RE (humidity control), the light progression of the image was examined. (
(measurement of low reflection density) From the above results, the following was clarified.

In any of yellow, magenta, and cyan light-sensitive materials, when only color pigments are used as color image forming substances, the light fastness of the images is strong, but the fresh density is low. (
Comparative Example 1, Comparative Example 2, Comparative Example 3). Furthermore, when only leuco dye is used, the fresh density is high, but the density decreases significantly over time due to poor light resistance. (Comparative example 4,
Comparative Example 5, Comparative Example 6, Comparative Example 7) On the other hand, when a pigment and a leuco dye were used simultaneously as color image forming substances, a high fresh density was exhibited, and the density remained high even after 3 weeks under xenon irradiation. was maintained. (Example 1, Example 2, Example 3).

Evaluation of transferred images The photosensitive materials A-1 to A-3 of the present invention were exposed using a tungsten bulb through a filter having a transmission density of 0 to 3.0 to a color temperature of 4800 under exposure conditions of 20001 ux for 10 seconds. The support side of the photosensitive material was placed on a hot plate heated to 155° C., and the photosensitive layer was brought into close contact with the photosensitive material and heat-developed for 2 seconds. Next, the photosensitive material was overlapped with the image-receiving material, and in that state was passed through a pressure roller of 1,000 mm. Then, the image receiving material is peeled off from the photosensitive material,
A clear positive image was obtained on the image receiving material.

Claims (1)

[Claims] A photosensitive material having, on a support, a photosensitive layer containing at least a silver halide, a reducing agent, a polymerizable compound, and a microcapsule containing a color image forming substance, wherein the color image forming substance is a color pigment and a colorless dye capable of forming a color. A photosensitive material characterized by comprising: