JPS61294434A - Photosensitive material - Google Patents

Abstract

PURPOSE:To increase the photosensitivity, to improve the aging stability and to form an image by simple operation by polymerizing a polymerizable compound by heating the electric current supplied to a heating element layer after imagewise exposure to produce a high molecular compound and to immobilize a color image forming substance. CONSTITUTION:A photosensitive layer and a heating element layer are formed on one side or both sides of a support. The photosensitive layer contains essen tially photosensitive silver halide, a reducing agent, a polymerizable compound and a color image forming substance. The polymerizable compound and the color image forming substance have been microencapsulated together. The polymerizable compound is polymerized by heating with electric current supplied to the heating element layer after imagewise exposure to produce a high molecu lar compound and to immobilize the color image forming substance. The pre ferred average particle size of the silver halide is 0.001-10mum and the amount of the silver halide applied is 1mg/m<2>-10g/m<2> (expressed in terms of silver). The resulting photosensitive material has high photosensitivity and superior aging stability and enables the formation of an image by simple operation.

Description

Detailed Description of the Invention (1) Background of the Invention Technical Field The present invention relates to a photosensitive material having a photosensitive layer containing microcapsules encapsulating a polymerizable compound and a color image forming substance and a heat generating layer. More specifically, a photosensitive silver halide is used as a sensor, and a polymer compound is generated in an imagewise manner by utilizing an imagewise latent image formed on this silver halide when irradiated with actinic radiation, thereby forming a coexisting color image. It relates to photosensitive materials that immobilize substances.

Prior art and its problems Various recording materials using microcapsules are known.

For example, Japanese Patent Publication No. 42-14344 (U.S. Pat. No. 3,2
No. 19,446), a light-sensitive sheet having many fluid droplets that become non-flowing when irradiated with light is imagewise exposed to light, and this is superimposed on an image-receiving sheet and pressure is applied to the entire sheet. A method is disclosed in which an image is transferred onto this image-receiving sheet in accordance with exposure.

Furthermore, in JP-A No. 52-89915, one component of a two-component thermosensitive coloring material and a photopolymerizable monomer are encapsulated in microcapsules, and the other component of the thermosensitive coloring material is mixed with the microcapsules to form a base sheet. A method is disclosed in which the photosensitive sheet is imagewise exposed to harden the microcapsules in the exposed areas, and then the entire surface is heated to develop color only in the unexposed areas, thereby obtaining an image.

Furthermore, JP-A-57-124343 and JP-A-57-179
No. 836 and No. 57-197538 describe an image forming method using microcapsules containing a vinyl compound, a photopolymerization initiator, and a dye precursor, which do not require heating by applying pressure to the entire surface after exposure. A method of forming an image is disclosed.

Also, Japanese Patent Publication No. 54-20852 (U.S. Patent No. 3.70
No. 0.439) discloses an image forming method in which Michler's ketone is encapsulated as a photosensitive substance and utilized.

U.S. Pat. No. 3,072,481 also discloses encapsulating a photosensitive material that is easily converted to a colored form in a liquid but is photoinsensitive when in a solid state, and layering this encapsulation. A method of forming an image by imagewise exposure of the compound and then rupturing the capsule to evaporate the solvent, a so-called photosensitive and pressure sensitive image forming method, has been disclosed.

The aforementioned micro forces? Various image forming methods using cells are known, but all of them have in common a low sensitivity to light, particularly a marked lack of sensitivity to green light and red light. In addition, when trying to increase this sensitivity, storage stability has the disadvantage of declining.

On the other hand, various types of image forming methods using silver halide as a photosensor are known, other than the so-called conventional photographic materials.

For example, British Patent No. 866.631 discloses a method of directly causing photopolymerization using silver halide as a catalyst. It is thought that it acts as a catalyst, and it is not possible to obtain as high a sensitivity as when silver halide is reduced by ordinary development.

Furthermore, Belgian Patent No. 642.477 discloses that after exposed silver halide grains are developed with an ordinary developer, polymerization is caused using the resulting silver image or unreacted silver halide as a catalyst to form a polymer compound image. Although a method for forming the same is disclosed, this requires complicated operations.

Zarani Kai Kosho No. 45-11149, No. 47-20741
No. 49-10697, No. 57-138632,
No. 58-169143 discloses that when exposed silver halide is developed using a reducing agent, the reducing agent is oxidized and at the same time coexisting vinyl compounds start polymerizing to form an image-like polymeric substance. However, this method requires a developing step using a liquid.

There are various known image forming methods that use silver halide as a photosensor, but all of them have drawbacks such as not being able to obtain high sensitivity or requiring complicated processing steps. have.

II. OBJECTS OF THE INVENTION The objects of the present invention are to provide high sensitivity to light (particularly sensitivity to green light and red light as required), excellent stability over time, and enable image formation with simple operations; The object of the present invention is to provide a photosensitive material that is easy to use.

■Disclosure of invention Such an object is achieved by the present invention described below.

That is, 1 the present invention has a photosensitive layer and a heat generating layer on a support, and the photosensitive layer and the heat generating layer may be formed on the same side of the support or on opposite sides,
This photosensitive layer contains at least a photosensitive silver halide, a reducing agent,
It contains a polymerizable compound and a color image forming substance, and at least the polymerizable compound and the color image forming substance are encapsulated in the same microcapsule, and after image exposure, the polymerizable compound is polymerized by heating the heating element layer with electricity. This photosensitive material is characterized in that it is configured to immobilize a one-color image forming substance by generating a polymer compound.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The photosensitive material of the present invention has a photosensitive layer and a heat generating layer, and the photosensitive layer contains at least a photosensitive silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, and at least the polymerizable compound and the color image forming substance. The imaging material is encapsulated in the same microcapsule. In the light-sensitive material of the present invention, after image exposure, the heating layer is heated with electricity to polymerize the polymerizable compound to produce a high molecular compound, thereby immobilizing the color image forming substance.

The photosensitive material of the present invention uses a photosensitive silver halide as a photosensor, and the silver halide produced by exposure to light.

The latent image nucleus acts as a catalyst to cause an oxidation-reduction reaction between the silver salt and the reducing agent, and the radical intermediate produced in the process is used as an initiator to carry out a polymerization reaction.

Alternatively, after the first reducing agent and the silver salt undergo an oxidation-reduction reaction, this product is further reacted with another compound, and a polymerization reaction is carried out using the generated radicals as an initiator.

It could not have been predicted from conventional knowledge that this series of reactions would be significantly accelerated by heating or uniform exposure.In particular, in a dry system that does not use a developer, the reaction between silver salt and reducing agent can generate radicals. The generation of intermediates is a completely new finding.

In the present invention, depending on the type of photosensitive silver halide used, it is possible to produce a polymer compound corresponding to both exposed and unexposed areas. In the part where a polymer compound is formed (microcapsule), the part where it is not formed (microcapsule) is
As a result, the pressure resistance is increased compared to microcapsules, and as a result, a color image can be formed using a color image-forming substance by transferring the part where a polymer compound is not produced to an image-receiving material by applying pressure. I can do it. Therefore, in the present invention, depending on the type of photosensitive silver halide used or the color image forming process adopted, it is possible to freely create either a negative image or a positive image on the original image, and in some cases, both negative and positive images can be created simultaneously. You can also do that.

For example, when obtaining a color image by transferring an area where no polymer compound is formed, a normal negative-working silver halide emulsion can be used to obtain a positive-working image with respect to the original image. In order to form a negative image, internal images described in U.S. Pat. No. 2,592.250, U.S. Pat. silver halide emulsion.

Also, mixtures of surface-imaged silver halide emulsions and internally imaged silver halide emulsions such as those described in U.S. Pat. No. 2,998,382 may be used.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan in the subtractive color method in the present invention, the photosensitive material must contain at least three types of halogens that are sensitive to different spectral regions. It is necessary to have a silver oxide emulsion. Typical combinations of at least three light-sensitive silver halide emulsions sensitive to different spectral regions include a combination of a blue-sensitive emulsion, a green-sensitive emulsion and a red-sensitive emulsion, a green-sensitive emulsion, a red-sensitive emulsion and an infrared-sensitive emulsion. Examples include combinations of light-sensitive emulsions, combinations of blue-sensitive emulsions, green-sensitive emulsions and infrared-sensitive emulsions, and combinations of blue-sensitive emulsions, red-sensitive emulsions and infrared-sensitive emulsions. Note that the infrared light-sensitive emulsion herein refers to an emulsion that is sensitive to light of 700 nm or more, particularly 740 nm or more.

For example, when using a combination of a blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion, the blue-sensitive microcapsules contain a yellow imaging material, the green-sensitive microcapsules contain a magenta imaging material and a red-sensitive The cyan image-forming substance may be contained in the cyan image-forming substance.

By using microcapsules in this way, it is possible to separate the image forming substances of yellow, magenta, and cyan and include them in the same photosensitive element, thereby making it possible to form color images with simple operations. .

When trying to form a color image using the above-mentioned known technology.

(1) No sensitivity to green light or red light, (2) Low sensitivity to blue light, (3) Poor stability over time.
(4) Requires complicated operations.

(5) Some disadvantages such as the need for a processing step using a liquid cannot be avoided, but the photosensitive material of the present invention can solve all of these problems.

Therefore, the light-sensitive material of the present invention can be particularly useful for color image formation.

The following examples can be given as configurations of the photosensitive element and image receiving element in the present invention.

The photosensitive element herein includes photosensitive/X silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, and at least the polymerizable compound and the color image-forming substance are contained in the same microcapsule. An encapsulated element is meant, while an image-receiving element is an element in which the color image-forming material emitted from the photosensitive element is immobilized and forms a color image. The structure of these elements and the method of image formation will be described below, but embodiments using the photosensitive material of the present invention are not limited thereto.

(1) When the color image-forming substance is itself a colored dye or pigment.

(a) A light-sensitive element and an image-receiving element are coated on separate supports to form a light-sensitive material and an image-receiving material, respectively, and the light-sensitive material is subjected to imagewise exposure, heating or uniform exposure, and then image-receiving. A color image is formed on the image-receiving material by pressing the materials together.

(b) A photosensitive element is coated on a support, a light-reflecting layer is coated thereon, and an image-receiving element is further coated thereon. This light-sensitive material is imagewise exposed from the side of the support, heated or uniformly exposed, and then the color image-forming substance is moved imagewise to the image-receiving element by applying pressure to form a color image on the image-receiving element.

(2) A case in which the color image forming substance itself is colorless or light-colored, but develops color when other energy is applied.

The configuration in this case may be the same as (a) and (b) in (1) above, but in either example, a step of applying energy for coloring the color image forming substance is required. However, if this color development occurs at the same time as (1) heating, exposure, or pressurization, no special process is required.

(3) The color image forming substance (referred to as a color former in this case) is itself colorless or light-colored.

When color develops when it comes into contact with other components (referred to as coloring agents).

(a) If the image-receiving element contains a color developer in the same manner as (a) of (1) above, the color image forming substance and the color developer come into contact with each other under pressure to form a color image. .

(b) In the same manner as (b) of (1) above, if a color developer is contained in the image-receiving element, the color image forming substance comes into contact with the color developer under pressure, and a color image is formed. Form.

(c) There is an embodiment in which the photosensitive element and the image receiving element are coated adjacent to each other on the support, or the components of these two elements are mixed and coated. In either case, when the color developer is used as a component of the image-receiving element, the light-sensitive material (which also serves as the image-receiving material) is imagewise exposed and then heated or uniformly exposed and then pressurized to destroy the microcapsules. The color image-forming substance and the color developer come into contact and develop color, forming a color image. In this case, since the color image forming material in the non-colored portion is substantially colorless, it can be visually seen directly as a color image.

In the present invention, the polymerizable compound in the area where the latent image is present is polymerized by heating to form a high molecular compound, and the heating can be carried out by contacting the photographic material with a large-capacity hot plate, laser, infrared rays, etc. These include methods of directly heating photographic materials by irradiating them with ultrasonic waves or high-frequency waves, and methods of passing photographic materials through heated gas.
However, these methods have many drawbacks and do not give satisfactory results. For example, the method using a hot plate takes time to bring the hot plate to a uniform temperature, consumes a lot of power, and is difficult to contact. If it is insufficient, there will be drawbacks such as difficulty in uniformly transmitting the temperature to the photosensitive material. Methods that use radiation such as lasers require large equipment, making it difficult to assemble a compact system, while methods that use gas take time because the heat capacity of the gas is small.

In order to improve these drawbacks, a method of using a conductive heating layer in combination with a heat-developable photosensitive layer has been proposed in U.S. Pat. .

On the other hand, various positive conductive heating element layers (herein referred to as conductive heating element layers whose electrical resistance increases as the temperature rises) for the purpose of sheet heaters have been developed ( For example, JP-A-49-82734, JP-A No. 49-8
No. 2735, No. 51-13991, No. 51-3974
No. 2, No. 51-3974'3, No. 52-87694).

These are designed to prevent overheating by taking advantage of the property that electrical resistance increases as the temperature rises.
It is applied to plain heaters, snow removal equipment, etc.

It is also possible to apply these positive conductive heating element layers to photographic materials, for example, as disclosed in Japanese Patent Application No. 58-2293.
It is described in No. 77.

The conductive heating element layer may be positive type as mentioned above, or negative type (a conductive heating element layer whose electrical resistance decreases as the temperature rises).
You can freely design it depending on the purpose, whether it is a type with resistance that does not depend on temperature. Furthermore, either a hydrophilic binder or a hydrophobic polymer binder using an organic solvent can be used as the binder, and the binder is selected depending on the characteristics of the intended electrically conductive heat generating layer.

This conductive heating element layer may have a single layer or multilayer structure. In particular, it may have a suitable structure for the purpose of reducing the dependence of resistance on environmental humidity or increasing physical strength against bending, folding, abrasion, etc. It is also advantageous to provide a protective layer.

From this standpoint, in the present invention, it is preferable to use a conductive heat generating layer.

The conductive substances contained in the conductive heating element layer include iron,
Metals such as copper, silver, nickel, and platinum, alloys containing nickel and chromium as main components known as nichrome wire and Kanthal wire, noble metal alloys such as platinum-rhodium alloy, silicon carbide, silicon molybdenum, and zirconia (Zr02) ), zinc oxide, titanium dioxide, oxide semiconductors such as doria (Th02), graphite, and carbon blacks are representative examples. Among these materials, graphite and carbon black are particularly preferably used because they are inexpensive. As carbon black, conductive carbon black is known, but not only conductive carbon black but various carbon blacks can be used. These carbon blacks are described in Carbon Black Yearbook, J.P. Donnet & N.P.
Carbon Black ((:arbon
Black)? -Six Jl/Detsuka-(Mar
Published by cel Dekker).

(1976), and also by the Columbian Carbon Company.
Company), Mitsubishi Chemical Industries, Ltd., etc.

Among these carbon blacks, carbon blacks having a measured value of dibutyl phthalate (DBP) oil absorption of 80 cc/100 g or more according to either method A or method B specified in JIS-6221 are preferred.

Such carbon black is manufactured by Cabot Co., Ltd. (
Cabot Corporation, Lion Akzo Co., Ltd., Columbian Carbon Japan Co., Ltd., etc. can be easily selected and obtained from carbon catalogs. A preferred example is Capot's BLACK.
PEARLS1300, BLACK PEARLS
looo, BLACK PEARLS880, BLA
CK PEARLS 700, BLACK PE
ARLS 2000, VULCAN XC-72,
VULCANP, VULCAN 9. REGAL30
0R1ELFTEX PELLETS115゜EL
FTEX8, ELFTEX12.5TERLING
So, 5TERLINGv, Jl11KETJENBLACK EC manufactured by Easy Co., Ltd. (sold by Lion Akzo Co., Ltd.)
C), ROYA of Columbian Carbon Japan Co., Ltd.
LSPECTRA, NEOSPECTRAMARK
I and ■, NEO 3PECTRA AG, 5UPERBA (NEOMK
n), NEOSPECTRAMARK rV, RAV
EN 5000゜RAVEN 7000, RAVE
N 5750, RAVEN 5250. RAVEN350
0, RAVEN 3200, RAVEN 1040. RAVEN 890POWDER, RAVAN 890HPOWDER, RAVEN 825BEADS, RAVEN 500, C0NDU
CTEX 40-220゜C0NDUCTEX
975 BEADS, C0NDUCTEX
900 B E A D S , C0
NDUCTEX SC,RAVENH20POWD
ER, RAVEN CBEADS, RAVEN
22 POWDER, RAVEN 16 POWDER, RAVEN 14 POWDER, etc.

In the present invention, various polymers can be used as binders in the conductive heat generating layer. Typical wood-philic binders are transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, and polyvinyl colloids. Among these, gelatin and polyvinyl alcohol are preferred, with gelatin being particularly preferred, including synthetic polymeric materials such as water-soluble polyvinyl compounds such as pyrrolidone, acrylamide polymers, and the like.

In addition, a tree-philic conductive polymer can also be used as a binder (in this case, the conductive substance also serves as a hydrophilic binder). Examples of the conductive polymer include polypiperidinium chloride, polyvinylbenzyltrimethylammonium chloride, etc. Cationic polymer electrolysis can be used. Conductive fine particles may be used in combination with a conductive polymer.

Other effective polymers include water-insoluble polymers containing monomers such as alkyl acrylates, alkyl methacrylates, acrylic acid, sulfoalkyl acrylates, or sulfoalkyl methacrylates, and Canadian Patent No. 77
Examples include those having a circulating sulfobetaine unit as described in No. 4,054. Preferred polymers include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene styrene copolymer, vinyl chloride. Examples include vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate phthalate, and the like. Among these polymers, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, and cellulose acetate butyrate are particularly preferred.If necessary, two or more types may be used in combination.These conductive fine particles or highly conductive The electrical resistance of a conductive film made of molecules singly or in combination is
A desired value can be obtained depending on the ratio of the conductive material to the binder, the method of dispersion, the properties of the binder, etc., but in the present invention, it is 0.01 to 10ΩclI, particularly 0.1 to 10ΩclI.
It is preferable to set the volume resistance to 1 Ωci+, and the method thereof is described in the above-mentioned literature or the technical data of each carbon black manufacturing company, and is well known in the industry.

The amount of conductive material used is generally 10 to 1 weight ratio.
90% by weight, preferably 15 (85% by weight). Approximately 0.1 g of carbon black is used as a conductive material.
~50 g/m'', preferably about 0.5 g/m'' to about 20 g/m''
Particularly good results can be obtained when rn' is used.

The carbon black content in this case is about 10% to about 90%, preferably about 15% to about 80% by weight.

The thickness of the conductive heat generating layer having the above structure is preferably in the range of 0.5 to 15p or less.

In addition, current may be supplied by attaching an electrode to the conductive heat generating layer.

The applied current may be direct current or alternating current, and the voltage can be determined depending on the volume resistance value and desired temperature described above. In addition, instead of constant voltage application, constant power application may be performed by devising a single circuit. In addition, in the case of constant voltage application, it is desirable to apply less than IKv from the viewpoint of safety.

In the present invention, the conductive heat generating layer and the photographic layer such as the photosensitive layer or the image receiving layer may be provided on the same side of the support or on opposite sides of the support.

The heating temperature at this time is generally 80℃~ The temperature is 200°C, preferably 100°C to 169°C.

Various patterns can be applied as the pattern for heating the photosensitive material. The most common method is heating at a constant temperature, but depending on the characteristics of the photosensitive material, multi-step heating may be used, such as heating at a high temperature for a short time and then lowering the temperature in stages.
is valid. In this case, the heating time is generally 5 seconds to 5 seconds.
minutes, preferably 5 seconds to 1 minute.

If the photosensitive material is susceptible to air oxidation during heating, it is effective to deaerate the area around the heating section or replace it with an inert gas. In addition, the surface of the photosensitive material may be brought into direct contact with the heated part or may be exposed to the air. When developing with the surface of the photosensitive material facing the air, evaporation of moisture and volatile components from the photosensitive material is prevented. It is also effective to attach a cover for heat retention purposes.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
It may be silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide.The halogen composition within the grains may be uniform, or the composition may differ between the surface and inside. (Unexamined Japanese Patent Publication Nos. 57-154232 and 57-154232).
No. 8-108533, No. 59-48755, No. 59-
52237, U.S. Patent No. 4,433.048 and European Patent No. 100984);
．． 5 microns or less, with a grain size of at least 0.6 microns and an average aspect ratio of 5 or more (U.S. Pat.
414,310, OLS No. 4.435.499, OLS No. 3,241.646A, etc.) or monodisperse emulsions with a nearly uniform particle size distribution (JP-A-57-178235, OLS No. 58). -100846, same 5
No. 8-14829, International Publication No. 83102338A.

No. 64,412A3. and 83.3 of the same
77A, etc.) may also be used in the present invention. Two or more types of silver halide with different crystal habits, halogen compositions, grain sizes, grain size distributions, etc. may be used in combination, and two or more types of monodispersed emulsions with different grain sizes are mixed to form You can also change the key.

The grain size of the silver halide used in the present invention is preferably one in which the average grain size is from 0.001 micron to 10 microns, and more preferably from 0.001 micron to 5 JL. The particles may be prepared by any method, neutral method or ammonia method, and the reaction method of soluble silver salt and soluble halogen salt may be one-sided mixing method, simultaneous mixing method or a combination thereof. A back-mixing method in which the formation is performed under ion excess or a Chondrald double-jet method in which the PAg is kept constant can also be employed. Furthermore, in order to accelerate the growth of one grain, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Unexamined Patent Publication No. 55-142
No. 329, No. 55-158124, U.S. Patent No. 3.6
50,757, etc.'').

Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, U.S. Pat. No. 4,094,
No. 884).

When silver halide is used alone without an organic silver salt saponifying agent in the present invention, it is preferable to use silver chloriodide, silver iodobromide, or Silver iodobromide. For example, silver bromide particles are prepared by adding a silver nitrate solution to a potassium bromide solution, and then potassium iodide is added to obtain silver iodobromide having the above-mentioned properties.

In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, and Japanese Patent Publication No. 47-1
Organic 1,000-onythyl derivatives described in No. 1386 or sulfur-containing compounds described in JP-A-53-144319 can be used. In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

Further, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (m, ■) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

Silver halide is used as an emulsion, and the emulsion may be free of soluble salts after precipitation or physical ripening, and thus can be subjected to the Tardel water washing method or the precipitation method. The silver halide emulsion may be used as it is after ripening, but it is usually used after being chemically sensitized. For emulsions for conventional sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526, JP-A-58-2156).
No. 44).

The silver halide emulsion of the present invention may be a surface latent image type in which a latent image is mainly formed on the grain surface, or an internal latent image type emulsion in which a latent image is formed inside the grain. Direct inversion emulsions in combination with nucleating agents can also be used. An internal latent image emulsion suitable for the purpose described in U.S. Patent No. 2.
592.250, 3.761,276, Japanese Patent Publication No. 58-3534, and Japanese Patent Publication No. 57-136641.

A preferred nucleating agent for combination is U.S. Pat.
．． No. 552, No. 4, No. 245, No. 037, No. 4.
No. 255.511, No. 4,266.013, No. 4
．． No. 276.364 and OLS No. 2
, 635, 316.

The coating amount of photosensitive silver halide used in the present invention is in the range of 1 mg to LOg/m'' in terms of silver.

In the present invention, an organic silver salt relatively stable to light can be used in combination with the photosensitive silver halide as an oxidizing agent. In this case, the coating amount of photosensitivity/silver halide is in the range of 1 mg to Log/m' in terms of silver.

In the present invention, an organic silver salt relatively stable to light can be used in combination with the photosensitive silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic silver salt must be in contact or at a close distance. When heated to a temperature of 80° C. or higher, preferably 100° C. or higher, the organometallic oxidizing agent is thought to participate in redox using the latent image of silver halide as a catalyst.

Examples of organic compounds that can be used to form such an organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. can be mentioned.

Silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, lylunic acid, and oleic acid. Typical examples include silver salts derived from adipic acid, sebacic acid, succinic acid, acetic acid, acetic acid, or camphoric acid.

Silver salts derived from fatty acid carboxylic acids having halogen atoms or hydroxyl groups or thioether groups of these fatty acids can also be used.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 3°5-dihydroxybenzoic acid, 0-lm- or P-methylbenzoic acid, 2,
4-dichlorobenzoic acid, acetamidobenzoic acid, p-phenylbenzoic acid, gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl-4-methyl-4-thiazoline- A typical example is a silver salt derived from 2-thione or the like.

As a silver salt of a compound having a mercapto or thiocarbonyl group, 3-mercapto-4-phenyl-1,2
, 4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-
Mercaptobenzthiazole, S-alkylthioglycolic acid (alkyl group having 12 to 22 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine, Mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1,2,4
-) Silver salts derived from mercapto compounds described in US Pat. No. 4,123,274, such as lyazole.

As a silver salt of a compound that accommodates imino groups,
30270 or 45-18416, or derivatives thereof, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, carboimides such as butylcarboimide benzotriazole Benzotriazoles, nitrobenazotriazoles described in JP-A No. 58-118839, sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole described in JP-A No. 58-118838, and hydroxybenzotriazole described in U.S. Patent No. 4. Typical examples include silver salts derived from 1,2,4-triazole, IH-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof described in No. 220.709.

Also, Research Disclosure Magazine 17029 (1
Organometallic salts other than silver salts such as silver salts and copper stearate described in June 1978), patent application No. 58-22153
Silver salts of carboxylic acids having an alkynyl group such as phenylpropiolic acid described in No. 5 can also be used in the present invention.

The above organic silver salts are 0 per mole of photosensitive silver halide.
．． 0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination.The total coating amount of the photosensitive silver halide and organic silver salt is suitably 1 mg to io g7 m'.

The emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-)dynyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthione, niazaindenes, such as doria Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a).

7) Tetraazaindenes), pentaazaindenes, etc.: Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can. For example, U.S. Patent No. 3.954.47
No. 4, No. 3,982,947, Special Publication No. 52-286
Those described in No. 60 etc. can be used.

The emulsions used in the light-sensitive materials of the present invention include, for example, polyalkylenoxides or their derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium compounds for the purpose of increasing sensitivity, increasing contrast, or accelerating development. May include chloride compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc., such as U.S. Pat. No. 2.400.5.
No. 32, No. 2,423,549, No. 2,716,
No. 062, No. 3.617,280, No. 3, 77
2,021, No. 3.808.003, and British Patent No. 1.488,991 can be used.

In the silver halide emulsion preparation method of the present invention, gelatin is preferably used as the protective colloid, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

In addition to lime-processed gelatin, acid-processed gelatin and Preten of the Society of Scientific Photography of Japan (B
ull, Soc, Sci, Phot.

Japan), number (No.) 16.30 pages (19
Enzyme-treated gelatin as described in 66) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The silver halide used in the present invention may be spectrally sensitized with dyes. The dyes used include methine dyes, cyanine dyes, merocyanine dyes, complex dianine dyes, complex merocyanine dyes, holopolar cyanine dyes, and hemicyanine dyes. Dyes include styryl dyes and hekioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus,
Pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring fused to these nuclei Nuclei, ie, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of one-strong color sensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
The emulsion may contain a substance exhibiting supersensitization, for example, an aminostyryl compound substituted with a nitrogen-containing heterocyclic group (
For example, U.S. Patent No. 2.933.390, U.S. Pat.
35,721), aromatic organic acid formaldehyde condensates (e.g., those described in U.S. Pat. No. 3,743,51),
No. 0), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 3,615,613.
No. 3゜615.641, No. 3,617,295
The combination described in No. 3,635,721 is particularly useful.

In order to incorporate these sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion, or they may be added to a welding solvent such as water, methanol, ethanol, acetone, methyl cellosolve, etc. alone or in combination. or after dissolving them in a substantially water-immiscible solvent such as phenoxyethanol,
The sensitizing dye may be dispersed in water or parent wood colloid, and this dispersion may be added to the emulsion.Furthermore, the sensitizing dye may be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. In addition, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately,
Alternatively, a mixture may be dissolved.

When added to an emulsion, they may be added simultaneously as a mixture, separately, or simultaneously with other additives.

The timing of addition to the emulsion may be during or before or after chemical ripening, and U.S. Pat.
It may be carried out before or after nucleation of silver halide grains according to No. 225,666.

The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

As a reducing agent that can be used in the present invention, Japanese Patent Publication No. 47-207
Compounds described in No. 41, No. 45-11149, No. 49-10697, No. 57-138632, and No. 58-169143, such as resorcinols, aminophenols, phenylenediamines, 5-pyrazolones,
Alkylphenols, alkoxyphenols, naphthols, aminonaphthols, naphthalene diols, alkoxynaphthols, hydrazines, etc. can be used.

Specific examples of these include resorcin, 2-methylresorcin, orcin, phloroglucin, phloroglucin monomethyl ether, phloroglucin dimethyl ether, m
-amitaf2nol, m-dimethylaminophenol,
m-diethylaminophenol, N,N-dimethyl-m
-phenylenediamine, N,N-diethyl-m-phenylenediamine, 3-methyl-5-pyrazolone, 3.4-
Dimethyl-5-pyrazolone, 1,3-dimethyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone, P-ethylphenol, P-dodecylphenol, P
-methoxyphenol, P-benzyloxyphenol, P-hydroxydiphenyl ether, 4-methyl-1
-Naphthol, 2-methyl-1-naphthol, 1-methyl-2-naphthol, 6-amino-1-naphthol, 8
-Amino-2-naphthol, 1,3-dihydroxynaphthalene, 4-methoxy-1-naphthol, 0-tolylhydrazine hydrochloride, P-tolylhydrazine hydrochloride, acetohydrazide, benzhydrazide, toluenesulfonylhydrazine, N, N' -Diacetylhydrazine, β-acylphenylhydrazines 1 such as β-acetylphenylhydrazine, β-acetyl-P-)lylhydrazine, β
-Acetyl-P-methoxyphenylhydrazine, β-7
Cetyl-P-aminophenylhydrazine, β-formyl-P-aminophenylhydrazine, β-formyl-2,
4-dimethylphenylhydrazine, β-benzoyl-2
, 4-dimethoxyphenylhydrazine, β-butyroyl-P-)lylhydrazine, β-piparoyl-P-acetylaminophenylhydrazine, β-propionyl-P-
Examples include dimethylaminophenylhydrazine, β-ethoxycarbonyl-P-aminophenylhydrazine, β-dimethylcarbamoyl-P-benzenesulfonamidophenylhydrazine, and β-morpholinocarbonyl-P-aminophenylhydrazine. Two or more types of these reducing agents can be used in combination if necessary. Also,
It is also possible to use the above-mentioned reducing agent together with a conventional photographic developer such as hydroquinone, catechol, P-substituted aminophenols, P-phenylenediamines, 3-pyrazolidones, and the like. The amount of reducing agent added can vary widely, but generally 0.1
-1500 mol%, preferably 10-300 mol%. Examples of the polymerizable compound that can be used in the present invention include addition-polymerizable monomers, oligomers and polymers thereof. As addition polymerizable monomers, compounds having one or more carbon-carbon unsaturated bonds can be used. Examples of these are acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, itaconic esters, and styrenes. , vinyl ethers, vinyl esters, N-vinyl heterocycles, aryl ethers, aryl esters, and derivatives thereof.

All of these compounds are useful in the present invention, but since a heat development process is performed in the present invention, compounds that are difficult to volatilize during heating and have a boiling point of 80°C or higher are preferred, and the S/N ratio of the resulting color image is In order to increase , a so-called polyfunctional monomer. Preferred examples of the polymerizable compound used in the present invention are shown below.

Acrylic acid, methacrylic acid, butyl acrylate, methoxyethyl acrylate, butyl methacrylate, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-acryloylmorpholine, N
-Acryloylpiperidine, glycidyl acrylate.

2-ethylhexyl acrylate, acrylic anilide, methacrylic anilide, styrene, vinyltoluene,
Chlorostyrene, methoxystyrene, chloromethylstyrene, l-vinyl-2-methylimidazole, 1-vinyl-2-undecylimidazole, 1-vinyl-2-undecylimidacillin, N-vinylpyrrolidone, N-vinylcarbazole , vinyl benzyl ether, vinyl phenyl ether, methylene-bis-acrylamide, trimethylene-bis-acrylamide, hexamethylene-bis-acrylamide, N,N'-diacryloylpiperazine, m-phenylene-bis-acrylamide, P-
Phenylene-bis-acrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, bis(4-acryloxypolyethoxyphenyl)propane, 1,5-bentanediol diacrylate, neopentyl glycol diacrylate acrylate, 1,6-hexanediol acrylate,
Polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, N-methylol acrylamide, diacetone acrylamide, triethylene glycol dimethacrylate, pentaerythritol tetraaryl ether.

Polymer compounds having a vinyl group or vinylidene group, for example, a polymer compound having a hydroxyl group, amine group, epoxy group, halogen atom, or sulfonyloxy group in the side chain, and acrylic acid, methacrylic acid, or a derivative thereof. Condensates and the like can also be used in the present invention.

Furthermore, compounds in which a vinyl group or vinylidene group is bonded to the core of the above-mentioned reducing agent, such as m-N, N-di(acryloyloxyethyl)aminophenol, P-acryloyloxyethoxyphenol, etc., can also be used as polymerizable compounds. In this case, the reducing agent and the polymerizable compound can be used together. Furthermore, a compound containing a vinyl group in the molecule of a color image-forming substance, such as a dye or a leuco dye, can also be used as a polymerizable compound, and in this case can serve both as a polymerizable compound and a color image-forming substance.

The polymerizable compound of the present invention is 0.0% relative to the silver halide salt.
It can be used in an amount of 5 to 1200% by weight, preferably 5 to 950% by weight.

There are a variety of color image-forming materials that can be used in the present invention. For example, dyes and pigments are examples of substances that are themselves colored. When these are used, a color image can be formed by destroying the portions (microcapsules) in which no polymer is formed and transferring them to an image-receiving material using an appropriate method. In addition to commercially available dyes and pigments, there are also known dyes and pigments described in various documents (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, published in 1972; "Latest Pigment Handbook" edited by Japan Pigment Technology Association, published in 1978). things are available. These dyes or pigments are
It is used after being dissolved or dispersed.

On the other hand, uncolored color image-forming substances include those that are colorless or pale in themselves but develop color when subjected to some kind of energy such as heating, pressure, or light irradiation; It is classified as one that develops color when it comes into contact with another component. Examples of the former include thermochromic compounds, piezochromic compounds,
Photochromic compounds and leuco compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes are known. All of these develop color upon heating, pressurization, light irradiation, or air oxidation. Examples of the latter include various systems that develop color through acid-base reactions, redox reactions, coupling reactions, chelate-forming reactions, etc. between two or more components. For example, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran used in pressure-sensitive paper, and an acidic substance (M1 coloring agent) such as acid clay or phenols; aromatic diazonium salts, diazotates, System using azo coupling reaction of diazosulfonates, naphthols, anilines, active methylenes, etc.; Reaction of hexamethylenetetramine with ferric ion and gallic acid Yaphenolphthalein-combrexons and alkaline earth Chelate-forming reactions such as reactions with similar 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.

Furthermore, as another example of a system in which color is developed by a reaction between two components, a case where this reaction proceeds by heating is known. In this case, it is necessary to heat the mixture at the same time or immediately after the two components are mixed by breaking the microcapsules during pressurization.

The color former in the color former/II color agent system is (
These include 1) triarylmethane compounds, (2) diphenylmethane compounds, (3) xanthine compounds, (4) thiazine compounds, and (5) spiropyran compounds. Specific examples include JP-A-55-27253, etc. Examples include those listed in.

Among them, (1) triarylmethane-based and (3) xanthine-based color formers are preferred because they cause less fog and provide high color density. Specific examples include crystal violet lactone, 3-diethylamino-6-chloro-7- (β-ethoxyethylamino)fluoran, 3-diethylamine-8-methyl-7-anilinofluoran,
3-Triethylamino-6-methyl-7-7nilinofluorane, 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7-
There are 0-chloroanilinofluorane and the like, and these can be used alone or in combination.

As the color developer, phenolic compounds, organic acids or metal salts thereof, oxybenzoic acid esters, acid clay, etc. are used.

Examples of phenolic compounds include 4.4”-isopropylidene-diphenol (bisphenol A), p
-t@rt-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-methylene-bis(2,6-tert-butylphenol), p-phenylphenol, ■, 1-bis (4-hydroxyphenyl)cyclohexane, 1゜1-bis(4-
hydroxyphenyl)-2-ethylhexane, 2,2-
Bis(4-hydroxyphenyl)butane, 2.2'-methylenebis(4-tert-butylphenol), 2.
2'-methylenebis(α-phenyl-p-cresol)
Thiodiphenol, 4,4'-thiobis(6-tart
-butyl-m-cresol)sulfonyldiphenol, p-tert-butylphenol-formalin condensate, p-phenylphenol-formalin condensate, and the like.

Examples of organic acids or metal salts thereof include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, 0-toluic acid, p-toluic acid, salicylic acid, 3-tert-
Butylsalicylic acid, 3゜5-di-tert-butylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3.5-
(α-methylbenzyl)salicylic acid, 3-tert-
Octylsalicylic acid and its zinc, lead, aluminum, magnesium, nickel salts, and the like are useful. In particular, salicylic acid derivatives and their zinc salts or aluminum salts are excellent in terms of color developing ability, fastness of colored images, and storage stability of recording sheets.

Examples of oxybenzoic acid esters include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, and benzyl p-oxybenzoate.

Further, an oil-absorbing white pigment can also be used in combination to diffuse and fix the capsule contents.

These color developers can be added as a eutectic with a thermofusible substance with a low melting point, or a low melting point compound can be added to the surface of the color developer particles in order to melt at a desired temperature and cause a color reaction. It is preferable to add it in a fused state.

Specific examples of low melting point compounds include higher fatty acid amides,
Examples include, but are not limited to, waxes such as stearamide, erucamide, palmitic acid amide, ethylene bisstearamide, or higher fatty acid esters, phenyl benzoate derivatives, aromatic ether derivatives, or urea derivatives. It's not a thing.

Other color formers/developer systems include, for example, phenolphthalein, fluorescein, 2', 4'
, ',7'-tetrapromo 3.4,5.6-titrachlorofluorescein, tetrabromophenol blue, 4°5.6.7-titrabu'romophenolphthalein, eosin, alarin cresol red, 2 −
These include naphtholphenolphthalein.

Color developers include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidacillins, and triazoles. Examples include nitrogen-containing compounds such as morpholines, piperidines, amidines, formazines, and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine,
Stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidacillin, 2°4.5- 1 Lyfuryl-2-imidacyline 1.1゜2-diphenyl-4,4-dimethyl-2-imidacyline, 2-phenyl-? -Imidacillin.

1.2.3-) Riphenylguanidine, 1.2-ditolylguanidine, 1.2-dicyclohexylguanidine,
1.2-dicyclohexyl-3-phenylguanidine,
1,2,3-tricyclohexylguanidine, guanidine trichloroacetate, N,N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-amino-benzothiazole, 2-benzoylhydra There are dino-benzothiazoles.

The color image-forming substance of the present invention is used in an amount of 0.5 to 20 parts by weight, particularly preferably 2 to 7 parts by weight, based on 100 parts by weight of the polymerizable compound. The IR colorant is used in an amount of about 0.3 to 80 parts by weight per 1 part by weight of the color former.

Furthermore, storage stability can be improved by encapsulating a thermal polymerization inhibitor in microcapsules. The amount of the thermal polymerization inhibitor added is preferably 20.1 to 10 mol% relative to the polymerizable compound.

The microcapsules used in the present invention can be produced by methods known in the art. For example, U.S. Patent No. 2,800,
457, 2,800.458, U.S. Pat. No. 3,287,154, British Patent No. 990.
．． No. 443, Special Publication No. 38-19574, No. 42-44
No. 6, interfacial polymerization method as seen in No. 42-711,
U.S. Patent No. 3,418゜25ρ, U.S. Patent No. 3.660.3
04, methods using incyanate-polyol wall materials as seen in U.S. Pat. No. 3,796,669, U.S. Pat. No. 3,914,
511, a method using incyanate wall materials, as seen in U.S. Patent No. 4. Ool, No. 140, No. 4,087,
Urea found in No. 376 and No. 4,089,802
A method using a formaldehyde-based or urea-formaldehyde-resorcinol-based wall forming material.

Melamine as seen in U.S. Patent No. 4,025,455
Methods using wall-forming materials such as formaldehyde resins and hydroxypropyl cellulose; 1 nsitu method by polymerization of monomers as seen in Japanese Patent Publication No. 36-9163 and Japanese Patent Publication No. 51-9079; British Patent Nos. 952,807 and 965; Polymerization dispersion cooling method found in No. 074.

U.S. Patent No. 3,111,407, British Patent No. 930.
There is a spray drying method as seen in No. 422.

Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

The microcapsule walls of the present invention can be made using a microencapsulation method that involves polymerization of glue actant from inside the oil droplet, which is particularly effective.In other words, it has a uniform particle size within a short period of time, and can be stored fresh. Capsules suitable for use as a photosensitive material with excellent properties can be obtained.

For example, when polyurethane is used as a capsule wall material, a polyvalent incyanate and a second substance (e.g., polyol, polyamine) that reacts with it to form the capsule wall are mixed in an oily liquid for encapsulation and emulsified and dispersed in water. Next, by increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming a microcapsule wall.
At this time, a co-solvent with a low boiling point and strong dissolving power can be used in the oily liquid.

In this case, regarding the polyvalent isocyanate to be used and the polyol and polyamine to be reacted with it, US Pat. -40347
No. 49-24159, JP-A-48-80191, and JP-A-48-84086, and these can also be used.

Examples of the polyvalent incyanate include m-phenylene diisocyanate, p-phenylene diisocyanate,
2.6-) lylene diisocyanate, 2.4-) lylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate), 3.3'-dimethoxy-4,4'-biphenylene diisocyanate), 3,3'-dimethyldifecolmethane-4,4'-diisocyanate, xylylene-1,4-
Diincyanate.

4.4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diincyanate, butylene-1,2-diincyanate, cyclohexylene-
1,2-diisocyanate, cyclohexylene-1,4
- diisocyanates such as diisocyanates, 4°4',
Triisocyanates such as 4″-triphenylmethane triisocyanate, toluene-2,4,6-) diisocyanate, 4,4′-dimethyldiphenylmethane-2
, 2', 5°5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylene diisocyanate and trimethylolpropane, xylylene diisocyanate and trimethylolpropane. There are incyanate prepolymers such as adducts of tolylene diisocyanate and hexanetriol.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers.

The following polyols described in Japanese Patent Application No. 158469/1982 can also be used.

ethylene glycol, 1,3-propanediol, 1,
4-butanediol, 1,5-bentanediol, 1.
6-hexanediol, 1,7-hebutanediol, 1
, 8-octanediol, propylene glycol, 2.
3-dihydroxybutane, l, 2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl-1
, 3-propanediol, 2,4-pentanediol,
2,5-hexanediol, 3-methyl-1,5-bentanediol, 1,4-cyclohexane dimetatool,
dihydroxycyclohexane, diethylene glycol,
1,2.6-)lihydroxyhexane.

2-Fyonylpropylene glycol, 1,1゜■-trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin 1゜4-di(2-hydroxyethoxy)benzene ,
Condensation products of aromatic polyhydric alcohols such as resorcinol dihydroxyethyl ether and alkylene oxides, p-xylylene glycol, m-xylylene glycol, α,α'-dihydroxy-p-diisopropylbenzene, 4,4'-dihydroxy -diphenylmethane, 2
-(p,p'-dihydroxyphenylmethyl)benzyl alcohol, an adduct of ethylene oxide to bisphenol A, an adduct of propylene oxide to hisphenol A, and the like. The polyol is preferably used in a proportion of hydroxyl groups of 0.02 to 2 moles per mole of incyanate groups.

Polyamines include ethylenediamine, trimethylenediamine, and tetramethylenediamine.

pentamethylene diamine, hexamethylene diamine, p
-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine.

Examples include tetraethylpentamine and amine adducts of epoxy compounds.

Polyvalent isocyanates can also react with water to form polymeric materials.

When making microcapsules, water-soluble polymers can be used, and the water-soluble polymers may be water-soluble anionic polymers, nonionic polymers, or amphoteric polymers. Both natural and synthetic compounds can be used, for example -Coo-.

Examples include those having -5o3- groups and the like.

Specific anionic natural polymers include gum arabic and alginic acid, while semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, and lignin sulfonic acid.

Synthetic products include maleic anhydride (including hydrolyzed) copolymers, acrylic (including methacrylic) polymers and copolymers, vinylbenzenesulfonic acid polymers and copolymers, Examples include carboxy-modified polyvinyl alcohol. As a nonionic polymer,
polyvinyl alcohol, hydroxyethylcellulose,
Examples include methylcellulose.

Examples of amphoteric compounds include gelatin.

These water-soluble polymers are used as a 0.01 to 10 wt% aqueous solution.

At least a polymerizable compound and a color image-forming substance are encapsulated in such microcapsules. In this case, silver halogenide, a reducing agent, etc. are usually also encapsulated in the capsule, but in any case, the substance to be encapsulated is either a polymerizable compound or a polymerizable compound with an organic solvent added. The mixture is dispersed or dissolved to form an oil phase, which is emulsified and dispersed into an aqueous phase in which the polymer is dissolved, and at the same time or subsequently, a capsule wall is formed by a well-known method to obtain capsules. ing.

The size of the capsule used in the present invention is 80 l or less,
In particular, 20 u or less is preferable from the viewpoint of storage stability and handling.Also, if the capsule is too small, there is a risk that it will disappear into the pores or fibers of the substrate, but this depends on the properties of the substrate or support, so it cannot be generalized. No, but 0.17
L or more is preferable.

The capsule used in the present invention does not substantially change under pressure of about 10 kg/m or less, and preferably breaks when a large pressure is applied. The magnitude of the pressure at which this breakage occurs depends on the application. Although it can be changed and is not limited to a specific value, it is approximately 500Kg/ca? These pressure characteristics can be controlled by controlling the particle size of the capsule, the thickness of the capsule wall, and the type of wall material used.

The photosensitive material of the present invention contains microcapsules or microcapsules containing hydroxy compounds, albic acid ester compounds, aromatic methoxy compounds, and organic sulfonamide compounds described in Japanese Patent Application No. 60-25838 in order to change thermal reactivity. Can be used outside of These compounds appear to alter the glass transition temperature of the microcapsule wall.

Various image formation accelerators can be used in the present invention. The image forming accelerator has functions such as promoting the redox reaction between the silver salt oxidizing agent and the reducing agent, and promoting the transfer of the image forming substance from the photosensitive material layer to the image receiving layer. They are also classified as base precursors, oils, thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound may have multiple functions. many.

Examples of preferred bases include, as inorganic bases, alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates; ammonium Hydroxides include hydroxides of quaternary alkylammonium; hydroxides of other metals, etc. Examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines).

aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[p-(dialkylamino)phenylcomethanes), heterocyclic amines , amidines,
Examples include cyclic amidines, guanidines, and cyclic guanidines, and those with pK& of 8 or more are particularly preferred. Base precursors include salts of organic acids and bases that are decarboxylated by heating, intramolecular nucleophilic substitution reactions, and Rossen rearrangement. , compounds that release amines through reactions such as Beckmann rearrangement, compounds that release bases through some kind of reaction upon heating, and compounds that generate bases through electrolysis or the like are preferably used. A preferred base precursor of the former type that generates a base upon heating is British Patent No. 9.
Salts of trichloroacetic acid described in No. 98.949, etc., salts of α-sulfonylacetic acid described in U.S. Pat. , 088, 496 No. 2
- Carboxycarboxamide derivatives, salts with thermally decomposable acids using alkali metals and alkaline earth metals in addition to organic bases as the base component (JP-A-59-195237), JP-A-59- using Rossen rearrangement Hydroxamic carbamates described in Japanese Patent Application No. 168440 and fludoxime carbamates described in Japanese Patent Application No. 31614/1983 which produce nitriles upon heating, and the like. Others include British Patent Nos. 998 and 945, and U.S. Patent No. 3,220,846.
No., Japanese Patent Application Publication No. 50-22625, British Patent No. 2,079
．． The base precursors described in No. 480 and the like are also useful.

The following compounds can be mentioned as compounds that generate bases by electrolysis.

For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation.

Through this reaction, carbonates of alkali metals and organic bases such as guanidines and amidines can be obtained extremely efficiently.

In addition, methods using electrolytic reduction include the production of amines by the reduction of nitro and nitroso compounds; the production of amines by the reduction of nitriles; the production of p-aminophenols and p-aminophenols by the reduction of nitro compounds, azo compounds, azoxy compounds, etc. - Generation of phenylenediamines and hydrazines, etc. p-aminophenols,
P-phenylenediamines and hydrazines can be used not only as bases, but also directly as color image forming substances. Of course, it is also possible to generate an alkaline component by electrolyzing water in the coexistence of one of various inorganic salts.

As the oil, a high boiling point organic solvent used as a solvent when emulsifying and dispersing a hydrophobic compound can be used.

Thermal solvents are solid at normal temperatures and serve as solvents when melted near the development temperature, such as ureas, urethanes, amides, pyridines, sulfonamides, sulfones, sulfonamides, and esters. , ketones, and ethers that are solid at 40° C. or lower can be used.

Examples of the surfactant include pyridinium salts, ammonium salts, and phosphonium salts described in JP-A-59-74547, and polyalkylene oxides described in JP-A-59-57231.

Examples of compounds that interact with silver or silver ions include imides, nitrogen-containing heterocycles described in JP-A-59-177550, thiols, thioureas, and thioethers as described in JP-A-59-111636. can be mentioned.

The image formation accelerator may be incorporated into either the light-sensitive material or the image-receiving material, or may be incorporated into both.The image-forming accelerator may also be incorporated into the emulsion layer, intermediate layer, protective layer, image-receiving layer, or any layer adjacent thereto. The same applies to a form in which a photosensitive layer and an image-receiving layer are on the same support, which may also be incorporated in a calendar.

The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained by using several types in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acid when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include oxime esters described in Japanese Patent Application No. 58-216928 and Japanese Patent Application No. 59-48305;
Examples include compounds that release acids through Rossen rearrangement as described in Japanese Patent Application No. 59-85834, and examples of electrophilic compounds that undergo a substitution reaction with bases upon heating include those described in Japanese Patent Application No. 59-858.
Examples include compounds described in No. 5838.

The image-receiving element of the present invention is an element for immobilizing color image-forming substances emitted from a photosensitive element.

Image-receiving by coating on the same support as the photosensitive element or coating on a different support from the photosensitive material containing the photosensitive element,
Make up the material.

Furthermore, the image receiving element of the present invention can have at least one layer containing a mordant, if necessary. If the image-receiving element is located on the surface, it can be provided with a protective layer. Further, if necessary, it may be composed of two or more layers using mordants having different mordant powers.

When using a mordant in the image-receiving layer, any mordant can be selected from among the mordants used in diffusion transfer type light-sensitive materials, but among them, polymer mordants are particularly preferred.
Here, the polymer mordant includes a polymer containing a tertiary amine group, a polymer having a nitrogen-containing heterocyclic moiety, and a polyamide containing these quaternary cation groups.

Polymers containing one unit of a vinyl monomer having a tertiary amine group are described in Japanese Patent Application No. 11i 1982-169012, Japanese Patent Application No. 166135/1980, etc., and polymers containing one vinyl monomer unit having a tertiary imidazole group are described in Specific examples include Japanese Patent Application Nos. 58-226497 and 58.
-232071, U.S. Patent No. 4,282,305,
It is described in the same No. 4,115,124, the same No. 3,148.061, etc.

Preferred specific examples of polymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent No. 2,0
No. 56,101, No. 2.093,041, No. 1,
No. 594.961, U.S. Patent No. 4,124,386;
No. 4,115,124, No. 4,273,853, No. 4,450,224, JP-A-48-28225
It is stated in the number etc.

Other preferred specific examples of polymers containing one vinyl nitrate unit having a quaternary ammonium salt include U.S. Pat. No. 3,709,690, U.S. Pat. Patent application 1986-16613
No. 5, No. 58-169012, No. 58-232070
No. 58-232072 and No. 59-91620
It is written in the number etc.

In the present invention, a solvent can be used in conjunction with the encapsulation of the polymerizable compound and color image forming substance. A solvent can also be used when introducing a reducing agent, color developer, etc. into necessary elements. For example, a solution dissolved in water or a hydrophilic organic solvent can be coated directly on the support together with a binder if necessary;
, 322,027, etc., into the necessary elements by known methods. By using a solvent in the microcapsules, it is also possible to control the degree of destruction of the capsules upon pressurization and the amount of transfer of the color image-forming substance within the capsules to the image receiving element. The amount of the solvent used in the capsule is preferably 1 to 500 parts by weight per 100 parts by weight of the polymerizable compound.

Natural oils or synthetic oils can be used alone or in combination as the solvent used in the present invention. Examples of these solvents include, for example, cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, and 1-phenyl-1-xylylethane, 1 - Diarylethanes such as phenyl-1-P-ethyl phenylethane, 1,1'-ditolylethane, etc., phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, trichloride), etc. diyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl aze) trimesates (e.g. tributyl trimesate), lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate,
Secondary butyl alcohol, methyl isobutyl ketone, β-
Examples include ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone.

The binders used in the photosensitive material and image-receiving material of the present invention may be contained alone or in combination. This binder can be mainly hydrophilic. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Other synthetic polymeric materials include synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers, particularly in the form of latexes, dispersed vinyl compounds that increase the dimensional stability of photographic materials.

The supports used in the light-sensitive material and image-receiving material in the present invention are those that can withstand processing temperatures.
Common supports include glass, paper, wood-free paper, synthetic paper, metals and their analogs, as well as acetylcellulose film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, and polyethylene terephthalate film. Includes films and their associated film or resin materials. Paper supports laminated with polymers such as polyethylene can also be used, U.S. Pat.
The polyester film described in No. 25.070 is preferably used.

The photosensitive material of the present invention may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a peeling layer, and a matting agent layer, if necessary. In particular, it is desirable that the protective layer contain an organic or inorganic matting agent for the purpose of preventing adhesion.

In addition, light-sensitive materials and image-receiving materials may contain antifoggants, fluorescent whitening agents, antifading agents, antihalation and irradiation dyes, pigments (including white pigments such as titanium oxide), and water release agents as necessary. , a thermal polymerization inhibitor, a surfactant, a vinyl compound dispersed in a thermal solvent, and the like.

Various exposure means can be used in the present invention. ? ! The image is obtained by imagewise exposure to radiation, including visible light. In general, commonly used light sources such as sunlight, strobes, flashes, tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser beams, and CRT light sources, plasma light sources,
Fluorescent tubes, light emitting diodes, etc. can be used as the light source. It is also possible to use an exposure means that combines a micro-shutter array using an LCD (liquid crystal), PLZT (lanthanum-doped lead titanium zirconate), etc., and a linear light source or a planar light source.

The type of light source and the amount of exposure can be selected depending on the wavelength to which silver halide is sensitive by dye sensitization and the sensitivity.

The original image used in the present invention may be a black and white image or a color image.

The original image may be a line image such as a technical drawing, or a photographic image with gradation, and it is also possible to use a camera to take a portrait or landscape image. The printing from the original image may be carried out by contact printing over the original image, or by printing in the form of a print, or by enlarging the image.

It is also possible to output images taken by a video camera or the like or image information sent from a television station directly to a CRT or FOT, and then form this image on a photosensitive material using a contact lens or a lens and print it. .

Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various devices. It is difficult to make an LED that effectively emits blue light. In this case, to reproduce a color image, three types of LEDs are used that emit green, red, and infrared light, and the emulsion portions that are sensitive to these lights contain yellow, magenta, and cyan image-forming substances, respectively. It should be designed like this.

That is, the green-sensitive area may contain a yellow image-forming substance, the red-sensitive area may contain a magenta image-forming substance, and the infrared-sensitive area may contain a cyan image-forming substance. Other combinations may be used as required. It is possible.

In addition to the above-mentioned method of directly attaching or projecting the original image, so-called image processing involves reading the original image illuminated by a light source using a light-receiving element such as a phototube or COD, storing it in the memory of a computer, etc., and processing this information as necessary. There is also a method of reproducing this image information on a CRT and using it as an image-like light source, or directly causing the three types of LEDs to emit light based on the processed information for exposure.

These exposure amounts vary depending on the type of silver halide used and the degree of sensitization.

■Specific effects of the invention According to the invention, the photosensitive layer contains at least a photosensitive silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, and at least the polymerizable compound and the color image-forming substance are encapsulated in the same microcapsule,
After image exposure, the heating element layer is heated with electricity to polymerize the polymerizable compound to form a high-molecular compound and immobilize the color image-forming substance. A photosensitive material can be obtained that has high sensitivity (to light and red light), excellent stability over time, and allows image formation with simple operations.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

Examples First, we will describe how to make a support with a heating element. Carbon black with a particle size of 20 mp and a DBP oil absorption of 150 24 gb) Gelatin
35gC) Kako Atlas Demol N
2.6gd) Nirasan Nonion N52QB, 5
L, 4 ge) Aerosol 0↑
5gf) Water 960c
c The above a) to f) were mixed and dispersed in a colloid mill to prepare a carbon black dispersion.

This dispersion was applied onto paper laminated with polyethylene to a wet film thickness of 70 cc and dried.

Next, how to make a photosensitive sheet and an image-receiving sheet will be described.

[Preparation of photosensitive silver halide emulsion]

(Emulsion I) The following solutions were prepared.

(Solution mA) Isopropyl alcohol loomM was added to 13 g of benzotriazole and 3 g of polyvinyl butyral and dissolved.

(Solution B) Add water to 17g of nitric acid fi and dissolve it to 50ml
And so.

(Solution C) 2.38 g of potassium bromide and 17 g of potassium iodide O were dissolved in water to make a 50 m solution.

Solution A was placed in a reaction vessel, and solution B was added thereto over 5 minutes at 40° C. with sufficient stirring.

Five minutes after this addition was completed, solution C was added over a period of five minutes. After the addition was completed, stirring was continued for 5 minutes, and then the liquid was filtered, and 200 mM of a 20% isopropyl solution of polyvinyl butyral was added to the solution, and emulsion I was prepared by dispersing the mixture in a homogenizer for 20 minutes. The yield of this emulsion was 250 g.

(Emulsion■) The following solutions were prepared.

(Solution A) 200 mM of isopropyl alcohol was added to 3 g of polyvinyl butyral and dissolved therein.

(Solution B) Water was added to 17 g of silver nitrate to dissolve it to make a 20 m solution.

(Solution C) Water was added to dissolve 11.9 g of potassium bromide and 0.83 g of potassium iodide to make a 50 m solution.

Solution A was placed in a reaction container, and solution B and solution C were simultaneously added to solution A over 10 minutes at 40° C. while stirring well. After 5 minutes have passed after the completion of this addition, this liquid is filtered,
Next, 200 ml of a 20% isopropyl alcohol solution of polyvinyl butyral was added to this, and the mixture was dispersed for 20 minutes using a homogenizer to obtain an emulsion (2). The yield of this emulsion was 250 g.

(Emulsion■) The following solutions were prepared.

(Solution A) 12 g of gelatin, 5.6 g of sodium chloride and 0.6 g of potassium bromide were dissolved in 1000 mfL of water.

(Solution B) 100 g of silver nitrate was dissolved in water to make 300 mM.

(Solution C) 40g of sodium chloride and 2g of potassium bromide
0g was dissolved in water to make 300ml.

Solution A was placed in a reaction vessel, and while maintaining the temperature at 50°C, solutions B and C were simultaneously added into solution A over a period of 90 minutes.

After removing excess salt from the produced silver chlorobromide emulsion by a well-known method, 70 g of water was added to adjust the pH to 6.0, and gold sensitization and sulfur sensitization were performed to yield 400 g of silver chlorobromide. Emulsion (m) was obtained.

[Preparation of microcapsules and production of photosensitive sheet]

0.7 g of N-phenylglycine (component C) was added to a seven-mer IR compound of 28 g of trimethylolpropane triacrylate and 7 g of methyl methacrylate, and dissolved using an ultrasonic disperser.

- 6 g of force-fielded methylene, 0.7 g of 4,4'-bis(diethylamino)benzophenone (component a) and 2,2'
-bis(0-chlorophenyl)-4,4',5.5'-
2.1 g of tetraphenylbiimidazole (component b) and 3-diethylamino-6-chloro-7 as a color former
2.1 g of -7 nylinofluorane was dissolved and added to the previous solution to form a 7-mer mixture.

Separately, for comparison, 3.5 g of benzoisobutyl ether was used in place of components a, b, and c and dissolved in a seven-mer mixture. Furthermore, in place of the above-mentioned components a, b, and c, the above-mentioned emulsions (I) to (m) are used, and each emulsion and β-
7 Cetyl-p-aminophenylhydrazine 0.03ft
! A mixture of - was prepared. In this case, emulsion CI
), 18 g of (TI)te and 5 g of emulsion (m) were used.

On the other hand, a mixture of 17.5 g of a 10% aqueous gum arabic solution, 18.8 g of a 12% inbutylene/anhydrous maleic acid aqueous solution, and 26.8 g of distilled water was added.

The pH was adjusted to 3.5 with sulfuric acid, and 4.6 g of urea and 0.6 g of resorcin were added, and the 7-mer mixture was emulsified and dispersed in this solution to make 3 JL. Next, 12.9 g of 36% formalin was added, and the temperature was raised to 60° C. with stirring. After 1 hour, 9.0 g of 5% ammonium sulfate aqueous solution was added, and the mixture was further stirred for 1 hour while being kept at 60° C., and then cooled. Thereafter, the pH was adjusted to 9.0 with NaOH.

1.53 g of a 15% polyvinyl alcohol aqueous solution, 3.47 g of distilled water, and 0.57 g of starch were added to 5 g of the capsule liquid thus obtained to prepare a coating liquid. Add this to a wet film thickness of 20.
Coating it on the support having the heating element so that
The photosensitive sheets 1 to 5 were obtained by drying at 50° C. for 15 minutes.

[Preparation of image receiving sheet] 0.6 g of 48% SBR latex in 21.8 g of water,
10% etherified starch aqueous solution 4g, zinc carbonate 2.1
g, 1.3 g of 50% aqueous sodium silicate solution, 0.1 g of sodium hexametaphosphate, and 13 g of Jilton F-242 clay were added, and the mixture was stirred with a homogenizer for 15 minutes.

This was applied to art paper to a wet film thickness of 351 L and dried to obtain an image receiving sheet.

Image reproduction was performed as follows.

350-5 obtained by passing a line drawing original onto the above-mentioned photosensitive sheet and passing it through a bandpass filter from an ultra-high pressure mercury lamp.
Light with a wavelength of 00 nm was irradiated.

On each of photosensitive sheets 1 to 5 after exposure A DC voltage of 240v was applied for 30 seconds.

These photosensitive sheets and image-receiving sheets were placed one on top of the other so that their coated surfaces faced each other, and passed through a pressure roller with a linear pressure of 100 kg/cm. The capsules in the unexposed areas were destroyed and transferred to the image receiving sheet. The transferred part has a density of 1. O
It gave a clear black image. The density of the part corresponding to the exposed area changes depending on the exposure amount, but the sensitivity (equivalent to foot sensitivity) is determined by the minimum exposure amount that achieves a 5 density of 0.1 or less.In other words, the lower the exposure energy, the higher the sensitivity. The results are shown in Table 1.

Table 1 Photosensitive sheet No. Ingredients used
Exposure energy (erg/m') 1 (ratio ID 4.4'-bis(diethylamino)
Benzophenone 2,2'-bis(0-chlorophenyl)-4,4',5
．． 5'-tetraphenylbi 10000 imidazole N-phenylglycine 2-benzoin butyl ether
800003 (present invention) Emulsion (I) β-7 cetyl-P-aminophenylhydra 1
00 Gin 4 (invention) Emulsion (n) β-acetyl-p-7 minophenyl hydra 1
00 Gin 5 (present invention) Emulsion (■) β-acetyl-p-aminophenylhydra
As can be seen from the results in Table 1, the photosensitive sheet of the present invention) (1) compared to the case where no silver halide emulsion was used (No.
No. 3, 4.5) shows a significant increase in sensitivity.
Furthermore, it was found that the structure of the present invention is effective because no image was observed in the photosensitive sheet of the present invention (No. 3.4.5) unless a voltage was applied, that is, without electrical heating.

From the above, the effects of the present invention are clear.

Authorized letter of procedure (spontaneous) Commissioner of the Japan Patent Office Black 1) Mr. Yu Akira September 18, 1986 2. Name of the invention Photosensitive material 3. Relationship to the case of the person making the amendment Patent applicant address Minamiashigara City, Kanagawa Prefecture 210 Nakanuma Name (520) Fuji Photo Film Co., Ltd. 4, Agent
Person 101 Telephone 864-4498 Address
3-2-2-6 Iwamoto-cho, Chiyoda-ku, Tokyo Contents of amendment (1) "Hexoxo" on page 38, line 15 of the specification is amended to "hemioxo".

(2) "Penzoxado" on page 39, line 8 is corrected to "benzoxazo."

(3) On page 48, lines 16 to 18, "The polymerizable compound is 0.05 to 1200% by weight based on the silver halide salt,
Preferably, it can be used in an amount of 5 to 950% by weight.

'' is corrected to ``5 to 1.2 x 105 parts by weight, preferably 12 to 1.2 x 104 parts by weight of the polymerizable compound can be used per 1 part by weight of the silver halide salt.''

(4) r42-71J on page 57, line 13 of r42-
Corrected to 771J.

(5) r36-9163J on page 58, line 8 of r36
Corrected to -9168J.

(6) "Albamic acid" on page 66, line 15 is corrected to "carbamic acid."

(7) On page 70, line 15, after “Available.”
Further, the amount of these bases or base precursors is preferably 50% by weight or less, more preferably 0.01 to 40% by weight, based on the total solid content of the photosensitive layer. ” is inserted.

(8) On page 71, line 5, after “I can.” “Also,
The amount of the thermal solvent is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, based on the total solid content of the photosensitive layer. ” is inserted.

Claims (1)

[Claims] It has a photosensitive layer and a heat generating layer on a support, and the photosensitive layer and the heat generating layer may be formed on the same side or opposite sides of the support, and the photosensitive layer has at least It contains a photosensitive silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, and at least the polymerizable compound and the color image-forming substance are encapsulated in the same microcapsule, and after image exposure, electricity is supplied to the heating layer. 1. A photosensitive material characterized in that it is configured to polymerize a polymerizable compound to produce a high molecular compound by heating and immobilize a color image forming substance.