JPH0651504A - Photosensitive material and image forming method using same - Google Patents

Abstract

PURPOSE:To provide a monosheet type photosensitive material having excellent graininess and high contrast. CONSTITUTION:When a photosensitive layer contg. silver halide, a reducing agent, a polymerizable compd. and two kinds of substances causing a color development reaction in a contact state is formed on a substrate to obtain a photosensitive material, one of the substances causing a color development reaction is incorporated into the polymerizable compd. and this compd. is allowed to exist in the form of drops of oil. The other is housed in microcapsules.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material for image formation having a highly sensitive photosensitive layer containing silver halide on a support and an image forming method using the same.

[0002]

2. Description of the Related Art A light-sensitive material having a light-sensitive layer containing a silver halide, a reducing agent, and a polymerizable compound on a support causes a latent image to be formed on the silver halide, and the polymerizable compound is polymerized correspondingly. The image forming method can be used. An example of this image forming method is Japanese Patent Publication No. 45-111149.
No. 47-20741, No. 49-10697, JP-A No. 57-138632, Japanese Patent Publication No. 1-47776,
1-47777, JP-A-57-21146, 58-107529, JP-B-3-73849, 3
No. 73850. These methods form an image-like polymer compound by polymerizing a coexisting polymerizable compound (eg, vinyl compound) when developing exposed silver halide using a developing solution. . 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, Japanese Patent Publication No. 3-12307
The publication describes a method capable of forming a polymer compound by dry treatment. In the above method, a latent image is formed by exposing a light-sensitive material having a photosensitive layer comprising a silver halide, a reducing agent, a polymerizable compound and a binder on a support to form a latent image, and then heating the latent image. A polymer compound is formed in the exposed portion.

Further, a method of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed is disclosed in JP-A-61 / 1986.
-183641, 61-260241, 62-
70836, 62-81635, JP-A 2-14
No. 1756, No. 2-141757, No. 2-20725
No. 4 and No. 2-262662. As described in JP-B-3-12308, these light-sensitive materials can easily form a color image by further containing a color image-forming substance. That is, a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance on a support is subjected to a heat development treatment simultaneously with or after the imagewise exposure to obtain a polymerizable material. The compound is polymerized and cured, thereby immobilizing the color image-forming substance in the cured portion, and then, by pressing the photosensitive material in a state of being superposed on the image-receiving material, the color image-forming substance in the uncured portion is transferred to the image-receiving material. Thus, a clear color image can be obtained on the image receiving material. The above method uses an image receiving material, but a monosheet type photosensitive material has also been proposed. Among them, JP-A-62-209444 and 63-
In the methods described in JP-A-261348 and JP-A-64-31146, two types of substances that cause a color reaction in a contact state are used, one of which is housed in a microcapsule together with a polymerizable compound and isolated from the other. . This photosensitive material is imagewise cured by exposure and heat development (the microcapsules are cured), and then the uncured microcapsules are ruptured by pressure, and only the uncured portions are colored to obtain an image.

[0004]

In the conventional mono-sheet type light-sensitive material, the microcapsules are generally ruptured by pressurization, so that the capsule size is several μm or more. In this case, the obtained image tends to be rough. Further, in the case of bursting by heating, a smaller size capsule can be used, but in this case, the minimum density is high and the contrast tends to be low. An object of the present invention is to provide a monosheet type photosensitive material having excellent graininess and high contrast, and an image forming method using the same.

[0005]

The object of the present invention is to provide a support with a photosensitive layer containing at least a silver halide, a reducing agent, a polymerizable compound, and two kinds of substances which cause a color reaction in a contact state. In the light-sensitive material, the polymerizable compound exists in the form of an oil droplet while containing one substance that causes the color forming reaction, and the other substance that causes the color forming reaction is in a microcapsule different from the oil droplet. This has been achieved by using a light-sensitive material characterized by being contained. Further, it was possible to achieve the object by obtaining a color image by exposing the light-sensitive material imagewise and heating at a temperature of 10 ° C. or more higher than the heat temperature after heat development.

The size of oil droplets and microcapsules used here is preferably 1 μm or less. Further, heating is preferably used to cause a color reaction. At this time, in the uncured portion, one of the substances contained in the polymerizable compound which causes a color-developing reaction penetrates into the microcapsules and contacts the other substance which causes a color-developing reaction to develop a color. Since the movement is controlled in the curing portion, no color is developed, the graininess is excellent, and an image with a low minimum density can be obtained. Examples of the reaction that develops color in the contact state include an acid-base reaction between two or more components,
There are redox reaction, coupling reaction, chelate forming reaction and the like. Among them, a system consisting of a coloring agent having a partial structure such as lactone, lactam, and spiropyran, which is used for pressure-sensitive paper, and an acidic substance (developing agent) such as acid clay and phenols, and an aromatic diazonium salt or diazotate. A system utilizing an azo coupling reaction between a diazo compound such as diazo sulfonates and a coupler such as naphthols, anilines and active methylenes is preferable. Specific examples of these are, for example, 29-58 of "Introduction to Special Paper Chemistry" by Hiroyuki Moriga (published in 1975).
And the compounds described on pages 87 to 95 can be used. When a color former and a developer are used, the color former is contained in the oil droplets of the polymerizable compound, and the developer is contained in the microcapsules, and the developer is contained in the oil droplets of the polymerizable compound. Any of the modes in which the color former is contained in microcapsules is possible. When utilizing the azo coupling reaction, it is preferable that the coupler is contained in the oil droplets of the polymerizable compound and the diazo compound is contained in the microcapsules.

The silver halide, reducing agent, polymerizable compound, microcapsule, support, and other components used in the light-sensitive material of the present invention will be described below. The light-sensitive material of the present invention contains, as silver halide, silver chloride, silver bromide,
Any grain of silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra, dodecahedrons and tetradecahedrons, grains having an irregular crystal system such as spheres and plates. It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.01 micron or less or large grains having a projected area diameter of up to about 10 microns, and a polydisperse emulsion is also available in US Pat. No. 3,574,628. Monodisperse emulsions described in, for example, 3,655,394 and British Patent 1,413,748 may be used.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
Engineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Further, two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No1.
7643 (Dec. 1978), pp. 22-23, "I.
"Emulsion preparation and types", and No. 18716 (November 1979), page 648, etc. The silver halide emulsion is usually prepared by physical ripening or chemical ripening. The ones that have been aged and spectrally sensitized are used, and the additives used in such a process are Research Disclosure No. 176.
43 and No. 18716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Additive type RD17643 RD18716 Chemical sensitizer, page 23, page 648, right column, sensitivity enhancer, same as above, spectral sensitizer, page 23-24, page 648, right column-supersensitizer, page 649, right column, antifoggant 24- See page 25, page 649, right column and stabilizers. For details of the above silver halide emulsion and photographic additives, refer to "Public Technology No. 5" (Aztec Co., Ltd.,
(Published March 22, 1991) 2 to 17 pages. The amount of silver halide used is 0.001 to 10 g, preferably 0.05 to ² g, in terms of silver per 1 m ² of the light-sensitive material. Further, in the present invention, an organic silver salt can be used together with silver halide. The organic silver salt is described on pages 17 to 18 of "Public Technology No. 5" mentioned above.

The reducing agent which can be used in the light-sensitive material of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. Examples of the reducing agent having the above function include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones and 5-amino. Uracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o-
Or p-sulfonamidophenols, o- or p
-Sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-
Sulfonamide indanones, 4-sulfonamido-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. The various reducing agents described above are described in detail on pages 18 to 35 of the above-mentioned "Known Technology No. 5". The addition amount of the reducing agent can be widely varied, but it is generally 0.1 to 1500 mol%, preferably 10 to 300 mol% with respect to the silver salt.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable. The compound having an ethylenically unsaturated group that can be used in the light-sensitive material, acrylic acid and its salts, acrylic acid esters,
Acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-
Examples include vinyl heterocycles, allyl ethers, allyl esters and their derivatives.

Specific examples of preferable polymerizable compounds that can be used in the light-sensitive material include acrylic acid esters, such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxyethyl. Acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylenated bisphenol A diacrylate,
2- (2-hydroxy-1,1-dimethylethyl) -5
-Hydroxymethyl-5-ethyl-1,3-dioxane acrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5,5-dihydroxymethyl-1,3-dioxane triacrylate, propylene of trimethylolpropane Examples thereof include triacrylate of an oxide adduct, hexaacrylate of a caprolactone adduct of dipentaerythritol, polyacrylate of hydroxypolyether, polyester acrylate and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Examples thereof include pentaerythritol tetramethacrylate and dioxymethacrylate of polyoxyalkylenated bisphenol A.

The above polymerizable compounds may be used alone or in combination of two or more kinds. Regarding a light-sensitive material in which two or more kinds of polymerizable compounds are used in combination, see JP-A-62-210445.
It is described in the official gazette. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the reducing agent described above can also be used as the polymerizable compound.

The silver halide and the reducing agent may be dispersed and dissolved in a polymerizable compound before use.

In the light-sensitive material of the present invention, a base precursor can be used as an image formation accelerator. As a base precursor that can be used in the light-sensitive material of the present invention, inorganic base and organic base base precursors (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used. Details of these base precursors and the techniques for using them are described in "Public Technology No. 5," pages 55-86.

Preferred base precursors are JP-A-59-180549, 59-180537, 59-195237, 61-32844 and 61.
-36743, 61-51140, 61-52.
No. 638, No. 61-52639, No. 61-53631.
No. 61-53634, No. 61-53635, No. 61-53636, No. 61-53637, No. 61-
53638, 61-53639, 61-536.
40, 61-55644, 61-55645.
No. 61, No. 61-55646, No. 61-84640, No. 61-107240, No. 61-2119950, No. 6
1-251840, 61-252544, 61
-313431, 63-316740, 64-
68746 and 64-54452, salts of organic acids and bases which are decarboxylated by heating, and JP-A-59-157637 and 59-16694.
Examples thereof include compounds capable of eliminating a base by heating as described in JP-A Nos. 3 and 63-96159.

Regarding the encapsulation method which can be used for the microcapsules of the present invention, the above-mentioned "Known technology No. 5" 88-
The method described on page 98 can be used. Among these, the wall is preferably made of polyurea resin, polyurethane resin, or melamine-formaldehyde resin. In particular, when what is accommodated in the microcapsules is a color former or diazo compound, polyurea or polyurethane capsules are preferable, and when those accommodated in the microcapsules are color developers, melamine-formaldehyde capsules are preferable. The color former, the color developer, or the diazo compound is preferably encapsulated in a state of being dissolved in the high boiling point organic compound. As the high boiling point organic compound,
In addition to the polymerizable compounds mentioned above, a high-boiling point organic solvent used as a dispersion solvent for a color material (a coupler, a dye-donor compound, etc.) of a general color light-sensitive material can also be used. For example, an alkyl phthalate (eg, dibutyl phthalate,
Dioctyl phthalate etc.), phosphoric acid ester (eg diphenyl phosphate, triphenyl phosphate etc.), citric acid ester (eg tributyl acetyl citrate), benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyl lauryl amide) ), Aliphatic esters (for example, dibutoxyethyl succinate, etc.), trimesic acid esters (for example, tributyl trimesic acid), carboxylic acids described in JP-A-63-85633, JP-A-59-83154, 59-59. 1
78451-178455, 59-178457.
And the like.

The oil droplets and microcapsules of the present invention are
It is preferable that the oily liquid is produced by emulsifying and dispersing it in an aqueous medium. In this case, it is preferable that the aqueous medium contains a water-soluble polymer. The water-soluble polymer is preferably a nonionic or anionic polymer. Examples of nonionic polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxypropyl cellulose and methyl cellulose. . Examples of anionic polymers include polystyrene sulfinic acid, styrene sulfinate copolymer, polystyrene sulfonate, styrene sulfonic acid copolymer,
Polyvinyl sulfate ester salt, polyvinyl sulfonate,
Maleic anhydride / styrene copolymer, maleic anhydride /
Examples thereof include an isobutylene copolymer. In this case, the concentration of the water-soluble polymer in the aqueous medium is 0.01 to
The range of 10% by weight is preferable, and 0.1 is more preferable.
Is in the range of up to 5% by weight. If necessary, the aqueous medium may further contain a surfactant. As examples thereof, the compounds described on pages 136 to 138 of the above-mentioned "Known Technology No. 5" can be used.

Materials for the support used in the light-sensitive material of the present invention include glass, paper, high-quality paper, baryta paper, coated paper,
Cast coated paper, synthetic paper, metal and its analogs, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, polyimide and other films, and resin materials and polyethylene and other polymers for lamination It is possible to cite the paper etc. However, when a transparent image is obtained using the light-sensitive material of the present invention, it is necessary to use a transparent material such as a polymer film.

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

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

Examples of the photopolymerization initiator include benzophenones, acetophenones, benzoins, thioxanthones and the like. Details thereof are described in "UV Curing System" (1989, Comprehensive Technical Center), pages 63 to 147, and the like. Various surfactants may be used in the light-sensitive material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-17.
No. 3463, No. 62-183457 and the like.

Various antifoggants or photographic stabilizers can be used in the present invention. For example,
Azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-168442.
Carboxylic acids and phosphoric acids containing nitrogen described in JP-A No. 59-111636, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957.

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-253159, pages (31) to (32), JP-A-1-724
No. 79, No. 1-3471, etc. are described.

In the light-sensitive material of the present invention, a protective layer may be provided on the light-sensitive layer. It is desirable that the protective layer has a large oxygen barrier effect. For example, a layer of a water-soluble polymer such as polyvinyl alcohol is preferable. An image forming method for forming an image using the light-sensitive material of the present invention will be described below. The light-sensitive material of the present invention is first exposed imagewise. The type of light source used for this exposure and the amount of exposure can be selected according to the photosensitive wavelength of silver halide (sensitized wavelength in the case of dye sensitization) and sensitivity.

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

The light-sensitive material of the present invention is imagewise exposed and then heated for thermal development. As this heating means, there is JP-A-61
As in the light-sensitive material described in Japanese Patent Publication No.-294434, a heating element layer may be provided on the surface of the support on which the light-sensitive layer of the light-sensitive material is not coated for heating. Further, JP-A-61-1472
As described in JP-A No. 44-44, a hot plate, an iron, and a heat roller are used, or as described in JP-A-62-144166, a method of heating a photosensitive material by sandwiching it between a heat roller and a belt is used. Good.

That is, the photosensitive material may be brought into contact with a heating element having a surface area larger than the area of the photosensitive material to heat the entire surface at the same time, or a heating element having a smaller surface area (heating plate,
The entire surface may be heated over time by bringing it into contact with a heat roller, a heat drum, etc. and scanning it.
In addition to the heating method in which the heating element and the photosensitive material are brought into direct contact with each other as described above, electromagnetic waves, infrared rays, hot air, etc. can be applied to the photosensitive material to heat them in a non-contact state. Further, the heat development by heating is carried out simultaneously with or after the imagewise exposure, but it is preferable to perform the heating after 0.1 seconds or more has passed after the imagewise exposure. The heating temperature is generally from 60 ° C to 250
C., preferably 80.degree. C. to 180.degree. C., the heating time is between 0.1 and 20 seconds, preferably between 0.5 and 5 seconds.

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

The light-sensitive material of the present invention is further heated in order to obtain a color image after the polymerizable compound is polymerized imagewise. At this time, pressure may be used together. The heating means is the same as the method used for the above thermal development. As a pressurizing method,
A conventionally known method can be used. A heated pressure roller may be used for heating and pressurizing while transporting.
The heating temperature for color development is preferably 10 ° C. or more higher than the temperature of heat development when pressure is not used in combination with roller conveyance (about 10 kg / cm ² or less). The light-sensitive material of the present invention has many uses such as a computer graphic hard copy sensitive material and a medical hard copy sensitive material.

[0033]

【Example】

Example 1 Preparation of Silver Halide Emulsion (EB-1) 24 g of lime-treated inert gelatin was added to 900 cc of distilled water and dissolved at 40 ° C. for 1 hour, and then KBrl. 5 g was added, and 1N sulfuric acid was added thereto to adjust the pH to 3.2. After 10 mg of (AGS-1) was added to this solution, the solution I and the solution II were allowed to precede the solution II by 10 seconds at 75 ° C.
The same flow rate was added over 0 minutes. Then liquid III and IV
The solution was added in the same manner for 30 minutes, and the solutions V and VI were added in the same manner for 30 minutes. During the addition of these liquids
The pAg was 8.1. After the addition is complete, adjust the pH to 1N NaOH
Adjusted to 5.3 with (AZ-1) 1.5 mg and (AZ
-4) 1.8 mg was added and the mixture was aged at 75 ° C for 60 minutes. After aging (SB-1), 160 mg was added and aging was carried out for 20 minutes, then the temperature was lowered to 35 ° C., and VII solution was added at an equal flow rate over 5 minutes after addition for 5 minutes. After that, the temperature is 60 ℃
To 160 mg (SB-3), 16 (SB-6)
0 mg was added and the mixture was aged for 20 minutes. To this emulsion (CK-1)
1.1 g was added and allowed to settle, washed with water so as to have a target electric conductivity, desalted, and then added with 6 g of lime-treated gelatin to dissolve, and 0.8 cc of a 3.5% aqueous solution of (ATR-3) and (ATR-1) 72% solution 1.5 cc and KBr
Was added to adjust the pH to 6.2 and pAg 8.7. Average particle size 0.60 μm, coefficient of variation 12%, conductivity 3.5 mS
550 g of a cm- ¹ monodisperse silver iodobromide emulsion (EB-1) was prepared.

Liquid I AgNO ₃ 17 g Distilled water 180 cc Liquid II KBr 12.5 g Distilled water 180 cc III Liquid AgNO ₃ 34 g Distilled water 180 cc IV Liquid KBr 24.4 g Distilled water 180 cc V liquid AgNO ₃ 69 g Distilled water 360 cc VI liquid KBr 49. 4g distilled water 360cc VII liquid KI 4.1g distilled water 650cc (CK-1) polyisobutylene-co-maleate monosodium

[0035]

[Chemical 1]

[0036]

[Chemical 2]

Preparation of Solid Dispersion (KB-1) 70 g of a 3% aqueous solution of PVA205 (polyvinyl alcohol) and serogen 6A were placed in a Dynomill dispersion container.
A mixture of 70 g of a 3% aqueous solution of (carboxymethyl cellulose), 60 g of a base precursor (BG-1) and 200 ml of glass beads having a diameter of 0.5 to 0.75 mm are added,
Disperse at 3000 rpm for 30 minutes, adjust the pH to 6.5 with 2N sulfuric acid, and use a base precursor (B
A solid dispersion (KB-1) of G-1) was obtained. Preparation of Solid Dispersion (KB-1) 180 g of a 3% aqueous solution of PVA205, 20 g of a reducing agent (RD-1), and 200 ml of glass beads were added to a dispersion container of Dynomill, and dispersed at 3000 rpm for 30 minutes to carry out reduction. A solid dispersion (KB-2) of the agent (RD-1) was obtained.

[0038]

[Chemical 3]

Preparation of Emulsion (EM-1) 51 g of the polymerizable compound (MN-1) was added to ethyl acetate 13.6.
g, and 6.8 g of a black coloring leuco dye (LB-1) were added and mixed and dissolved. PV in a 200 ml homogenizer container
A mixture of 119 g of a 3% aqueous solution of A217 and 6.8 g of a 5% aqueous solution of sodium dodecylbenzenesulfonate was added, the above (MN-1) solution was added, and the mixture was emulsified and dispersed at 8000 rpm for 10 minutes to obtain an emulsion (EM -1) was obtained.

[0040]

[Chemical 4]

Microcapsules containing color developer (CB-1)
Preparation of 3,5-di-α-methylbenzyl zinc salicylate 15 g
Was dissolved in 85 g of diisopropyl naphthalene. A 4.5% aqueous solution of sodium polystyrene sulfonate was added to this solution 1
In addition to 00 g, it was emulsified with a homogenizer. On the other hand, water 2
Melamine 4.4g and formalin 7.2g were added to 3.6g, and it heated at 60 degreeC for 30 minutes, and obtained the transparent melamine formalin prepolymer. 22 g of the above emulsion (148 g) was added, the above melamine / formalin prepolymer was added, and the mixture was adjusted to pH 6.0 with 1N sulfuric acid and then heated at 65 ° C. for 90 minutes to give a color developer-containing microcapsule (CB-1). Got

Preparation of photosensitive material 101 (EM-1) 10.5 g (KB-1) 1.0 g, (K
B-2) 1.3 g, (CB-1) 20 g, (EB-1)
0.4 g, 0.5 of 2-mercaptobenzimidazole
% 1-methoxy-2-propanol solution (0.1 g) was added, and the mixture was stirred at 40 ° C. for 15 minutes. Further, 2 g of water was added, and a polyethylene terephthalate film undercoated with gelatin was coated and dried at a coating amount of 100 cc / m ² . A 10% aqueous solution of PVA205 was applied onto this, coating amount of 20 cc / m ²
To obtain a photosensitive material 101.

Image formation The light-sensitive material 101 was exposed for 1 second at 200 lux through a wedge having a continuously changing transmission density of 0 to 4.0 using a halogen lamp adjusted to a color temperature of 3100 ° K. Then, apply 15 to the opposite side of the coated surface of the photosensitive material.
It was brought into close contact with a drum heated to 0 ° C. and developed by heating for 1 second. After that, when it was passed through a roller having a surface temperature of 70 ° C. and a pressure of 200 kg / cm ² at a speed of 2 cm / sec, a black and white positive image with good contrast was obtained. This image could also be observed in transmission.

Example 2 Preparation of Emulsion (EM-2) 50 g of the polymerizable compound (MN-1) was mixed with 10 g of eral acetate,
15 g of 3,5-di-α-methylbenzyl salicylic acid was added and mixed and dissolved. A 200 ml homogenizer container was charged with a mixture of 120 g of a 4% aqueous solution of PVA217 and 6 g of a 5% aqueous solution of sodium dodecylbenzenesulfonate, the above (MN-1) solution was added, and the mixture was emulsified and dispersed at 8000 rpm for 10 minutes to obtain an emulsion. (EM-2) was obtained.

Leuco dye-containing microcapsules (CB-
Preparation of 2) Leuco dye (LB-1) 18.
2 g and (LB-2) 1.8 g were dissolved. Takenate D110N (Takeda, polyvalent isocyanate)
15g was added and mixed. 60 g of a 6% aqueous solution of PVA217 was placed in a 100 cc homogenizer container, the above leuco dye solution was added, and the mixture was stirred at 8000 rpm for 3 minutes.
An emulsion was obtained. The emulsion was replaced in a 300 cc container, 70 g of a 0.92% aqueous solution of tetraethylenepentamine was added, and the mixture was heated and stirred at 32.5 ° C. for 30 minutes and at 40 ° C. for 3 hours. Water equivalent to the amount evaporated during this heating was added to the leuco dye-containing microcapsules (CB
-2) was obtained.

[0046]

[Chemical 5]

Preparation of photosensitive material 102 (EM-2) 20 g, (KB-1) 4 g, (KB-2)
1.2 g, (CB-2) 10 g, (EB-1) 0.5
g, 0.5% of 2-mercaptobenzimidazole 1-
Add 0.1 g of methoxy-2-propanol solution to 40
Stir for 15 minutes at ° C. Further, ² cc of water was added, and a polyethylene terephthalate film undercoated with gelatin was coated and dried at a coating amount of 100 cc / m ² . A 10% aqueous solution of PVA205 was applied onto this so that the coating amount was 20 cc / m ^2, and dried to obtain a light-sensitive material 102.

Image formation The light-sensitive material 102 was exposed for 1 second at 200 lux through a wedge having a continuously changing transmission density of 0 to 4.0 using a halogen lamp adjusted to a color temperature of 3100 ° K. Then, the light-sensitive material was heated at 140 ° C. for 5 seconds and then passed through a heat roller having a surface temperature of 170 ° C. at a speed of 2 cm / second, whereby a black and white positive image was obtained. This image could also be observed in transmission.

Example 3 Preparation of Emulsion (EK-3) A mixture of 30 g of the polymerizable compound (MN-1) and 20 g of dipentaerythritol hexaacrylate was added to 1 g of ethyl acetate.
0 g, 2-hydroxy-3-naphthoic acid anilide 15 g
Was added and mixed and dissolved. A 200 ml homogenizer container was charged with a mixture of 120 g of a 4% aqueous solution of PVA217 and 6 g of a 5% aqueous solution of sodium dodecylbenzene sulfonate, and the above (MN-1) solution was added to the homogenizer at 8000 rpm.
The mixture was stirred for 0 minutes to obtain an emulsion (EM-3). Preparation of diazo-containing microcapsules (CB-3) 3.45 g of diazo compound (LB-3) and Takenate D
110N18 was added to and dissolved in a mixed solvent of 24 g of tricresyl phosphate and 5 g of ethyl acetate. This solution is PVA2
It was added to 60 g of an 8% aqueous solution of 17 and emulsified and dispersed by a homogenizer to obtain an emulsion having an average particle diameter of 2.5 μ. 100 g of water was added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, diazo-containing microcapsules (CB-
3) was obtained.

[0050]

[Chemical 6]

Preparation of Photosensitive Material 103 (EM-3) 25 g was added with 5% of guanidine trichloroacetic acid.
Aqueous solution 6 g, (KB-2) 1.2 g, (CB-3) 10
g, (EB-1) 0.5 g, and 2-mercaptobenzimidazole 0.5% 1-methoxy-2-propanol solution 0.1 g were added, and the mixture was stirred at 40 ° C. for 15 minutes. This solution was coated on a polyethylene terephthalate film undercoated with gelatin so that the coating amount was 100 cc / m ^2, and dried. A 10% aqueous solution of PVA205 was applied on this to give 20
The photosensitive material 103 was obtained by coating and drying so as to obtain cc / m ² .

Image formation The light-sensitive material 103 was exposed to 200 lux for 1 second as in Example 1. Then, the photosensitive material was heated at 120 ° C. for 5 seconds and then passed through a heat roller having a surface temperature of 150 ° C., whereby a blue positive image was obtained. This image could also be observed in transmission.

Example 4 Preparation of Silver Halide Emulsion (EB-2) Agitated aqueous gelatin solution (1 ml gelatin in 1500 ml water).
An aqueous solution containing 6 g and 0.5 g of sodium chloride, which was adjusted to pH 3.8 with 1N sulfuric acid and kept at 60 ° C.), and 71 g of potassium bromide in 300 ml.
And an aqueous silver nitrate solution (containing 0.59 mol of silver nitrate dissolved in 300 ml of water) were simultaneously added at an equal flow rate for 50 minutes. Ten minutes after this was completed, 100 ml of an aqueous solution containing 2.9 g of potassium iodide and an aqueous solution of silver nitrate (0.018 mol of silver nitrate dissolved in 100 ml of water) were simultaneously added over 5 minutes. Thus, a monodisperse tetradecahedral silver iodobromide emulsion having an average grain size of 0.22μ was prepared. The above emulsion was washed with water and desalted, and then 94 ml of a 0.5% methanol solution of the infrared sensitizing dye described below and 75 ml of a 2% aqueous solution of the compound (a) shown below were added to the emulsion.
And a yield of 600 g of silver halide emulsion (EB-
2) was obtained.

[0054]

[Chemical 7]

Preparation of Photosensitive Material 104 A photosensitive material 104 was obtained in the same manner as in the preparation of the photosensitive material 101 except that 1 g of (EB-2) was used instead of 0.4 g of (EB-1). Image formation The light-sensitive material 104 was imagewise exposed using a semiconductor laser having a peak wavelength of 810 nm. After that, when the same processing as in Example 1 was performed, a monochrome image was obtained. This image could also be observed in transmission.

Claims (2)

[Claims] 1. A support having at least silver halide,
In a light-sensitive material provided with a photosensitive layer containing a reducing agent, a polymerizable compound, and two kinds of substances that cause a color reaction in a contact state, the polymerizable compound exists in the form of oil droplets while containing one of the substances that cause the above color reaction. In addition, the light-sensitive material is characterized in that the other substance that causes the color-forming reaction is contained in a microcapsule different from the oil droplet. 2. An image forming method for obtaining a color image by exposing the light-sensitive material of claim 1 imagewise and heat-developing, and then heating at a temperature of 10 ° C. or higher than the heat-developing temperature.