JP2524528B2 - Photosensitive material manufacturing method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing a light-sensitive material in which a light-sensitive layer containing a light-sensitive silver halide, a reducing agent, a base precursor and a polymerizable compound is provided on a support. .

BACKGROUND OF THE INVENTION A light-sensitive material having a support and a light-sensitive layer containing a light-sensitive silver halide, a reducing agent and a polymerizable compound is used in an image forming method in which a polymerizable compound is polymerized imagewise. There is. For these photosensitive materials, see Japanese Examined Patent Publication No. 45-11149.
JP-A-61-69062 and the like.

Regarding the arrangement of the components in the photosensitive layer, the above-mentioned photosensitive material,
There are various modes. In a typical embodiment, photosensitive microcapsules containing photosensitive silver halide, a reducing agent and a polymerizable compound are contained in the photosensitive layer. The photosensitive microcapsules are disclosed in JP-A Nos. 62-169147 and 62-16.
9148, 62-209439 and 63-121837, etc.

In each of the above publications, a base or a base precursor is described as an optional component added to the light-sensitive material. A base or a base precursor is an important component that acts as an image formation accelerator in image forming processing (developing processing of a light-sensitive material).

However, it is difficult to store a base or a base precursor in a microcapsule, and practically it has hardly been carried out. In conventional light-sensitive materials, a base or base precursor is contained in the light-sensitive layer outside the microcapsules. Then, a method of permeating a base or a base precursor into the inside of the microcapsule in the development processing of the light-sensitive material has been mainly adopted.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a photosensitive material containing a base precursor.

It is also an object of the present invention to provide a method for producing a light-sensitive material having a high developing speed and high sensitivity.

The present invention comprises (1) a photosensitive silver halide,
In a method for producing a photosensitive material provided with a photosensitive layer containing a reducing agent, a base precursor and a polymerizable compound, in an oil medium containing the polymerizable compound 0.1 to 100% by weight,
It is intended to provide a method for producing a light-sensitive material, which comprises a step of emulsifying an aqueous dispersion of a base precursor.

The method for producing a light-sensitive material of the present invention preferably has the following modes.

(2) A step of emulsifying an aqueous dispersion of a base precursor and a photosensitive silver halide emulsion in an oil medium containing 0.1 to 100% by weight of a polymerizable compound; a step of emulsifying the obtained oil emulsion in an aqueous medium. And the resulting aqueous emulsion is applied to a support, and the reducing agent is the above-mentioned oily medium, an aqueous dispersion of a base precursor, a photosensitive silver halide emulsion, an oily emulsion, an aqueous medium and an aqueous emulsion. Add to any of the things.

(3) The aqueous emulsion obtained in the step of emulsifying the oily emulsion of the aspect of (2) above in an aqueous medium is microencapsulated.

(4) Step of emulsifying an aqueous dispersion of a base precursor in an oily medium containing a polymerizable compound in an amount of 0.1 to 100% by weight; emulsifying the obtained oily emulsion in an aqueous medium containing a photosensitive silver halide emulsion Alternatively, the method comprises the steps of emulsifying the oily emulsion in an aqueous medium, or adding a photosensitive silver halide emulsion to the oily emulsion; and coating the obtained aqueous emulsion on a support. Then, the reducing agent is added to any of the above-mentioned oily medium, an aqueous dispersion of a base precursor, a photosensitive silver halide emulsion, an oily emulsion, an aqueous medium and an aqueous emulsion.

(5) The aqueous emulsion obtained in the step of emulsifying the oily emulsion of the aspect of (4) above in an aqueous medium is microencapsulated.

(6) Step of emulsifying an aqueous dispersion of a base precursor in an oil medium containing 0.1 to 100% by weight of a polymerizable compound; Step of emulsifying the obtained oily emulsion in an aqueous medium; And a photosensitive silver halide emulsion on the obtained coated material, and the reducing agent is the above-mentioned oily medium, an aqueous dispersion of a base precursor, and a photosensitive halogen. It is added to any of a silver halide emulsion, an oily emulsion, an aqueous medium and an aqueous emulsion.

(7) The aqueous emulsion obtained in the step of emulsifying the oily emulsion according to the aspect (6) in an aqueous medium is microencapsulated.

(8) A step of emulsifying an aqueous dispersion of a base precursor and a photosensitive silver halide emulsion in an oil medium containing 0.1 to 100% by weight of a polymerizable compound; and coating the obtained oil emulsion on a support. The reducing agent is added to any of the above-mentioned oily medium, an aqueous dispersion of a base precursor, a photosensitive silver halide emulsion and an oily emulsion.

(9) In the above aspect (8), the oil medium contains 0.1 to 90% by weight of an oil-soluble binder polymer.

(10) A step of emulsifying an aqueous dispersion of a base precursor in an oily medium containing 0.1 to 100% by weight of a polymerizable compound; a step of applying the obtained oily emulsion onto a support; and an obtained coated product. The process comprises coating a photosensitive silver halide emulsion on the above, and the reducing agent is added to any of the above-mentioned oily medium, an aqueous dispersion of a base precursor, a photosensitive silver halide emulsion and an oily emulsion.

(11) In the embodiment of (10) above, the oil medium contains 0.1 to 90% by weight of an oil-soluble binder polymer.

(12) Base precursor is a salt composed of carboxylic acid and organic base.

(13) The base precursor is a salt composed of a carboxylic acid and an organic base, and the organic base has a partial structure corresponding to an atomic group obtained by removing one or two hydrogen atoms from an amidine represented by the following formula (I). A diacid or tetraacid base consisting of 2 to 4 and at least one hydrocarbon residue or heterocyclic residue as a linking group of the partial structure: [In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic residue, Is a monovalent group selected from the group consisting of (each group may have one or more substituents), and any two groups selected from R ¹ , R ² , R ³ and R ⁴ are ,
They may combine with each other to form a 5- or 6-membered heterocycle consisting of nitrogen and carbon atoms].

(12) The base precursor is a salt composed of a carboxylic acid and an organic base, and the organic base has a partial structure corresponding to an atomic group obtained by removing one or two hydrogen atoms from guanidine represented by the following formula (IV). Diacid to tetraacid to 2 to 4 and at least one hydrocarbon residue or heterocyclic residue as a linking group of the partial structure (total carbon atoms are 6 times or less of the number of partial structures) Is: [In the above formula (IV), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocycle. A monovalent group selected from the group consisting of residues (each group may have one or more substituents), and is selected from R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ Any two groups may be joined together to form a 5- or 6-membered heterocycle consisting of nitrogen and carbon atoms].

(13) Add a color image forming substance to the light-sensitive material.

(14) Add a thermal polymerization initiator to the light-sensitive material.

(15) Add a photopolymerization initiator to the light-sensitive material.

(16) A hydrophilic polymer is dissolved in an aqueous dispersion of a base precursor.

(17) The concentration of the base precursor in the aqueous dispersion of the base precursor is 1 to 90% by weight.

(18) The average particle size of the droplets of the aqueous dispersion of the base precursor emulsified in the oil medium is 0.1 to 100 μm.

(19) The average particle size of the solid particles of the base precursor in the aqueous dispersion of the base precursor is 0.01 to 30 μm.
Is.

(20) The base precursor is contained in the range of 0.5 to 200% by weight based on the polymerizable compound.

[Effect of the Invention] In the method for producing a light-sensitive material of the present invention, a polymerizable compound is added in an amount of 0.1
It is characterized in that it comprises a step of emulsifying an aqueous dispersion of a base precursor in an oil medium containing 1 to 100% by weight.

According to the research conducted by the present inventor, when an aqueous dispersion of a base precursor is emulsified in an oil medium containing a polymerizable compound, the base precursor is contained in the oil medium in a fine and uniform state. Furthermore, the dispersion state of the base precursor in the oil medium (that is, the emulsified state of the aqueous dispersion) is extremely stable.

As described above, the base precursor contained in the oily medium in a fine and uniform state has a high decomposition rate (base generation rate) during development. Therefore, in the light-sensitive material manufactured according to the present invention, the base precursor rapidly promotes the development reaction. Therefore, the light-sensitive material produced according to the present invention has a high developing speed and high sensitivity.

DETAILED DESCRIPTION OF THE INVENTION The light-sensitive material produced according to the present invention is provided with a light-sensitive layer containing a light-sensitive silver halide, a reducing agent, a base precursor and a polymerizable compound on a support.

The above-mentioned photosensitive material has various modes regarding the arrangement of each component contained in the photosensitive layer. A step which is a feature of the method for producing a light-sensitive material of the present invention, that is, 0.1
The step of emulsifying the aqueous dispersion of the base precursor in an oily medium containing 1 to 100% by weight can be applied to any of the embodiments.

Hereinafter, the five main modes of the photosensitive material and the respective manufacturing methods will be described with reference to the drawings.

FIG. 1 is a schematic sectional view showing a first embodiment of a photosensitive material.

A photosensitive layer (11) is provided on the support (12). The photosensitive layer (11) contains a photosensitive silver halide (Δ), a reducing agent, a base precursor (·) and a polymerizable compound. An oily medium containing a photosensitive silver halide, a base precursor and a polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets. The reducing agent may be contained in the oil droplet of the oil medium or in the photosensitive layer outside the oil droplet.

The oil droplets of the oily medium are preferably in a microcapsule state by providing an outer shell.

When the first embodiment of the light-sensitive material shown in FIG. 1 is produced according to the present invention, the production method is as follows: an aqueous dispersion of a base precursor and photosensitivity in an oil medium containing 0.1 to 100% by weight of a polymerizable compound. Emulsifying the silver halide emulsion; emulsifying the obtained oil-based emulsion in an aqueous medium; and coating the obtained aqueous emulsion on a support.

The reducing agent is added to any of the oily medium, the aqueous dispersion of the base precursor, the photosensitive silver halide emulsion, the oily emulsion, the aqueous medium and the aqueous emulsion.

When the oil droplets of the oily medium are formed into microcapsules, the aqueous emulsion obtained in the step of emulsifying the oily emulsion in an aqueous medium is microencapsulated.

FIG. 2 is a schematic sectional view showing a second embodiment of the photosensitive material.

A photosensitive layer (21) is provided on the support (22). The photosensitive layer (21) contains a photosensitive silver halide (Δ), a reducing agent, a base precursor (·) and a polymerizable compound. An oily medium containing a base precursor and a polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets. The photosensitive silver halide is contained in the photosensitive layer outside the oil droplets. The reducing agent may be contained in the oil droplet of the oil medium or in the photosensitive layer outside the oil droplet.

The oil droplets of the oily medium are preferably in a microcapsule state by providing an outer shell.

When the second embodiment of the light-sensitive material shown in FIG. 2 is produced according to the present invention, the production method is as follows: an aqueous dispersion of a base precursor is emulsified in an oil medium containing 0.1 to 100% by weight of a polymerizable compound. Step; emulsifying the obtained oil-based emulsion in an aqueous medium containing a photosensitive silver halide emulsion, or emulsifying the oil-based emulsion in an aqueous medium, and then photosensitizing the resulting aqueous emulsion A step of adding a silver emulsion; and a step of coating the obtained aqueous emulsion on a support.

The reducing agent is added to any of the oily medium, the aqueous dispersion of the base precursor, the photosensitive silver halide emulsion, the oily emulsion, the aqueous medium and the aqueous emulsion.

When the oil droplets of the oily medium are formed into microcapsules, the aqueous emulsion obtained in the step of emulsifying the oily emulsion in an aqueous medium is microencapsulated.

FIG. 3 is a schematic sectional view showing a third embodiment of the photosensitive material.

The first photosensitive layer (31) and the second photosensitive layer (32) are provided on the support (33). The first photosensitive layer (31) contains a photosensitive silver halide (Δ). The second photosensitive layer contains a base precursor (.) And a polymerizable compound. The oily medium containing the base precursor and the polymerizable compound is dispersed in the second photosensitive layer in the form of oil droplets. The reducing agent may be contained in the oil droplet of the oil medium, in the second photosensitive layer outside the oil droplet, or in the first photosensitive layer.

The first photosensitive layer containing the photosensitive silver halide and the second photosensitive layer containing the base precursor and the polymerizable compound may be provided on the support in the reverse order. However, the order shown in FIG. 3 is preferable.

The oil droplets of the oily medium are preferably in a microcapsule state by providing an outer shell.

When the third embodiment of the light-sensitive material shown in FIG. 3 is produced according to the present invention, the production method is as follows: an aqueous dispersion of a base precursor is emulsified in an oil medium containing 0.1 to 100% by weight of a polymerizable compound. Step; Step of emulsifying the obtained oily emulsion in an aqueous medium; Step of applying the obtained aqueous emulsion on a support; and Application of a photosensitive silver halide emulsion on the obtained coating material Consists of steps.

The step of applying the aqueous emulsion on the support and the step of applying the photosensitive silver halide emulsion may be reversed.

It comprises a step of coating a photosensitive silver halide emulsion on the obtained coating material.

The reducing agent is added to any of the oily medium, the aqueous dispersion of the base precursor, the photosensitive silver halide emulsion, the oily emulsion, the aqueous medium and the aqueous emulsion.

When the oil droplets of the oily medium are formed into microcapsules, the aqueous emulsion obtained in the step of emulsifying the oily emulsion in an aqueous medium is microencapsulated.

FIG. 4 is a schematic sectional view showing a fourth embodiment of the light-sensitive material.

A photosensitive layer (41) is provided on the support (42). The photosensitive layer (41) is composed of an oily medium containing a photosensitive silver halide, a (Δ) reducing agent, a base precursor (.) And a polymerizable compound.

When the fourth embodiment of the light-sensitive material shown in FIG. 4 is produced according to the present invention, the production method is as follows: an aqueous dispersion of a base precursor and a photosensitizer in an oil medium containing 0.1 to 100% by weight of a polymerizable compound. Emulsifying the silver halide emulsion; and coating the obtained oily emulsion on a support.

The reducing agent is added to any of the above-mentioned oily medium, an aqueous dispersion of a base precursor, a photosensitive silver halide emulsion and an oily emulsion.

The oily medium preferably comprises 0.1 to 90% by weight of oil-soluble binder polymer.

FIG. 5 is a schematic sectional view showing a fifth aspect of the photosensitive material.

The first photosensitive layer (51) and the second photosensitive layer (52) are provided on the support (53). The first photosensitive layer (51) contains a photosensitive silver halide. The second photosensitive layer comprises an oily medium containing a base precursor and a polymerizable compound. The reducing agent is
It may be contained in the first photosensitive layer or in the second photosensitive layer.

The first photosensitive layer containing the photosensitive silver halide and the second photosensitive layer containing the base precursor and the polymerizable compound may be provided on the support in the reverse order. However, the order shown in FIG. 5 is preferable.

When the fifth embodiment of the light-sensitive material shown in FIG. 5 is produced according to the present invention, the production method is as follows: an aqueous dispersion of a base precursor is emulsified in an oil medium containing 0.1 to 100% by weight of a polymerizable compound. Step; coating the obtained oily emulsion on a support; and coating a photosensitive silver halide emulsion on the obtained coating.

The step of applying the oily emulsion on the support and the step of applying the photosensitive silver halide emulsion may be reversed.

The reducing agent is added to any of the above-mentioned oily medium, an aqueous dispersion of a base precursor, a photosensitive silver halide emulsion and an oily emulsion.

The oily medium preferably comprises 0.1 to 90% by weight of oil-soluble binder polymer.

The process of emulsifying an aqueous dispersion of a base precursor in an oil medium containing 0.1 to 100% by weight of a polymerizable compound, which is a feature of the method for producing a light-sensitive material of the present invention, will be described below.

As used herein, the oily medium means a hydrophobic liquid that is substantially immiscible with water. Since the polymerizable compound (details will be described later) is usually a liquid having the above definition, only the polymerizable compound can be used as the oily medium (that is, the oily medium contains 100% by weight of the polymerizable compound).

However, the oil medium can contain a hydrophobic component other than the polymerizable compound. The hydrophobic component added to the oil medium is preferably an oil-soluble binder polymer and / or an organic solvent.

Specific examples of the oil-soluble binder polymer used in the present invention include poly (meth) acrylate, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl acetate-ethylene copolymer, polyvinyl chloride, polyvinylidene chloride, and chloride. Vinyl-vinylidene chloride copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated polyethylene, chlorinated polypropylene, polycarbonate, diacetyl cellulose, cellulose acetate butyrate, triacetyl cellulose, ethyl cellulose, polyvinyl pyridine,
Polyvinyl imidazole etc. are mentioned.

Among these polymers, the polymers described in JP-A No. 64-17047, which have a crosslinkable ethylenic double bond in the side chain, are particularly preferable. To give a specific example,
Examples thereof include homopolymers or copolymers of monomers such as allyl (meth) acrylate, hydroxyethyl (meth) acrylate, and maleic anhydride.

The molecular weight of the polymer is not particularly limited, but is preferably in the range of about 10,000 to 500,000.

Dispersant copolymers, as described further below, are also included in the above polymers.

As the organic solvent, any solvent capable of simultaneously dissolving the polymerizable compound and the binder polymer can be selected and used. As a specific example, acetone,
Methyl ethyl ketone, methyl cellosolve, propylene glycol monomethyl ether, ethylene glycol, methanol, ethanol, isopropanol, dimethylformamide, toluene, xylene and the like can be mentioned.

In the fourth and fifth aspects of the light-sensitive material described above, that is, in the aspect in which the oil medium is directly applied to the support, the oil-soluble polymer acts as a binder,
It is preferable to use a relatively large amount. As a specific example, the oil medium in the fourth and fifth aspects preferably contains 1 to 90% by weight of an oil-soluble polymer.

The aqueous dispersion of the base precursor preferably contains the base precursor in the range of 1 to 90% by weight, more preferably 5 to 70% by weight.

The average particle size of the solid particles of the base precursor in the aqueous dispersion of the base precursor is preferably 0.01 to 30 μm, more preferably 0.05 to 5 μm.

The hydrophilic polymer may be dissolved in the aqueous dispersion of the base precursor. When preparing an aqueous dispersion of a base precursor, it is preferable to disperse solid fine particles of the base precursor in an aqueous solution of a hydrophilic polymer. Examples of hydrophilic polymers include gelatin, cellulose derivatives, starch, gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, polystyrene sulfinate and the like. The hydrophilic polymer is preferably used as an aqueous solution of 0.1 to 70% by weight.

In the method for producing a light-sensitive material of the present invention, the aqueous dispersion of the above base precursor is emulsified in an oil medium. In the emulsification, it is preferable that the aqueous dispersion of the base precursor has an average particle size of droplets of 0.1 to 100 μm,
It is more preferable to set the thickness to 10 μm.

In the method for producing a light-sensitive material of the present invention, the base precursor is preferably used in the range of 0.5 to 200% by weight, more preferably 3 to 30% by weight, based on the oil medium.

The component substances used in the method for producing the light-sensitive material of the present invention will be described in detail below.

Photosensitive silver halide: As the photosensitive silver halide, any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used. Can be used.

The halogen composition of the photosensitive silver halide grains may be uniform or non-uniform on the surface and inside. Photosensitive silver halide grains having various structures having different compositions on the surface and inside are described in JP-A-57-154232 and 58-1085.
No. 33, No. 59-48755, No. 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 100984.

There is also no particular limitation on the crystal habit of the photosensitive silver halide grains. Two or more kinds of photosensitive silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination. There is no particular limitation on the grain size distribution of the photosensitive silver halide grains.

The average grain size of the photosensitive silver halide grains is 0.001
˜5 μm, more preferably 0.01-2 μm.

The photosensitive silver halide emulsion may be prepared by any known method such as an acidic method, a neutral method or an ammonia method.

The reaction between the soluble silver salt and the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. An inverse mixing method in which grains are formed under silver ion excess conditions and a controlled double jet method in which pAg is kept constant can also be employed. Also, to accelerate particle growth,
The concentration, amount or rate of addition of the silver salt and the halogen salt to be added may be increased (see JP-A-55-158124 and US Pat. No. 3650757).

The light-sensitive silver halide emulsion 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 in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent image type emulsions suitable for this purpose are described in US Pat.
No. 3761276, and Japanese Patent Publication No. 58-3534
And Japanese Patent Laid-Open No. 58-136641. Preferred nucleating agents for combination with the above emulsions are described in US Pat.
No. 27552, No. 4245037, No. 4255511, No. 4266013
No. 4,276,364 and West German Published Patent (OLS) No. 26.
No. 35316 is described in each specification.

In the preparation of the photosensitive silver halide emulsion, it is preferable to use a hydrophilic colloid as the protective colloid. Examples of hydrophilic colloids are gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, proteins such as casein, hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose, cellulose sulfate ester, sodium alginate,
Such as sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. Mention may be made of synthetic hydrophilic polymeric substances. Among these,
Gelatin is preferred. As the gelatin, in addition to coal-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The photosensitive silver halide emulsion is prepared by forming ammonia and an organic thioether derivative as a silver halide solvent in the step of forming silver halide grains (see Japanese Patent Publication No. 47-386).
Further, sulfur-containing compounds (see JP-A-53-144319) and the like can be used. In addition, cadmium salt, zinc salt, lead salt, thallium salt and the like may coexist in the process of particle formation or physical thermal formation. Further, for the purpose of improving high illumination failure and low illumination failure, iridium chloride (III or I
V), water-soluble iridium salts such as ammonium hexachloroiridium salt, or water-soluble rhodium salts such as rhodium chloride can be used.

In the light-sensitive silver halide emulsion, soluble salts may be removed after the formation of precipitate or after the physical heat treatment. In this case, it can be carried out according to the Nudel washing method or the precipitation method. The light-sensitive silver halide emulsion may be used in an unripened state, but is usually chemically sensitized before use. Well-known emulsions for conventional type sensitizers, such as sulfur sensitization method, reduction sensitization method, and noble metal sensitization method can be used alone or in combination. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (see JP-A-58-126526 and JP-A-58-215644).

When the sensitizing dye is added to the photosensitive silver halide emulsion, it is preferable to add it at the stage of preparing the photosensitive silver halide emulsion. When a nitrogen-containing heterocyclic compound is added as a compound having a fog-preventing function and / or a development-accelerating function, which will be described later, in the preparation of the photosensitive silver halide emulsion, the photosensitive silver halide grain forming step or ripening step is performed. Is preferably added.

An organic silver salt oxidizing agent described below can be used in combination with the photosensitive silver halide. In that case, an organic silver salt emulsion can be prepared by a method similar to the method for preparing the photosensitive silver halide emulsion.

The amount of photosensitive silver halide contained in the photosensitive material (photosensitive layer) is 0.1 m in terms of silver including an organic silver salt which is an optional component.
It is preferably in the range of g to 10 g / m ² . Further, in terms of silver halide alone, it is preferably 0.1 g / m ² or less, and particularly preferably 1 mg to 90 mg / m ² .

There is no particular limitation on the photosensitive silver halide sensitizing dye,
Photosensitive silver halide sensitizing dyes known in the photographic art can be used. The sensitizing dyes are methine dyes,
Examples include merocyanine dyes, complex cyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

These sensitizing dyes may be used alone or in combination. Particularly, for the purpose of supersensitization, it is general to use a sensitizing dye in combination.
Further, together with the sensitizing dye, a dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light but exhibits supersensitization may be used together.

The addition amount of the sensitizing dye is generally in the range of 10 ^-2 -10 ^-8 mol per mol of silver halide. The sensitizing dye is preferably added at the stage of preparing the silver halide emulsion described above.

Organic silver salts are effective in heat development processing. That is, when heated to a temperature of 80 ° C. or higher, it is considered that the above organic silver salt participates in the redox reaction using the latent image of silver halide as a catalyst. In this case, it is preferable that the silver halide and the organic silver salt are in a contact state or a close state.
Examples of the organic compound that constitutes the organic silver salt include an aliphatic or aromatic carboxylic acid, a thiocarbonyl group-containing compound having a mercapto group or α-hydrogen, and an imino group-containing compound. Benzotriazole is particularly preferred. Organic silver salts are generally silver halide 1
The amount used is 0.01-10 mol, more preferably 0.1-1 mol, per mol. Similar effects can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the photosensitive material instead of the organic silver salt.

A compound having an antifoggant function and / or a development promoting function can be used. Light-sensitive materials using antifoggants are disclosed in JP-A-62-151838, JP-A-62-151841 for compounds having a cyclic amide structure, and JP-A-62-151842 for thioether compounds. JP-A-62-151842 for thiol derivatives, JP-A-62-178232 for acetylene compounds.
Japanese Patent Application Laid-Open No. 62-
Japanese Patent No. 183450 discloses a quaternary ammonium salt.
63-91653, respectively.

Reducing agent: The reducing agent has a function of reducing and developing silver halide and a function of accelerating (or suppressing) the polymerization of the polymerizable compound. However, two or more types of reducing agents each having these two functions may be used in combination.

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-sulfonamidoindanones, 4 -Sulfonamide-5-pyrazolones, 3-
There are sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, hydrazines and the like.

By adjusting the type and amount of the reducing agent, the polymerizable compound can be polymerized in either the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. For example, when hydrazines are used as the reducing agent, it is possible to cause a polymerization reaction in the portion where the latent image of silver halide is formed. Further, as a reducing agent, 1-
By using phenyl-3-pyrazolidones and further using a polymerization initiator which decomposes by heat or light to uniformly generate radicals, a polymerization reaction can be caused in a portion where a latent image is not formed. Regarding the latter, JP-A-61-1
75342, 61-243449, 62-70836, 62-8163
5 publications, US Pat. No. 4649098 and EP patent 020249
It is described in each specification of 0B1.

The reducing agent having the above function is disclosed in JP-A-61-183640.
61-188535, 61-228441, 62-86354, 6
2-86355, 62-264041, and 62-198849 (including those described as a developing agent or a hydrazine derivative). Regarding reducing agents, see “The Theory of the Photographic Process”, 4th edition, 2 by T. James.
Pages 91-334 (1977), Research Disclosure magazine 170th
Vol. 170, No. 17029, June 1978 (pages 9 to 15), and ibid. 1
76, 17643, December 1978 (pages 22-31).

Further, instead of the reducing agent, a reducing agent precursor capable of releasing the reducing agent under heating or in contact with a base may be used.

These reducing agents may be used alone or in combination of two or more kinds. As the interaction of the reducing agent in the latter case, firstly, promoting reduction of silver halide (and / or organic silver salt) by so-called superadditivity, secondly, silver halide (and / or Or the oxidized form of the first reducing agent generated by the reduction of (organic silver salt) causes the polymerization of the polymerizable compound (or suppresses the polymerization) via the redox reaction with other coexisting reducing agents. Things can be considered. However, in reality, the above reactions can occur simultaneously, so it is difficult to specify which of these actions.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-3-pyrazolidone, 5-phenyl-3-pyrazolidone, 1,5 -Diphenyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol , 1-acetyl-2-phenylhydrazine, 1-formyl-2- (2
-Methoxyphenyl) hydrazine, 1-formyl-2-
(2-chlorophenyl) hydrazine, 1-formyl-2
-(2-butoxyphenyl) hydrazine, 1- (3,5-
Dichlorobenzoyl) -2-phenylhydrazine, 1-
(3,5-dichlorobenzoyl) -2- (2-chlorophenyl) hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-2-{(p- or o-) aminophenyl) hydrazine, 1-formyl- 2-{(p- or o-) aminophenyl} hydrazine, 1-acetyl-2-{(p- or o-) methoxyphenyl} hydrazine, 1-lauroyl-2-{(p- or o-) aminophenyl } Hydrazine, 1-trityl-2- (2,6-
Dichloro-4-cyanophenyl) hydrazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2-
(2,4,6-Trichlorophenyl) hydrazine, 1- {2
-(2,5-di-t-pentylphenoxy) butyroyl}
-2-{(p- or o-) aminophenyl} hydrazine, 1- {2- (2,5-di-t-pentylphenoxy)
Butyroyl} -2-{(p- or o-) aminophenyl} hydrazine pentadecyl fluorocaprylate,
3-indazolinone, 1-trityl-2-[(2-N-
Butyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl] hydrazine, 1- {4- (2,5-
Di-t-pentylphenoxy) butyroyl} -2-
{(P- or o-) methoxyphenyl} hydrazine,
1- (methoxycarbonylbenzohydryl) -2-phenylhydrazine, 1-formyl-2- [4- {2- (2,
4-di-t-pentylphenoxy) butylamido} phenyl] hydrazine, 1-acetyl-2- [4- {2-
(2,4-di-t-pentylphenoxy) butyramide}
Phenyl] hydrazine, 1-trityl-2-[{2,6-
Dichloro-4- (N, N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine, 1- (methoxycarbonylbenzohydryl) -2- (2,4-dichlorophenyl) hydrazine, 1-trityl-2-[{ 2- (N-ethyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl] hydrazine, 1-benzoyl-2-
Trityl hydrazine, 1- (4-butoxybenzoyl)
-2-Tritylhydrazine, 1- (2,4-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4-dibutylcarbamoylbenzoyl) -2-tritylhydrazine and 1- (1-naphthoyl) -2-tritylhydrazine Can be mentioned.

The reducing agent is preferably used in the range of 0.1 to 1500 mol% with respect to 1 mol of silver (including silver halide and organic silver salt).

Polymerizable compound: The polymerizable compound is not particularly limited, and known compounds can be used. However, it is preferable to use a compound having a high boiling point (for example, a boiling point of 80 ° C. or higher) that is hard to volatilize during heating. A polyfunctional polymerizable compound having two or more polymerizable functional groups in the molecule is preferable. The polymerizable compound is an addition-polymerizable or ring-opening polymerizable compound. The addition-polymerizable compound includes a compound having an ethylenically unsaturated group, and the ring-opening polymerizable compound includes a compound having an epoxy group. Among them, the addition-polymerizable compound is particularly preferable.

These compounds include (meth) acrylic acid and salts thereof, or esters, (meth) acrylamide, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and those. There are derivatives and the like.

Specific examples of the polymerizable compound include n-butyl acrylate, cyclohexyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate. Acrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylenated bisphenol A diacrylate, 2,2- Dimethyl-3-hydroxypropionaldehyde and trimethyl -Propane condensate diacrylate, 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol condensate triacrylate, hydroxypolyether polyacrylate, polyester acrylate, polyoxyethylenated bisphenol F diacrylate, polyurethane Examples thereof include acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, and those obtained by substituting a part or all of the acryloyl group of the above-mentioned polymerizable compound with a methacryloyl group.
These compounds can also be selected from commercial products. As a specific example, Kayarad R-604, R-684, R-712, R-3
10, R-167, HX220 (above, Nippon Kayaku Co., Ltd.),
Aronix M-309, M-310, M-400, M-210 (above, Toa Gosei Chemical Co., Ltd. make) etc. can be mentioned.

These polymerizable compounds may be used alone or in combination of two or more.

The polymerizable compound is preferably used in the range of 50,000 to 100,000 parts by weight with respect to 1 part by weight of the photosensitive silver halide. A more preferred range of use is 10 to 10,000 parts by weight.

Dispersion method of aqueous liquid: A method of using a copolymer as a dispersant to stably emulsify and finely disperse an aqueous liquid such as a silver halide emulsion and an aqueous dispersion of a base precursor in an oil medium such as a polymerizable compound. Is preferred. The copolymer is preferably dissolved in an oily medium before emulsification. Specific examples and use examples of the copolymer are described in JP-A-62-209449 and 63-2878.
It is described in each gazette of No. 44.

Further, as another method for stably dispersing the above-mentioned aqueous liquid in an oil medium, a method of microencapsulating the aqueous liquid as described in JP-A-62-164041 can be used.

Base precursor: As a base precursor, a salt of carboxylic acid (which is decarboxylated by heating) and a base, a compound that releases amines by a reaction such as intramolecular nucleophilic substitution reaction, Rossen transfer, Beckmann transfer, etc. can be reacted by heating. It is preferred to use compounds that wake up to release the base. Further preferred is a salt consisting of a carboxylic acid and an organic base.

Specific examples of known base precursors consisting of salts of carboxylic acids and organic bases include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid,
p-Toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, phenylsulfonyl acetate guanidine, 4-chlorophenylsulfonyl acetate guanidine, 4-methyl-sulfonylphenylsulfonyl acetate guanidine and 4-
Guanidine acetylamine methyl propiolate and the like can be mentioned.

The base precursor is a salt composed of a carboxylic acid and an organic base, as described in JP-A-63-316760, wherein the organic base has one hydrogen atom from an amidine represented by the following formula (I). Or a diacid or tetraacid base consisting of 2 to 4 partial structures corresponding to an atomic group excluding 2 and at least one hydrocarbon residue or heterocyclic group as a linking group of the partial structure. Precursors are particularly preferred.

R ¹ , R ² , R ³ and R ⁴ in the above formula (I) are each a group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic residue. It is a monovalent group selected from the following.
Among them, a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group are preferred. Each group may have one or more substituents. The alkyl group, alkenyl group and alkynyl group preferably have 1 to 6 carbon atoms. An example of the cycloalkyl group is a cyclohexyl group. An example of an aralkyl group is a benzyl group. A phenyl group is mentioned as an example of an aryl group.

Any two groups of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a 5- or 6-membered heterocycle consisting of a nitrogen atom and a carbon atom.

R ¹ and R ² are bonded to each other to form the following formula (I-
It is particularly preferable to form the cyclic amidine represented by 2).

R ¹⁵ in the above formula (I-2) is a divalent group selected from an ethylene group, a propylene group, a trimethylene group, a vinylene group and a propenylene group. Each group may have one or more substituents. Of these, ethylene group, propylene group and trimethylene group are particularly preferable. That is, the cyclic amidine is preferably 2-imidazoline, 1,4,5,6-tetrahydropyrimidine or a derivative thereof,
Particularly preferred is 4,5,6-tetrahydropyrimidine or a derivative thereof.

R ¹⁶ is the same as R ³ in formula (I). A hydrogen atom or an alkyl group is particularly preferable. R ¹⁷ is the same as R ^{4 in} formula (I). A hydrogen atom is particularly preferable.

The heterocyclic ring, the aliphatic group (eg, cyclohexane), and / or the aromatic ring may be condensed with the cyclic amidine of the formula (I-2).

The base precursor is a salt composed of a carboxylic acid and an organic base, as described in JP-A-64-68746, wherein the organic base has one hydrogen atom from guanidine represented by the following formula (IV). Alternatively, a diacid or tetraacid base (total carbon) consisting of 2 to 4 partial structures corresponding to atomic groups excluding 2 and one or more hydrocarbon residue or heterocyclic residue as a linking group of the partial structure A base precursor whose number of atoms is 6 times or less of the number of partial structures) is also particularly preferable.

In the above formula (IV), R ^{41 to} R ⁴⁵ are each a monovalent group selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic residue. Yes (each group may have one or more substituents), any two groups selected from R ^{41 to} R ⁴⁵ are bonded to each other and are 5 or 6 consisting of a nitrogen atom and a carbon atom. It may form a heterocycle of a member ring.

The base precursor used in the present invention is insoluble or hardly soluble in water and an oily medium to be used (solubility is 10% or less, more preferably 3%) among those described above.
The following) can be selected and used.

Color Image-Forming Substance: In the present invention, a color image-forming substance can be used (in the image-forming composition) as an optional component. Known pigments and dyes can be added as color image forming substances (colorants). The type, hue and amount of addition are arbitrary. These are effective as a halation or anti-irradiation agent as well as visualizing an image after development processing.

As the color image forming substance, a dye precursor that develops a color by energy such as heating, pressurization, air oxidation and light irradiation can be used. Examples thereof include leuco bodies such as thermochromic compounds, piezochromic compounds, photochromic compounds, triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes.

As the color image-forming substance, a dye precursor that develops a color by reacting with another substance can be used. Various systems that develop color by acid-base reaction, redox reaction, coupling reaction, chelate formation reaction, etc. between two or more components. For example, Hiroyuki Moriga "Introduction to Special Paper Chemistry" (Showa 50)
Years), pressure-sensitive copying paper (pages 29-58), azography (pages 87-95), and thermosensitive color development due to chemical changes (118
A known coloring system such as −120 page) can be used.

Specifically, lactone used for non-carbon paper,
Coloring system consisting of colorant having partial structure such as lactam, spiropyran, etc. and acidic substance (developing agent) such as acid clay and phenols; aromatic diazonium salt or diazotate, diazosulfonates and naphthols, anilines, System using azo coupling reaction of active methylenes; chelate forming reaction such as reaction of hexamethylenetetramine with ferric ion and gallic acid, reaction of phenolphthalein-complexone with alkaline earth metal ion, etc .; A redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol is used.

The color image forming substance is preferably in the range of 0.5 to 30% by weight of the polymerizable compound.

Polymerization initiator: In the present invention, the reducing agent is one whose oxidant suppresses the polymerization reaction (for example, the above-mentioned 1-phenyl-
3-pyrazolidones), the polymerizable compound can be polymerized in the portion where the latent image is not formed. In this case, it is preferable to use a thermal polymerization initiator or a photopolymerization initiator in order to uniformly generate radicals.

The thermal polymerization initiator is described, for example, on pages 6-18 of “Additional Polymerization / Ring-Opening Polymerization” (1983, Kyoritsu Shuppan) edited by the Society of Polymer Science and the Society for Polymer Experiments Editorial Committee. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1′-
Azo compounds such as azobis (1-cyclohexanecarbonitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), azobisdimethylvaleronitrile, and benzoyl peroxide , Ji-
t-butyl peroxide, dicumyl peroxide,
Examples thereof include organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate, and sodium p-toluenesulfinate.

The photopolymerization initiator is described in, for example, “Chemical Revi” by Oster et al.
ew, Vol. 68 (1968), pages 125-151 and by Kosar, "Lig
ht-Sensitive System "(John Willey & Sons, 1965)
Carbonyl compounds (for example, α-alkoxyphenyl ketones, polycyclic quinones, benzophenone derivatives, xanthones, thioxanthones, benzoins), halogen-containing compounds (for example, Chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, fluorenones), haloalkanes, α-halo-α-phenylacetophenones, photoreducible dyes and reductions Redox couples with agents, organic sulfur compounds, peroxides, photo-semiconductors (eg titanium dioxide, zinc oxide), metal compounds (eg iron (I) salts, metal carbonyls, metal complexes, uranyl salts), halogenations Silver, azo and diazo compounds, US Pat. No. 4 Such as a compound consisting of the specification described Patent 772,530 ionic dye and the counter ions are used.

Specific examples of the photopolymerization initiator include 2-dimethoxy-2
-Phenylacetophenone, 2-methyl- {4- (methylthio) phenyl} -2-morpholino-1-propanone, benzoisobutyl ether, benzoisoisopropyl ether, benzophenone, Michler's ketone, 4,
4'-diethylamine nobenzophenone, chloromethylbenzophenone, chlorosulfonylbenzophenone, 9,
10-anthraquinone, 2-methyl-9,10-anthraquinone, chlorosulfonylanthraquinone, chloromethylanthraquinone, 9,10-phenanthrenequinone, xanthone, chloroxanthone, thioxanthone, chlorothioxanthone, 2,4-diethylthioxanthone , Chlorosulfonylthioxanthone, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, fluorene, carbon tetrabromide, and the like. Examples of the photoreducing dye include methylene blue, thionin, rose bengal, erythrosine-β, eosin, rhodamine, phloxine-β, safranin, acriflavine, riboflavin, fluorescein, uranine, benzoflavin, acridine orange, acridine Yellow, Benzanthrone and the like.

Examples of reducing agents (hydrogen-donating compounds) used with these dyes include β-diketones such as dimedone and acetylacetone, amines such as triethanolamine, diethanolamine, monoethanolamine, diethylamine and triethylamine, p-toluenesulfinic acid, Examples include sulfinic acids such as benzenesulfinic acid and salts thereof, N-phenylglycine, L-ascorbic acid and salts thereof, thiourea, allylthiourea and the like.
The molar ratio of the photoreducible dye and the reducing agent is preferably in the range of 1 / 0.1-1 / 10.

As the photopolymerization initiator, commercially available products such as "Irgacure 651, -907" manufactured by Ciba-Geigy can be preferably used.

The polymerization initiator is 0.001 to 0.5 g per 1 g of the polymerizable compound,
More preferably, it can be used in the range of 0.01-0.2 g.

Support: As the support, paper, synthetic paper, paper laminated with synthetic resin (eg polyethylene, polypropylene, polystyrene, etc.), plastic film (eg polyethylene terephthalate, polycarbonate, polyimide, etc.)
Nylon, cellulose triacetate, etc.), metal plate (eg aluminum, aluminum alloy, zinc,
Iron, copper, etc.), paper or plastic film laminated or vapor-deposited with the above metals, and the like are used.

Method for producing microcapsules: When an oil-based image forming composition (or a photosensitive composition) is microencapsulated, the composition is generally emulsified in water containing a water-soluble polymer as a protective colloid to form oil-based droplets. Form a capsule wall around. Examples of microencapsulation methods include methods utilizing the coacervation of hydrophilic wall forming materials as described in US Pat. Nos. 2,800,457 and 2,800,458; US Pat. No. 3,287,154 and British Patent No., 990,443. , And Japanese Patent Publication 38-19
No. 574, No. 42-446, No. 42-771, the interfacial polymerization method described in each publication; U.S. Pat. Nos. 3,418,250 and 3,660,304; polymer precipitation method; U.S. Pat.
Method using isocyanate-polyol wall material described in 96669; Method using isocyanate wall material described in US Pat. No. 3,914,511; US Pat. No. 4,001
No. 140, No. 4087376, No. 4089802, a method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall material; melamine-formaldehyde resin described in US Pat. No. 5,025,455. , Using a wall material such as hydroxypropyl cellulose; JP-B-36-9168 and JP-A-51-90.
In-situ by polymerization of monomers described in each publication of No. 79
Method; Polymerization dispersion cooling method described in each specification of British Patent Nos. 927807 and 965074; Spray drying method described in each specification of US Pat. No. 3111407 and British Patent 930422, etc. You can

As the wall material forming the outer shell of the microcapsule,
Polyamide resin and / or polyester resin, polyurea resin and / or polyurethane resin, amino
Aldehyde resin, gelatin, epoxy resin, composite resin of polyamide resin and polyurea resin, composite resin of polyurethane resin and polyester resin and the like are particularly preferable.

The average particle size of the microcapsules is preferably in the range of 3-20 μm.

At least 70% by weight of the silver halide contained in the microcapsules is preferably present in the wall material constituting the capsule shell. The silver halide grains enclosed in the microcapsules are preferably 1/5 or less of the particle size of the microcapsules, and the silver halide grains contained in one microcapsule are preferably 5 or more.

Image Receiving Material: The image receiving material is generally prepared by providing an image receiving layer on a support. The image-receiving layer can contain various compounds according to the color-forming system of the color image-forming substance. When the color image-forming substance is a dye precursor that develops color by reacting with a developer, the image-receiving layer preferably contains a developer. When the color image-forming substance is a dye, the image-receiving layer may contain a mordant. The mordant can be selected from compounds known in the photographic art and used. The image receiving layer may contain a polymer as a binder. The polymer used in the photosensitive layer of the photosensitive material is used as the binder. The image-receiving layer may contain fine particle powder. Even if the powder is a colorless inorganic pigment (for example, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, etc.), it is also disclosed in JP-A-62-28.
[0071] Thermoplastic organic substances described in JP-A-62-280739 and JP-A-62-280739 (for example, polymers such as polyethylene, polypropylene, polytetrafluoroethylene, waxes, etc.)
It may be. These powders have the effect of increasing the porosity in the image receiving layer and increasing the oil absorption amount to increase the density of color development. When a thermoplastic powder is used as the powder, the image-receiving layer can be made glossy or transparent by heating after transfer. Further, as described in JP-A-1-154789 and JP-A-1-154790, it is also possible to use an image receiving layer obtained by phase separation using two or more kinds of binder polymers which are hard to be compatible with each other. This has the effect of increasing the porosity and increasing the color density.

The thickness of the image receiving layer is 0.1 to 100 μm, more preferably 1-
It is in the range of 20 μm.

As the support of the image receiving material, the same support as that used for the support of the photosensitive material is used.

Image forming process: To form an image, the light-sensitive material is uniformly heated after imagewise exposure or at the same time. The silver halide on which a latent image is formed by heating is thermally developed, and at the same time, the polymerizable compound in that portion (or in the portion where the latent image is not formed) is polymerized to cure the oil phase or the microcapsules. After that, the light-sensitive material is brought into close contact with the image-receiving material and is pressed and / or heated to transfer the uncured oil droplets or the oil phase in the microcapsules to the image-receiving element, and a colored image is formed or uncured. Part of the photosensitive layer, the solvent (water, alkali, acid,
It is dissolved and removed with an organic solvent or the like) to form a colored image on the photosensitive material. In the case of the embodiments shown in FIGS. 1 to 3, the former (transfer method)
Is preferred, and in the case of the embodiments of FIGS. 4 to 5, the latter (dissolution method) is preferred.

The exposure is performed using a light source that emits light having a wavelength corresponding to the spectral sensitivity (sensitizing dye) of silver halide. For example, lamps such as tungsten lamps, halogen lamps, xenon lamps, mercury lamps, carbon arc lamps, various lasers (semiconductor laser, helium neon laser,
Argon laser, helium cadmium laser, etc.),
Light emitting diodes, CRT tubes, etc. are used. Generally, the exposure wavelength is preferably visible light, near ultraviolet light, or near infrared light. The exposure amount is determined mainly by the sensitivity of the silver halide emulsion, but generally 0.01-10,000 ergs / cm ² , more preferably 0.1-1,000 er.
It is in the range of gs / cm ² .

The heating can be performed by contact with a heated object (for example, a plate or roller), by heating with radiant heat of a lamp rich in infrared rays, or by immersing in a medium such as heated oil. Since the inhibition of the polymerization reaction by the oxygen in the air entering during heating is reduced, it is preferable to cover the surface of the light-sensitive material with a substance that hardly permeates oxygen and heat the surface. For example, a method of bringing the surface of the photosensitive material into close contact with a heated object is preferable. The heating temperature is 80-200 ° C, more preferably 100-15
It is in the range of 0 ° C. The heating time is 1-180 seconds, more preferably 5-60 seconds.

The following examples further illustrate the present invention. However, the present invention is not limited to these.

Example 1 Preparation of Aqueous Dispersion of Base Precursor Powder of the following base precursor (mostly insoluble in water)
200 g was dispersed in 800 g of a 3 wt% aqueous solution of polyvinyl alcohol using a Dynomill disperser. The particle size of the base precursor was 0.5 μm or less.

100 g of this dispersion and 200 g of water were mixed and concentrated using a centrifuge to obtain an aqueous dispersion having a base precursor concentration of 64% by weight.

Preparation of silver halide emulsion Silver halide emulsion (A) (blue-sensitive) Agitated gelatin aqueous solution (16 g of gelatin in 1500 ml of water)
And 0.5 g of sodium chloride containing 0.5 g of silver nitrate dissolved in 300 ml of an aqueous solution containing 71 g of potassium bromide in pH 3.2 adjusted to pH 3.2 with 1N sulfuric acid and kept at 50 ° C. ) Was added simultaneously at an equal flow rate over 50 minutes. One minute after the completion of this, 43 ml of a 1% methanol solution of the following sensitizing dye (A) was added, and 15 minutes after the addition of the sensitizing dye, an aqueous solution containing 2.9 g of potassium iodide 10
0 ml and an aqueous silver nitrate solution (0.018 mol of silver nitrate dissolved in 100 ml of water) were simultaneously added over 5 minutes. To this emulsion, 1.2 g of poly (isobutylene-monosodium coumarate) was added and allowed to settle, washed with water and desalted, and then 12 g of gelatin was added and dissolved, and further sodium thiosulfate was added.
0.5 mg was added and chemically sensitized at 60 ° C for 15 minutes. Monodisperse tetradecahedral silver iodobromide emulsion (A) 1000 having an average grain size of 0.22 µm.
g was prepared.

Silver halide emulsion (B) (edge sensitive) Agitated gelatin aqueous solution (20 g gelatin in 1600 ml water)
200 ml of an aqueous solution containing 71 g of potassium bromide in 200 ml of an aqueous solution containing 71 g of potassium bromide in a solution containing 0.5 g of sodium chloride, adjusted to pH 3.2 with 1 N sulfuric acid and kept at 42 ° C., and 0.59 mol of silver nitrate dissolved in 200 ml of water. ) Was added simultaneously at equal flow rates over 30 minutes. One minute after the completion of this, 48 ml of a 1% methanol solution of the following sensitizing dye (B) was added, and 10 minutes after the addition of the sensitizing dye, an aqueous solution containing 2.9 g of potassium iodide 10 was added.
0 ml and an aqueous silver nitrate solution (0.018 mol of silver nitrate dissolved in 100 ml of water) were simultaneously added over 5 minutes. To this emulsion was added 1.2 g of poly (isobutylene-monosodium coumarate), which was allowed to settle, washed with water to desilver, and then added with 18 g of gelatin to dissolve it.
0.7 mg was added and chemically sensitized at 60 ° C. for 15 minutes to obtain a monodisperse tetradecahedral silver iodobromide emulsion (B) 10 having an average grain size of 0.12 μm.
00g was produced.

Silver halide emulsion (C) (red-sensitive) Agitated aqueous gelatin solution (20 g gelatin in 1600 ml water)
200 ml of an aqueous solution containing 71 g of potassium bromide in 200 ml of an aqueous solution containing 71 g of potassium bromide in a solution containing 0.5 g of sodium chloride and 0.5 g of pH adjusted to 3.5 with 1N sulfuric acid, and dissolving 0.59 mol of silver nitrate in 200 ml of water. ) Was added simultaneously at equal flow rates over 30 minutes. One minute after this was completed, 48 ml of a 0.5% methanol solution of the following sensitizing dye (C) was added, and 15 minutes after adding the sensitizing dye, 100 ml of an aqueous solution containing 3.65 g of potassium iodide and an aqueous silver nitrate solution (water: 100 ml of silver nitrate) 0.022 mol dissolved) was added simultaneously over 5 minutes.
To this emulsion was added 1.2 g of poly (isobutylene-coumaric acid 63 sodium salt) to cause precipitation, followed by washing with water to desalt, and then adding 10 g of gelatin to dissolve, and further adding sodium thiosulfate.
0.45 mg was added and chemically sensitized at 55 ° C. for 20 minutes, and a monodisperse tetradecahedral silver iodobromide emulsion (C) 1000 having an average grain size of 0.13 μm.
g was prepared.

Preparation of Photosensitive Composition Photosensitive Composition (A) (Blue Sensitive) 15 g of the following yellow color image-forming substance was dissolved in 100 g of trimethylolpropane triacrylate (polymerizable compound) to give an oil phase.

1.8 g of the following copolymer was dissolved in 60 g of this oil phase.
To this, 16.6 g of an aqueous dispersion of the base precursor prepared as described above was added and a homogenizer was used to obtain 7000 min.
The mixture was stirred for 60 minutes by rotation and the aqueous dispersion of base precursor was emulsified in the oil phase. In addition, in this stirring, most of the water in the aqueous dispersion was evaporated, but part of the water remained.

To 59 g of this emulsion, the following hydrazine compound (reducing agent) 3.9 g, the following developing agent (reducing agent) 3.3 g, the following mercapto compound precursor 0.05 g, the following mercapto compound 0.01 g and the following surfactant 0.5 g Was dissolved. Furthermore, a mixture of 8 g of the silver halide emulsion (A) described above and 1.3 g of a 10% aqueous solution of potassium bromide was added to the obtained emulsion, and a homogenizer was used at 40 ° C. at 10,000 rpm. The mixture was stirred for 10 minutes to prepare a photosensitive composition in the oil phase.

Photosensitive Composition (B) (Edge Sensitivity) A photosensitive composition (B) was prepared in the same manner as in the photosensitive composition (A) except that a part thereof was changed as described below.

Instead of the yellow color image-forming substance, 24 g of the following magenta color image-forming substance, 0.015 g of the mercapto compound instead of 0.01 g, and 8 g of the silver halide emulsion (B) instead of the silver halide emulsion (A) are used.

Photosensitive Composition (C) (Red Sensitivity) A photosensitive composition (C) was prepared in the same manner as in the photosensitive composition (A) except that a part thereof was changed as follows.

Instead of the yellow color image forming substance, the following cyan color image forming substance 19g, 0.00 g instead of 0.01 g of the mercapto compound
75 g, 8 g of silver halide emulsion (C) is used instead of silver halide emulsion (A).

Preparation of Photosensitive Microcapsule Dispersion Liquid Photosensitive Capsule Dispersion Liquid (A) 4.8 g of an isocyanate compound (Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) was dissolved in the above-mentioned photosensitive composition (A). This solution was added to 113 g of a 10% aqueous solution of sodium salt of polystyrenesulfonic acid (trade name: VersaTL502, manufactured by National Starch), and the mixture was stirred with a homogenizer at 40 ° C for 30 seconds at 9000 rpm to obtain a photosensitive composition. Was emulsified in an aqueous solvent.

While stirring the above aqueous emulsion at 1200 rpm at 25 ° C, a melamine-formaldehyde prepolymer (186 g of water was added).
Melamine (34.5 g) and formalin (57 g) were added to the above, and a solution (32 g) obtained by stirring at 60 ° C. at 600 rpm for 30 minutes was added, and then pH was adjusted to 6. Further, this solution was heated to 60 ° C. and stirred at 1200 rpm for 90 minutes, and then the pH was adjusted to 7.0 to prepare a photosensitive microcapsule dispersion (A).

Photosensitive microcapsule dispersion (B) In the photosensitive microcapsule dispersion (A),
A photosensitive microcapsule dispersion (B) was prepared in the same manner except that the photosensitive composition (B) was used instead of the photosensitive composition (A).

Photosensitive microcapsule dispersion (C) In the photosensitive microcapsule dispersion (A),
A photosensitive microcapsule dispersion (C) was prepared in the same manner except that the photosensitive composition (C) was used instead of the photosensitive composition (A).

Preparation of paper support 20 parts of LBSP and LBKP80 were refined to 290 cc of Canadian Freeness (CSF) using a refinery, 0.3 parts of alkyl ketene dimer (Acorbel 12, manufactured by Dick Hercules) as a neutral sizing agent, and polyamide polyamine epichlorohydrin as a fixing agent. (Kaymen 557, manufactured by Dick Hercules) 0.5 parts, and cation-modified polyacrylamide (trade name; Polystron) as a paper strengthening agent.
0.5 parts of 705 and Arakawa Chemical Co., Ltd. were added at an absolute dry weight ratio of pipe. Then, using a Fourdrinier paper machine, the above stock material was made into a base paper having a weight of 60 g / m ² and a thickness of 66 μm.

Moisture-proof layer forming coating solution made of polyvinylidene chloride resin on the surface (felt surface) of the base paper produced as described above, and 100 parts of SBR latex (trade name: SN-304, Sumitomo Nogatak Co., Ltd.), Sodium polyacrylate (trade name: Aron T40, manufactured by Toagosei Kagaku Kogyo Co., Ltd.) 1 part, clay (trade name: UW-90, manufactured by Engelhard Co.) 200 parts, and petroleum resin (trade name: Carbomul R) , manufactured by Dick Hercules Inc.) a composition consisting of 100 parts of moisture-proof layer coating solution were each prepared, respectively weighed by sequentially an air knife coater coating solution was applied at a coverage of from ^{16g / m 2, 5g / m} 2 To produce a paper support.

Preparation of Photosensitive Material 10 g each of the photosensitive microcapsule dispersions (A), (B) and (C), 5% aqueous solution of the surfactant 2
g, 40 g of a 40% aqueous solution of urea and 40 g of water were added to prepare a coating solution for the photosensitive layer.

A dry film thickness of about 10μ was applied to the paper support described above.
A full-color light-sensitive material was prepared by applying the coating solution so as to have a thickness of m and drying.

Preparation of image-receiving material In 123 g of water, 2.5 g of sodium hexametaphosphate was dissolved, and further thereto, 22 g of zinc 3,5-di-α-methylbenzyl salicylate and 53 g of 55% calcium carbonate slurry
And were mixed and dispersed by a Dynamill disperser. To 40 g of the obtained liquid, 8 g of an 8% polyvinyl alcohol aqueous solution, 10%
4 g of an aqueous gelatin solution, 1.6 g of zinc chloride and 34 g of water were added and mixed uniformly. This mixed liquid was applied onto art paper having a weight of 43 g / m ² so as to have a wet film thickness of 90 μm, and then dried to prepare an image receiving material.

Evaluation of photosensitive material The photosensitive material obtained as described above was imagewise exposed through a step wedge with a halogen lamp at an illuminance of 2000 lux for 1 second, and then the photosensitive layer was adhered to a heating plate heated to 155 ° C. And developed by heating. Then, the light-sensitive material was overlaid on the above image-receiving material and, in this state, it was passed through a pressure roller of 500 kg / cm ² , and a positive image was obtained on the image-receiving material with respect to a black original (wedge). Minimum concentration is 0.1
The heating time required to obtain the following images was about 7 seconds.

Comparative Example 1 Preparation of Photosensitive Composition Photosensitive Composition (A) (Blue Sensitivity) In 100 g of trimethylolpropane triacrylate,
15 g of the yellow image-forming substance of Example 1 was dissolved to form an oil phase. In 49 g of this oil phase, used were 1.8 g of the copolymer used in Example 1, 3.9 g of a humanazine compound, 3.3 g of a developing agent, 0.05 g of a precursor of a mercapto compound, and 0.0 g of a mercapto compound.
1 g and 0.5 g of surfactant were dissolved. Furthermore, a mixed solution of 8 g of the silver halide emulsion (A) of Example 1 and 1.3 g of a 10% aqueous solution of potassium bromide was added thereto, and the mixture was stirred at 40 ° C. at 10,000 rpm for 10 minutes using a homogenizer. Thus, a photosensitive composition (A) was produced.

Photosensitive Composition (B) (Sensitivity) A photosensitive composition (B) was prepared in the same manner except that the photosensitive composition (A) was partially modified as described below.

Instead of the yellow image-forming substance, 24 g of the magenta color image-forming substance of Example 1 and 0.01 g of the mercapto compound were used instead of 0.01 g.
015 g, 8 g of the silver halide emulsion (B) of Example 1 is used instead of the silver halide emulsion (A).

Photosensitive Composition (C) (Red Sensitivity) A photosensitive composition (C) was prepared in the same manner as in the photosensitive composition (A) except that a part thereof was changed as follows.

Instead of the yellow image-forming substance, 19 g of the cyan image-forming substance of Example 1 and 0.01 g of the mercapto compound were used instead of 0.01 g.
Instead of the silver halide emulsion (A), 8 g of the silver halide emulsion (C) of Example 1 is used.

Preparation of Photosensitive Microcapsule Dispersion Liquid except that the photosensitive composition prepared as described above was used,
In the same manner as in Example 1, photosensitive microcapsule dispersions (A), (B) and (C) were prepared.

Preparation of Aqueous Dispersion of Base Precursor Powder of the base precursor used in Example 1 200 g
Was dispersed in 800 g of a 3 wt% aqueous solution of polyvinyl alcohol using a Dynomill disperser to obtain an aqueous dispersion of a base precursor.

Preparation of Photosensitive Material 10 g of each of the photosensitive microcapsule dispersions (A), (B) and (C) prepared as described above, 7 g of the above base precursor aqueous dispersion, and the surface active agent used in Example 1 were used. 2g of 5% aqueous solution of agent, 2.5g of 40% aqueous solution of urea
And 33 g of water were added to prepare a coating solution for the photosensitive layer.

This coating solution was applied onto the paper support used in Example 1 so that the dry film thickness was about 10 μm, and dried to give a photosensitive material containing a base precursor in the photosensitive layer outside the photosensitive microcapsules. It was made.

Evaluation of Light-Sensitive Material The light-sensitive material obtained as described above was used to form an image on an image-receiving material in the same manner as in Example 1. The heating time required to obtain an image having a minimum density of 0.1 or less was about 17 seconds. there were.

Comparative Example 2 Preparation of Photosensitive Composition Photosensitive Composition (A) (Blue Sensitivity) In 100 g of trimethylolpropane triacrylate,
15 g of the yellow image-forming substance of Example 1 was dissolved to form an oil phase. 15 g of the powder of the base precursor (mostly insoluble in the oil phase) used in Example 1 was dispersed in 85 g of this oil phase using a Dynomill disperser. The particle size of the base precursor was 0.5 μm or less.

59 g of oil phase in which the base precursor was dispersed in this way
In addition, 1.8 g of the copolymer used in Example 1, 3.9 g of human lazine compound, 3.3 g of developer, 0.05 g of mercapto compound precursor, 0.01 g of mercapto compound and 0.01 g of surfactant.
0.5 g was dissolved. Furthermore, a mixed solution of 8 g of the silver halide emulsion (A) of Example 1 and 1.3 g of a 10% aqueous solution of potassium bromide was added thereto, and the mixture was mixed with a homogenizer at 40 ° C. for 10 minutes per minute.
The photosensitive composition (A) was produced by stirring at 000 rpm for 10 minutes.

Photosensitive Composition (B) (Green Sensitivity) A photosensitive composition (B) was prepared in the same manner except that the photosensitive composition (A) was partially modified as described below.

Instead of the yellow image-forming substance, 24 g of the magenta color image-forming substance of Example 1 and 0.01 g of the mercapto compound were used instead of 0.01 g.
015 g, 8 g of the silver halide emulsion (B) of Example 1 is used instead of the silver halide emulsion (A).

Photosensitive Composition (C) (Red Sensitivity) A photosensitive composition (C) was prepared in the same manner as in the photosensitive composition (A) except that a part thereof was changed as follows.

Instead of the yellow image-forming substance, 19 g of the cyan image-forming substance of Example 1 and 0.01 g of the mercapto compound were used instead of 0.01 g.
Instead of the silver halide emulsion (A), 8 g of the silver halide emulsion (C) of Example 1 is used.

Preparation of Photosensitive Microcapsule Dispersion Liquid except that the photosensitive composition prepared as described above was used,
In the same manner as in Example 1, photosensitive microcapsule dispersions (A), (B) and (C) were prepared.

Preparation of Photosensitive Material A photosensitive material was prepared in the same manner as in Example 1 except that the photosensitive microcapsule dispersion liquid prepared as described above was used.

Evaluation of Photosensitive Material An image was formed on the image-receiving material of the photosensitive material obtained as described above in the same manner as in Example 1. The minimum density of the image was
Even after heating for 30 seconds, it was 0.7, and no image was substantially obtained.

As is clear from the above results, when the photosensitive composition of the present invention containing a base precursor in the form of an aqueous dispersion is used, a photosensitive material having a high developing speed and high sensitivity can be obtained.

[Example 2] A silver halide emulsion and a photosensitive composition were prepared in the same manner as in Example 1.

To 10 g of the photosensitive composition (A), 1 part of polyvinyl alcohol
5000 revolutions / in a 50% 0% aqueous solution using a homogenizer
The mixture was stirred for 5 minutes for emulsification to prepare a photosensitive emulsion (A). Similarly, the photosensitive compositions (B) and (C) were emulsified to prepare photosensitive emulsions (B) and (C).

Photosensitive emulsion (A), (B) and (C), respectively
Mix 10 g and 40 g of water on the paper support of Example 1,
A full-color light-sensitive material was prepared by coating and drying so that the dry film thickness was about 10 μm.

When the image receiving material of Example 1 was used and evaluated in the same manner as in Example 1, a black positive image similar to that of Example 1 was obtained on the image receiving material.

[Example 3] A silver halide emulsion (B) was prepared in the same manner as in Example 1.

A silver halide-free composition was prepared in the same manner as in the preparation of the photosensitive composition (B) of Example 1, except for the emulsification step of the mixed solution of the silver halide emulsion and the potassium bromide aqueous solution. (B) was prepared.

Then 10 g of the above composition was added to 1 part of polyvinyl alcohol.
5000 revolutions / in a 50% 0% aqueous solution using a homogenizer
The mixture was stirred for 5 minutes to emulsify to prepare an emulsion (B).

30 g of the above emulsion (B), 0.5 of the above silver halide emulsion
g and 40 g of water were mixed and coated on the paper support of Example 1 so that the dry film thickness was about 10 μm, and dried to prepare a light-sensitive material.

When the image-receiving material of Example 1 was used and evaluated in the same manner as in Example 1, a magenta-color positive image was obtained on the image-receiving material.

[Brief description of drawings]

1 to 5 are schematic sectional views showing various aspects of the light-sensitive material produced according to the present invention. 11,21,41: Photosensitive layer 31,51: First photosensitive layer 32,52: Second photosensitive layer 12,22,33,42,53: Support

Claims (1)

(57) [Claims] 1. A method for producing a light-sensitive material comprising a support and a light-sensitive layer comprising a light-sensitive silver halide, a reducing agent, a base precursor and a polymerizable compound, wherein the content of the polymerizable compound is 0.1 to 100% by weight. In an oily medium,
A method for producing a light-sensitive material, comprising a step of emulsifying an aqueous dispersion of a base precursor.