JPH02146041A - Production of photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having high developing speed and high sensitivity by emulsifying an aq. dispersion of a basic precursor in an oily medium contg. a polymerizable compd., and using a photosensitive compsn. contg. the basic precursor dispersed in aq. medium. CONSTITUTION:An aq. dispersion of a basic precursor is emulsified in an oily medium contg. 0.1-100wt.% polymerizable compd. and obtd. oily emulsified product is emulsified in an aq. medium contg. s photosensitive silver halide emulsion, or the photosensitive silver halide emulsion is emulsified simultaneously with the basic precursor. Obtd. aq. emulsion is coated on a base body. A reducing agent is added to either one of the oily medium, or the aq. dispersion of the basic precursor, etc. Thus, a photosensitive material having high developing speed and high sensitivity is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive silver halide, a reducing agent, a
The present invention relates to a method for producing a photosensitive material provided with a photosensitive layer containing a base precursor and a polymerizable compound.

[Background of the Invention] A photosensitive material in which a photosensitive layer containing a photosensitive silver halide, a reducing agent, and a polymerizable compound is provided on a support is used in an image forming method in which a polymerizable compound is polymerized in an imagewise manner. There is. Regarding these photosensitive materials, Japanese Patent Publication No. 45-111
There are descriptions in JP-A No. 49, JP-A-61-69062, and the like.

The above-mentioned photosensitive materials have various aspects regarding the arrangement of components in the photosensitive layer. In a typical embodiment, photosensitive microcapsules containing photosensitive silver halide, a reducing agent, and a polymerizable compound are included in the photosensitive layer. This photosensitive microcapsule is described in JP-A-62-169147, JP-A-62-169-148, JP-A-62-209439 and JP-A-63-121837.

Each of the above-mentioned publications describes a base or a base precursor as an optional component added to a photosensitive material. A base or a base precursor is an important component that acts as an image formation accelerator in image formation processing (development processing of photosensitive materials).

However, it is difficult to contain bases or base precursors in microcapsules, and this has rarely been done. In conventional photosensitive materials, the base or base precursor was contained in the photosensitive layer outside the microcapsules. In the development process of photosensitive materials, a method of infiltrating a base or a base precursor into the inside of microcapsules has mainly been unsuccessful.

[Summary of the Invention] An object of the present invention is to provide a method for producing a photosensitive material containing a base precursor.

Another object of the present invention is to provide a method for producing a photosensitive material having a fast development speed and high sensitivity.

The present invention provides (1) photosensitive silver halide on a support;
In a method for producing a photosensitive material provided with a photosensitive layer containing a base agent, a base precursor, and a polymerizable compound, a step of emulsifying 1 Lti of aqueous molecules of the base precursor in an oily medium containing from Ol to 100% by weight of the polymerizable compound. The present invention provides a method for producing a photosensitive material characterized by comprising:

The method for producing a photosensitive material of the present invention preferably has the following embodiments.

(2) i[j collaboration compound from 0.1 to 100I[jf
Emulsifying the aqueous dispersion of the base precursor and the photosensitive silver halide emulsion in an oily medium containing 1% i. The reducing agent is added to any of the above-mentioned oil-based medium, aqueous dispersion of base precursor, photosensitive silver halide emulsion, oil-based emulsion, aqueous medium, and aqueous emulsion. .

(3) The aqueous emulsion obtained in the step of emulsifying the oil-based emulsion of the embodiment (2) above in an aqueous medium is microencapsulated.

(4) Polymerizable compound at 0.1 to 100, ili
emulsifying an aqueous dispersion of a 5-base precursor in an oily medium containing 11%; emulsifying the resulting oily emulsion in an aqueous medium containing a light-sensitive silver halide emulsion; 1. After converting the aqueous emulsion into 1L, a photosensitive silver halide emulsion is added to the obtained aqueous emulsion. It is added to any of the above oily medium, aqueous dispersion of a base precursor, photosensitive silver halide emulsion, oily emulsion, aqueous medium and aqueous emulsion.

(5) The aqueous emulsion obtained in step L of emulsifying the oil-based emulsion of embodiment (4) above in an aqueous medium is microencapsulated.

(6) Emulsifying the aqueous dispersion of the base precursor in an oily medium containing 0.1 to 100% by weight of a polymerizable compound; Emulsifying the resulting oily emulsion in an aqueous medium: The resulting aqueous emulsion Apply the emulsion to the support! A photosensitive silver halide emulsion is applied onto the coated product.
The reducing agent is added to the oil distribution medium, the aqueous dispersion of the base precursor, the photosensitive silver halide emulsion, the oil emulsion, the aqueous medium, and the aqueous emulsion.

(7) The aqueous emulsion obtained in the step of emulsifying the oil-based emulsion of the embodiment (6) above in an aqueous medium is microencapsulated.

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

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

(10) emulsifying an aqueous dispersion of a base precursor in an oily medium containing 0.1 to 1001'lf% of a polymerizable compound; coating the obtained oily emulsion on a support; and The process consists of coating a photosensitive silver halide emulsion on the coated material, and a reducing agent is added to any of the above-mentioned oil-based medium, aqueous dispersion of base precursor, photo-sensitive silver halide emulsion, and oil-based emulsion. Added.

(11) In the aspect of (10) above, the oily medium is 0.
Contains 1 to 90% by weight of oil-soluble binder polymer.

(12) A base precursor is a salt consisting of a carboxylic acid and an organic base.

(13) The base precursor is a salt consisting 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 to tetraacid base consisting of two to four hydrocarbon residues or one or more heterocyclic residues as a linking group of the partial structure: [In the above formula (I), )jl )j2. R3 and R4 are each a monovalent group selected from the 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 (each branch is -
), and any two groups selected from R1, R2, R3 and R4 are bonded to each other to form a three- or six-membered group consisting of a nitrogen atom and a carbon atom. may form a heterocycle].

(12) The base precursor is a salt consisting 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). A diacid to tetraacid base consisting of 2 to 4 carbon atoms, and one or more hydrocarbon residues or heterocyclic residues as a linking group for the partial structure (the total number of carbon atoms is 6 times or less the number of the partial structure) [In the above formula (IV), R"R"R"R" and R45 each represent 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; (Each branch may have one or more substituents), and any two groups selected from R43R44 and R45 are bonded to each other. may form a three- or six-membered heterocycle consisting of a nitrogen atom and a carbon atom].

(13) Adding a color image-forming substance to the photosensitive material.

(14) Adding a thermal polymerization initiator to the photosensitive material.

(15) Adding a photopolymerization initiator to the photosensitive 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 oily medium is from 0.1 to 100.
It is μm.

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

(20) The base precursor is 0.0% relative to the polymerizable compound.
It is contained in a range of 5 to 200% by weight.

[Effect of the invention] In the method for producing a photosensitive material of the present invention, the polymerizable compound is
It is characterized in that it includes a step of emulsifying an aqueous dispersion of a base precursor in an oily medium containing from 100% by weight.

According to the research of the present inventors, when an aqueous dispersion of the salt J↓ precursor is emulsified in an oily medium containing a polymerizable compound, the base precursor is contained in the oily medium in a fine and uniform state. Furthermore, the dispersion state of the base precursor in the oily medium (ie, the emulsified state of the aqueous dispersion) is extremely stable.

The base precursor contained in the oily medium in a fine and uniform state has a high decomposition rate (base production rate) during development. Therefore, in the photosensitive material produced according to the present invention, the base precursor rapidly accelerates the development reaction. Therefore, the photosensitive material produced according to the present invention is
The development speed is fast and it has a high 1 degree.

[Detailed Description of the Invention 1 The photosensitive material produced according to the present invention is provided with a photosensitive layer containing a photosensitive silver halide, a reducing agent, a base precursor, and a polymerizable compound on a support.

The photosensitive material described in Section I has various configurations regarding the arrangement of each component contained in the photosensitive layer. The characteristic step of the method for producing a photosensitive material of the present invention is to convert the polymerizable compound into O6
The step of emulsifying the aqueous dispersion of the base precursor in an oily medium containing from 1 to 100% by weight can be applied to either embodiment.

Hereinafter, five main types of photosensitive materials and their respective manufacturing methods will be explained with reference to the drawings.

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

A photosensitive layer (11) is provided on the support (12). The photosensitive layer (11) contains photosensitive silver halide (△), a reducing agent,
Contains 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 droplets of the oil-based medium or in the photosensitive layer outside the oil droplets.

The oil droplets of the oily medium are preferably in the form of microcapsules by providing an outer shell.

When manufacturing the first embodiment of the photosensitive material shown in FIG. 1 according to the present invention, the manufacturing method includes adding 0.1
A step of emulsifying an aqueous dispersion of a base precursor and a photosensitive silver halide emulsion in an oily medium containing from 100% by weight; a step of emulsifying the obtained oily emulsion in an aqueous medium; and a step of emulsifying the obtained aqueous emulsion in an aqueous medium; It consists of the step of coating on a support.

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

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

FIG. 2 is a schematic cross-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 photosensitive silver halide (△), a reducing agent,
Contains 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 a photosensitive layer outside the oil droplets.

The reducing agent may be contained in the oil droplets of the oil-based medium or in the photosensitive layer outside the oil droplets.

The oil droplets of the oily medium are preferably in the form of microcapsules by providing an outer shell.

When manufacturing the second embodiment of the photosensitive material shown in FIG. 2 according to the present invention, the manufacturing method involves emulsifying an aqueous dispersion of a base precursor in an oily medium containing 0.1 to 100% by weight of a polymerizable compound. Step of emulsifying the obtained oil emulsion in an aqueous medium containing a photosensitive silver halide emulsion, or emulsifying the oil emulsion in an aqueous medium and adding a photosensitive halogen to the obtained aqueous emulsion. It consists of a step of adding a silveride emulsion; and a step of coating the obtained aqueous emulsion on a support.

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

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

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

A first photosensitive layer (31) and a second photosensitive layer (32) are provided on the support (33). The first photosensitive layer (31) contains photosensitive silver halide (Δ).

The second photosensitive layer contains a base precursor (.) and a polymerizable compound. An oily medium containing a base precursor and a polymerizable compound is dispersed in the second photosensitive layer in the form of oil droplets. The reducing agent may be contained in the oil droplets of the oil-based medium, in the second photosensitive layer outside the oil droplets, or in the first photosensitive layer.

Note that the first photosensitive layer containing a photosensitive silver halide and the second photosensitive layer containing a base precursor and a polymerizable compound may be provided on the support in the reverse order.

However, the order shown in FIG. 3 is preferred.

The oil droplets of the oily medium are preferably in the form of microcapsules by providing an outer shell.

When manufacturing the first embodiment of the photosensitive material shown in FIG. 3 according to the present invention, the manufacturing method involves using a polymerizable compound at 0.
emulsifying an aqueous dispersion of a base precursor in an oily medium containing 1 to 100% by weight; emulsifying the obtained oily emulsion in an aqueous medium; coating the obtained aqueous emulsion on a support. Step: This consists of a step of coating a photosensitive silver halide emulsion on the obtained coated product.

Note that the order of the step of coating the aqueous emulsion on the support and the step of coating the photosensitive silver halide emulsion may be reversed.

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

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

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

FIG. 4 is a schematic cross-sectional view showing a fourth embodiment of the photosensitive material.

A photosensitive layer (41) is provided on the support (42). The photosensitive layer (41) includes photosensitive silver halide, (△) reducing agent,
It consists of an oily medium containing a base precursor (.) and a polymerizable compound.

When manufacturing the fourth embodiment of the photosensitive material shown in FIG. 4 according to the present invention, the manufacturing method includes adding 0.1
It consists of a step of emulsifying an aqueous dispersion of a base precursor and a photosensitive silver halide emulsion in an oily medium containing 1% to 100% by weight; and a step of coating the obtained oily emulsion onto a support.

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

Preferably, the oil-based medium contains 0.1 to 90% by weight of an oil-soluble binder polymer.

FIG. 5 is a schematic cross-sectional view showing a fifth embodiment of the photosensitive material.

A first photosensitive layer (51) and a second photosensitive layer (52) are provided on the support (53). The first photosensitive layer (51) contains photosensitive silver halide. The second photosensitive layer consists of an oily medium containing a base precursor and a polymerizable compound. The transition agent may be contained in the first photosensitive layer or the 73 second photosensitive layer.

Note that the first photosensitive layer containing the photosensitive silver halide and the first 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 preferred.

When manufacturing the fifth embodiment of the photosensitive material shown in FIG. 5 according to the present invention, the manufacturing method involves adding a polymerizable compound of 0.1
A step of emulsifying an aqueous dispersion of a base precursor in an oily medium containing 100% to 100% by weight; a step of applying the obtained oily emulsion to a support; and a step of exposing the obtained coated material to light. The process consists of coating a silver halide emulsion.

Note that the order of the step of coating the oil-based emulsion on the support and the step of coating the photosensitive silver halide emulsion may be reversed.

The transition agent is added to any of the above-mentioned oil-based medium, aqueous dispersion of base precursor, photosensitive silver halide emulsion, and oil-based emulsion.

Preferably, the oil-based medium contains 0.1 to 90% by weight of an oil-soluble binder polymer.

Hereinafter, the process of emulsifying an aqueous dispersion of a base precursor in an oily medium containing 0.1 to 100% of a polymerizable compound, which is a feature of the method for producing a photosensitive material of the present invention, will be described.

As used herein, 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 polymerizable compounds are used as oily vehicles (i.e.
The oily medium can contain 100.1i [%] of the polymerizable compound.

However, the oil-based medium may contain hydrophobic components other than the [■ collaboration compound]. As the hydrophobic component to be added to the oily medium, oil-soluble polymers and/or solvents are preferred.

Specific examples of the oil-soluble polymer used in the present invention include poly(meth)acrylate, polyvinyl butyral, polyhinyl formal, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl acetate-ethylene copolymer, polyvinyl chloride, polyvinylidene chloride, Vinyl chloride-vinylidene chloride copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated polyethylene, chlorinated polypropylene, polycarbonate, diacetylcellulose, cellulose acetate butyrate, triacetylcellulose, ethylcellulose, polyvinylpyridine, polyvinylimidazole, and the like.

Among stiff polymers, polymers having crosslinkable ethylenic double bonds in their side chains, which are described in JP-A-64-17047, are particularly preferred. Specific examples include allyl (meth)acrylate, hydroxyethyl (
These include homopolymers or copolymers of monomers such as 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.

Furthermore, dispersant copolymers as described below are also included in the above polymers.

As the organic solvent, any color of solvent that can dissolve the polymerizable compound and the binder polymer at the same time can be used. Specific examples include acetone, methyl ethyl ketone, methyl cellosolve, propylene glycol monomethyl ethyl, ethylene glycol, methanol, ethanol, isopropanol, dimethylformamide, toluene, xylene, and the like.

In the fourth and fifth embodiments of the photosensitive material mentioned above, that is, in the embodiment in which the oil-based medium is directly coated onto the support, the oil-soluble polymer acts as a binder, so it is preferable to use it in a relatively large amount. Specifically, the oil-based medium in the fourth and fifth embodiments 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 an amount of 1 to 90% by weight, 1i1%,
It is more preferable that the content ranges from 40 to 90% by weight and 11%.

The average particle diameter of the solid fine particles of the base precursor in the aqueous dispersion of the base precursor is 0.01 to 30μ.
The thickness is preferably 0.05 to 5 μm, and more preferably 0.05 to 5 μm.

A hydrophilic polymer may be dissolved in the aqueous dispersion of the base precursor. When preparing an aqueous dispersion of a base precursor, it is preferred 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 a 0.1 to 70% by weight aqueous solution.

In the method for producing a photosensitive material of the present invention, the aqueous dispersion of the base precursor described above is emulsified in an oily medium. In emulsification, the average particle size of the droplets of the aqueous base precursor dispersion is preferably 0.1 to 100 μm, more preferably 0.5 to 10 μm.

In the method for producing a photosensitive material of the present invention, the base precursor is preferably used in an amount of 0.5 to 2001π%, more preferably 3 to 30fi%, based on the oil medium.

Hereinafter, the constituent substances used in the method for producing the photosensitive material of the present invention will be described in detail.

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. Particles can also be used.

The halogen composition of the photosensitive silver halide grains may be uniform on the surface and inside, or may be non-uniform. Regarding photosensitive silver halide grains having a multilayer structure with different compositions on the surface and inside, Japanese Patent Laid-Open Nos. 57-154232 and 57-154232 disclose
No. 8-108533, No. 59-48755, No. 59-
No. 52237, US Pat. No. 4,433,048, and European Patent No. 100,984.

There are no particular limitations on the crystal habit of the photosensitive silver halide grains. Two or more types of photosensitive silver halide grains having different halogen compositions, crystal habits, grain sizes, etc. can be used together. There is also no particular restriction on the grain size distribution of the photosensitive silver halide grains.

The average grain size of the photosensitive silver halide grains is 0.00
The range is 1-5 μm, more preferably 0.01-2 μm.

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

The reaction format between soluble silver salt and soluble halogen salt is as follows:
Either one side mixing method, simultaneous mixing method or a combination thereof may be used. A back mixing method in which particles are formed under a silver ion excess condition F and a Chondral double jet method in which PAg is kept constant can also be employed. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Laid-Open No. 55-15812
4, US Pat. No. 3,650,757, IJ).

The photosensitive silver halide emulsion may be of a surface latent image type in which a latent image is mainly formed on the surface of the grains, or of an internal latent image type in which a latent image is formed inside the grains. It is also possible to use a direct reversal emulsion which is a combination of an internal latent image type emulsion and a nucleating agent. An internal latent image emulsion suitable for this purpose is disclosed in U.S. Pat.
No. 50, No. 3761276, 8, Japanese Patent Publication No. 58-3534, Japanese Patent Application Laid-Open No. 58-136641, etc. Preferred nucleating agents for combination with the above emulsions are U.S. Pat.
No. 037, No. 4255511, No. 4266013
No. 4276364, and West German Published Patent Application No. 4276364 (O
LS) No. 2635316.

In the preparation of photosensitive silver halide emulsions, it is preferable to use woody colloids as protective colloids. Examples of hydrophilic colloids include gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, albumin,
Proteins such as casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc., sugar derivatives such as sodium alginate, starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolitone, polyvinyl alcohol, etc. Examples include synthetic hydrophilic polymeric substances such as single or copolymers of acrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. Among these, gelatin is preferred. As gelatin, in addition to coal-treated seratin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

A photosensitive silver halide emulsion is prepared by using ammonia, an organic thioether derivative (see Japanese Patent Publication No. 47-386), and a sulfur-containing compound (Japanese Patent Application Laid-open No. 144319-1988) as a silver halide solvent in the stage of forming silver halide grains. (see publication) etc. can be used. Further, in the process of particle formation or physical ripening, a cadmium salt, a lead salt, a lead salt, a thallium salt, etc. may be allowed to coexist. Furthermore, in order to improve high-light failure and low-light failure, we developed iridium chloride (■
or ■), a water-soluble iridium salt such as ammonium hexachloroiridium salt, or a water-soluble rhodium salt such as rhodium chloride can be used.

The soluble salts may be removed from the photosensitive silver halide emulsion after precipitation or physical ripening. In this case, it can be carried out according to the Tardel water washing method or the precipitation method. The photosensitive silver halide emulsion may be used as it is after ripening, but it is usually used after being chemically sensitized. Sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc., which are known for emulsions for conventional sensitive materials, can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (JP-A-58-126526, JP-A-58-215).
(Refer to each publication No. 644).

In addition, when adding a sensitizing dye to a photosensitive silver halide emulsion, it is preferably added at the stage of preparing the photosensitive silver halide emulsion. In addition, when a nitrogen-containing i-aryl ring compound is added as a compound having an anti-fogging function and/or a development accelerating function, which will be described later, it may be added at the formation stage of photosensitive silver halide grains or during ripening in the preparation of a photosensitive silver halide emulsion. Preferably, it is added in stages.

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

The amount of photosensitive silver halide contained in the photosensitive material (photosensitive layer) is 0.1 in terms of silver including organic silver salt as an arbitrary component.
It is preferable to set it in the range of mg to 10 g/m''.In addition, when converting only silver halide into silver, 0.1 g/rr+
'Preferably less than 1 mg to 90 mg
/nf is particularly preferable.

The photosensitive silver halide sensitizing dye is not particularly limited, and any photosensitive silver halide sensitizing dye known in the photographic technology can be used. Sensitizing dyes include methine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, and the like.

The stiff sensitizing dyes may be used alone or in combination. Especially when the purpose is supersensitization, it is common to use a combination of sensitizing dyes. Further, together with the sensitizing dye, a dye that itself does not have a spectral sensitizing effect, or a substance that does not substantially absorb visible light but exhibits supersensitization may be used in combination.

The amount of sensitizing dye added is generally per mole 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 thermal development processing.

That is, when heated to a temperature of 80° C. or higher, the organic silver salt is considered to participate in an oxidation-reduction reaction catalyzed by the latent image of silver halide. In this case, it is preferable that the silver halide and the organic silver salt are in contact with or in close proximity to each other. Examples of the organic compound constituting the organic silver salt include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Particularly preferred is benzotriazole. The organic silver salt is generally used in an amount of 0.0f-10 mol, more preferably 0.1-1 mol, per mol of silver halide. In addition, instead of organic silver salt,
A similar effect can be obtained by adding the constituent organic compound (eg, benzotriazole) to the photosensitive material.

A compound having an antifogging function and/or a development accelerating function can be used. Photosensitive materials using antifoggants are described in JP-A-62-151838, and compounds having a cyclic amide structure are described in JP-A-62-15.
1841, thioether compounds in JP 62-151842, thiol derivatives in JP 62-151842, acetylene compounds in JP 62-178232, sulfonamide derivatives. For details, see JP-A No. 62-18345.
For quaternary ammonium salts, see Japanese Patent Application Laid-Open No. 63
-91653, respectively.

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

As reducing agents having the above functions, hydroquinones,
Catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 53-aminopyrazoles, 4-amino-5-virazolones, 5-aminouracils, 4.5-dihydroxy-6-aminopyrazoles Midines, reductones, amyl reductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfones Examples include amide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines.

By adjusting the type and amount of the above-mentioned reducing agent, the polymerizable compound can be polymerized either in the area where the silver halide latent image is formed or in the area where the latent image is not formed. For example, when hydrazine is used as a reducing agent, a polymerization reaction can occur in a portion where a latent image of silver halide is formed. In addition, by using 1-phenyl-3-pyrazolidones as a reducing agent and a polymerization initiator that uniformly generates radicals when decomposed by heat or light, it is possible to Can cause polymerization reactions. Regarding the latter, please refer to JP-A-61-
No. 75342, No. 61-243449, No. 62-70
No. 836, No. 62-81635, US Pat. No. 4,649,098, and EP Patent No. 0202490B1.

A reducing agent having the above functions is disclosed in Japanese Patent Application Laid-open No. 61-18364.
No. 0, No. 61-188535, No. 61-228441
No. 62-86354, No. 62-86355, No. 62-264041, and No. 62-198849 (including those described as developers or hydrazine derivatives). Regarding reducing agents, T, J
'The Theory of the P' by ames
Photographic Process 4th edition, 29
pp. 1-334 (1977), Re5search Di
sclosure magazine, Volume 170, June 1978, No. 1
No. 7029 (pages 9-15), and the same magazine Vol. 176, 1
It is also described in No. 17643, December 978 (pages 22-31).

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

These reducing agents may be used alone, or two or more types of reducing agents may be used in combination. In the latter case, the interaction of the reducing agent is, first, to promote the formation of silver halide (and/or organic silver salt) by so-called superadditivity, and second, to promote the formation of silver halide (and/or organic silver salt). The oxidized product of the first raw material produced by the reduction of (or organic silver salt) causes +rU merizable compound combination (or polymerization) through redox reaction with other coexisting reducing agents. ) may be considered. However, in reality, the above reactions occur simultaneously, so it is difficult to specify which effect is responsible.

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-phenyl4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-
4-hexadecyloxy-5-t octylphenol,
2-phenylsulfonylamino-4-t-butyl-5-
hexadecyloxyphenol, 2-(N-butylcarbamoyl)4-phenylsulfonylamine naphthol,
2(N-methyl-N-octadecylcarbamoyl)-4
-Sulfonylaminonaphthol, 1-acetyl-2-phenylhydrazine, 1-formyl-2-(2-methoxyphenyl)hydrazine, 21-formyl-2-(2-chlorophenyl)hydrazine, 1-formyl-2-2-butoxy phenyl)hydrazine, 1-(3,5-dichlorobenzoyl)-2-phenylhydrazine, 1-(3,5
=dichlorobenzoyl)-2-(2-chlorophenyl)
hydrazine, 1-acetyl-2-phenylhydrazine,
1-Acetyl-2-((p- or 0-)aminophenyl)hydrazine,! -formyl-2-((p- or 0
-) aminophenyl) hydrazine,! -acetyl 2-
((p- or 0-)methoxyphenyl)hydrazine,
! -Lauroyl-2-((p- or 0-)aminophenyl)hydrazine, 1-trityl-2-(2,6 dichloro-4-cyanophenyl)hydrazine, 1-trityl-
1-herazine on 2-phenyl, 1-phenyl-2-(2,
4,6-Dolichlorophenyl)hydrazine, 1-(2-
(2,5-t-pentylphenoxy)butyroyl)
-2-((p- or 0-)aminophenyl)hydrazine, 1(2-(2,5-di-t-pentylphenoxy)
butyroyl)-2-((p- or o-)aminophenyl)hydrazine pentadecylfluorocaprylate,
3-indazolinone, 1-trityl 2-[((1-N
-butyl-N-octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, 1- (4-(2
,5-di-t-pentylphenoxy)butyroyl) -
2-((p or 0-)methoxyphenyl)hydrazine51-(methoxylponylhenzohydryl)2-phenylhydrazine, l-formyl-2[4-(2-(2,
4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine, l-acetyl-2-[4-(:2-
(2,4-di-t-pentylphenoxy)butylamido)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-tritylhydrazine, 1-(4-butoxybenzoyl)-2-tritylhydrazine, 1-(2゜4 -dimethoxyhendiyl)-2-1-lythylhydrazine, 1-
(4-dibutylcarbamoylbenzoyl)-2-tritylhydrazine and! -(1-naphthoyl)-2-)lythylhydrazine and the like can be mentioned.

The transition agent is preferably used in an amount of 0.1 to 1500 mol % based on 1 mol of silver (including silver halide and organic silver salt).

There are no particular restrictions on the polymerizable compound, and known compounds can be used. However, it has a high boiling point (
For example, it is preferable to use a compound having a boiling point of 80° C. or higher. Further, a polyfunctional polymerizable compound having two or more polymerizable functional groups in the molecule is preferred. 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 which addition-compatible compounds are particularly preferred.

These compounds include (meth)acrylic acid and its salts or esters, (meth)acrylamides, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and There are derivatives of

Specific examples of polymerizable compounds include n-butyl acrylate, cyclohexyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethyl acrylate, dicyclohexyloxyethyl acrylate,
Nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylated bisphenol Diacrylate of A, diacrylate of condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane, triacrylate of condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol, hydroxypoly Ether polyacrylate, polyester acrylate, polyoxyethylenated bisphenol F diacrylate, polyurethane acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, and some or all of the acryloyl groups of the above polymerizable compounds are converted into methacryloyl groups. Examples include those with substitutions. These compounds can also be selected from commercially available products. Specific examples include Kayalad R-604, R-684, R-712,
R-310, R-167, HX220 (manufactured by Nippon Kakane Kogyo), Aronix M-309, M-310%
Examples include M-400 and M-210 (manufactured by Toagosei Kagaku ■).

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

The polymerizable compound is preferably used in an amount of 50,000 to 100,000 parts by weight per 1 part by weight of the photosensitive silver halide. The more preferable usage range is! 0～toooo stoneq
Department.

-- of --: In order to stably emulsify and finely disperse an aqueous liquid such as a silver halide emulsion or an aqueous dispersion of a base precursor in an oily medium such as a polymerizable compound, a method using a copolymer as a dispersant is used. preferable. Preferably, the copolymer is dissolved in an oily medium prior to emulsification. For specific examples and usage examples of copolymers, see JP-A-62-209449 and JP-A-62-209449.
It is described in each publication of No. 3287844.

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

Precursor: Base precursors include salts of carboxylic acids (decarboxylated by heating) and bases, compounds that release amines through reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, Beckmann rearrangement, etc. It is preferable to use a compound that releases a base upon reaction. More preferred are salts 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
Examples include guanidine -toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonylacetate, guanidine 4-chlorophenylsulfonylacetate, guanidine 4-methyl-sulfonylphenylsulfonylacetate, and guanidine 4-acetylaminomethylpropiolate.

As described in JP-A-63-316760, the base precursor is a salt consisting of a carboxylic acid and an organic base, in which the organic base removes one hydrogen atom from an amidine represented by the following formula (I). or a base precursor that is an acid to tetraacid base consisting of 2 to 4 partial structures corresponding to the atomic group with 2 removed, and one or more hydrocarbon residues or heterocyclic groups as a linking group for the partial structures. is particularly preferred.

R1, R2, R3 and R4 in the above formula (I) are each selected from the 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 the basis of valence. Among these, hydrogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups and aryl groups are preferred. Note that the 8 groups may have one or more substituents.

The number of carbon atoms in the alkyl, alkenyl, and alkynyl groups is preferably 1 to 6. Examples of the cycloalkyl groups include cyclohexyl groups. Examples of the aralkyl groups include benzyl groups. Aryl An example of a group is a phenyl group.

Any two groups of RI R2)j3, )j4 are
They may be bonded to each other to form a 5- or 6-membered heterocycle consisting of a nitrogen atom and a carbon atom.

Note that R1 and R2 are bonded to each other to form the following formula (I-
It is particularly preferable that it constitutes a cyclic amidine represented by 2).

RI5 in the above formula (I-2) is two groups selected from an ethylene group, a propylene group, a trimethylene group, a vinylene group, and a propenylene group. Note that the 8 groups may have one or more substituents. Among these, ethylene, propylene, and trimethylene groups are particularly preferred. That is, cyclic amidines include 2-imidacillin, 1,4,5. “6
-Tetrahydropyrimidine or a derivative thereof is preferred, and 1,4,5,6-tetrahydropyrimidine or a derivative thereof is particularly preferred.

R16 is the same as R3 in formula (I). Particularly preferred is a hydrogen atom or an alkyl group. R" is the same as R4 in formula (I). A hydrogen atom is particularly preferred.

The cyclic amidine of formula (I-2) may be fused with other heterocycles, aliphatic groups (eg, cyclohexane), and/or aromatic rings.

As described in JP-A No. 64-68746, the base precursor is a salt consisting of a carboxylic acid and an organic base, where the organic base is one hydrogen atom removed from guanidine represented by the following formula (rV). Or a diacid or a defined base (total carbon Particularly preferred are base precursors in which the number of atoms is 6 times or less the number of substructures.

In the above formula (IV), R4I-R" is 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, respectively. (Each store may have one or more substituents), 1lt41 ft4
', any two groups selected from
It may form a 5- or 6-membered heterocycle consisting of a central atom and a carbon atom.

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

A color image-forming substance (in an image-forming composition) can be used as an optional component (in an image-forming composition) In the present invention, known pigments and dyes are added as color image-forming substances (colorants). be able to. The type, hue, and amount added are arbitrary. These make images after development visible, and are also effective as antihalation or irradiation agents.

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

As the color image-forming substance, a dye precursor that develops color by reacting with another substance can be used.

These are various systems that generate color through acid-base reactions, redox reactions, coupling reactions, chelate-forming reactions, etc. between two or more components. ) Pressure-sensitive copying paper (29
Known coloring systems such as azography (pages 87-95), thermal coloring by chemical change (pages 11B-120) can be used.

Specifically, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, spiropyran, etc. used in non-carbon paper, and an acidic substance (color developer) such as acid clay or phenols: aromatic diazonium salt. Systems that use azo coupling reactions of diazotate, diazosulfonates, naphthols, anilines, activated methylenes, etc.; reactions of hexamethylenetetramine with ferric ions and gallic acid, and reactions of phenolphthalein-combrecranes with alkalis. Chelate-forming reactions such as reactions with earth metal ions; redox reactions such as reactions between ferric stearate and pyrogallol and reactions between silver behenate and 4-methoxy-1-naphthol are used.

The color image-forming substance is 0.5-30% by weight of the polymerizable compound.
A range of is preferred.

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

Thermal polymerization initiators are described, for example, in ``Addition Polymerization/Ring-Opening Polymerization'' (Kyoritsu Shuppan, 1983) by the Editorial Committee of the Japan Society for Polymer Science and Technology, pp. 6-18. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1.
l゛-azobis(1-cyclohexanecarbonitrile)
, dimethyl 2,2'-azobisisobutyrate, 2,2
Azo compounds such as azobis(2-methylbutyronitrile), azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. Organic peroxides, inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate,
Examples include sodium p-toluenesulfinate.

Light I [intermediate initiator is, for example, Che
micat Review J Volume 68 (1968)
1251s t (H and Kosar r Lig
hL-5intensive 5yste+++7 (
John 1fiLIcy & 5ons, 1965
Carbonyl compounds (e.g., α-alkoxyphenyl ketones, polycyclic quinones, benzophenone derivatives 2 xanthones, thioxanthones, hengeynes), halogen-containing compounds ( For example, chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylhensiphenones (5 fluorenones), haloalkanes, α-halo α-phenylacetophenones, optical elements redox couples between the sex pigment and the y-group, organic sulfur compounds, peroxides, light chloride, monomers (e.g., titanium dioxide,
Zinc oxide), metal compounds (e.g. iron(I) salts, metal carbonyls, metal complexes, uranyl salts), silver halides, azo and diazo compounds, U.S. Pat. No. 4,772.530
Compounds consisting of an ionic dye and a counter ion described in No. 2003-11-3 are used.

Specific examples of photopolymerization initiators include 2-dimethoxy-2-
Phenylacetophenone, 2-methyl(4-(methylthio)phenyl)-2-morpholino-1-propanone, henzoinptyl ether, benzoin isopropyl ether, hensifhenone, Michler's ketone, 4,4°
-diethylaminenohenzophenone, chloromethylbenzophenone, chlorosulfonylbenzophenone, 9゜1
0-anthraquinone, 2-methyl-9,10-anthraquinone, chlorosulfonylanthraquinone, chloromethylanthraquinone, 9.10-zenathraquinone, xanthone, chloroxanthone, thioxanthone, chlorothioxanthone, 2,4-diethylthioxanthone, Examples include chlorosulfonylthioxanthone, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, fluorene, carbon tetrabromide, and the like. Examples of photoreducible dyes include methylene blue, thionine, rose hengal, erythrosin-β, eosin, rhodamine, phloxine-β, safranin, acriflahine, rifoflavin, fluorescein, uranine, benzoflavin, acridine orange, and acridine yellow. , Henzanthrone, etc.

Examples of the quinary agent (hydrogen-bearing compound) used with these dyes include β-diketones such as dimedone and acetylacetone, and triethanolamine.

Amines such as jetanolamine, monoethanolamine, diethylamine, triethylamine, sulfinic acids such as p-toluenesulfinic acid and hensensulfinic acid and their salts, N-phenylglycine, L-ascorbic acid and its salts, thiourea , allylthiourea, etc. The molar ratio of photoreducible pigment and mouth agent is 11
A range of 0.01-1/10 is preferred.

As the photopolymerization initiator, commercially available ones such as "Irgacure 651 and Irgacure 907°" manufactured by Ciba Geigy are also suitably used.

The polymerization initiator is 0°001-0 per 1g of polymerizable compound.
．． It can be used in an amount of 5g, more preferably 0.01-0.2g.

Support materials include paper, synthetic paper, paper laminated with synthetic resin (e.g. polyethylene, polypropylene, polystyrene, etc.), plastic film (e.g. polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate, etc.) , a metal plate (for example, aluminum, aluminum alloy, curved lead, iron, copper, etc.), paper or plastic film on which the above-mentioned metals are laminated or vapor-deposited, etc. are used.

″ of microcapsules: When an oil-based imaging composition (or 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. Examples of microencapsulation methods include methods utilizing coacervation of lignophilic wall-forming materials as described in U.S. Pat. Nos. 2,800,457 and 2,800,458; 3
No. 287154, British Patent No. 990443, and the interfacial polymerization method described in Japanese Patent Publications No. 38-19574, No. 42-446, and No. 42-771; Polymer precipitation method described in each specification; U.S. Patent No. 3
Methods using isocyanate-polyol wall materials described in US Pat. No. 796,669; Methods using isocyanate wall materials described in US Pat. No. 3,914,511; US Pat.
A method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall material as described in each specification of No. 089802; US Pat. No. 502,545
Melamine-formaldehyde resin described in specification No. 5,
Method using wall materials such as hydroxypropyl cellulose; Japanese Patent Publication No. 36-9168 and Japanese Patent Application Laid-open No. 51-9079
1n-sit by polymerization of 1,000 yen as described in each publication of No.
U method; British Patent Nos. 927807 and 965074
Polymerization dispersion cooling method described in each specification a of No. 3: U.S. Patent No. 31
Examples include the spray drying method described in each specification of No. 11407 and British Patent No. 930422.

The wall materials constituting the outer shell of the microcapsules include 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, and polyurethane resin. Particularly preferred are composite resins of polyester resin and polyester resin.

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

Preferably, at least 70% by weight of the silver halide contained in the microcapsules is present in the wall material constituting the capsule shell. The silver halide particles encapsulated in the microcapsules are preferably one-fifth or less of the particle size of the microcapsules, and the number of silver halide particles contained in - microcapsules is preferably 5 or more. .

z1 koshi bill stop Image-receiving materials are generally prepared by providing an image-receiving layer on a support.

The image-receiving layer can contain various compounds depending on the color-forming system of the color image-forming material.

When the color image-forming substance is a dye precursor that develops color by reacting with a color developer, the image-receiving layer preferably contains the color developer. When the color image-forming substance is a dye, the image-receiving layer can include a mordant. The mordant can be selected from compounds known in photography and the like. The image-receiving layer can contain a polymer as a binder. As the binder, the polymer used in the photosensitive layer of the photosensitive material is used. The image-receiving layer can include particulate powder.

The powder may be a colorless inorganic pigment (for example, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, etc.) or may be a colorless inorganic pigment (e.g., calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, etc.),
Thermoplastic organic substances (for example, polymer waxes such as polyethylene, polypropylene, polytetrafluoroethylene, etc.) described in Japanese Patent No. 0739 may also be used.

These powders have the effect of increasing the density of color development by increasing the porosity in the image-receiving layer and increasing the amount of oil absorption. When a thermoplastic powder is used, the image-receiving layer can be made glossy or transparent by heating after transfer. Also, a special application for 1986-31
As described in No. 3483 and No. 62-313484, it is also possible to use an image-receiving layer which is phase-separated using two or more binder polymers that are hardly 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 in the range of 0.1-100 μm, more preferably 1-20 μm.

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

irin process: To form an image, a light-sensitive material is uniformly heated after or simultaneously with imagewise exposure. The silver halide on which the latent image has been formed by heating is thermally developed, and at the same time, the polymerizable compound in that area (or in the area where the latent image is not formed) is polymerized and the oil phase or microcapsules are hardened. Thereafter, the photosensitive material is brought into close contact with the image-receiving material and pressurized and/or heated to transfer the uncured oil droplets or the oil phase in the microcapsules to the image-receiving material, forming a colored image thereon, or forming a colored image thereon. A colored image is formed on the photosensitive material by dissolving and removing the photosensitive layer on the photosensitive material using a solvent (water, alkali, acid, organic solvent, etc.). In the case of the embodiments shown in Figs. 1 to 3, the former (transfer method) is preferable, and in the case of the embodiments shown in Figs. 4 to 5, the latter (dissolution method).
Or preferable.

Exposure is performed using a light source that emits light of a wavelength corresponding to the spectral sensitivity (sensitizing dye) of the silver halide. For example, lamps such as tungsten lamps, halogen lamps, xenon lamps, mercury lamps, carbon arc lamps, various lasers (semiconductor lasers, helium neon lasers, argon lasers, helium cadmium lasers, etc.), light emitting diodes, CRT tubes, etc. are used. It will be done. Generally, the exposure wavelength is preferably visible light, near ultraviolet light, or near infrared light. The exposure amount is mainly determined by the sensitivity of the silver halide emulsion, but is generally 0.01-10.000 ergs/cm', more preferably 0.000 ergs/cm'. It is in the range of 1-1,000 ergs/clo2.

Heating can be accomplished by contacting a heated object (for example, a plate or roller), heating with radiant heat from an infrared-rich lamp, or immersing in a medium such as heated oil. In order to reduce the inhibition of the polymerization reaction by oxygen in the air that enters during heating, it is preferable to cover the surface of the photosensitive material with a substance that does not easily allow oxygen to pass therethrough before heating. For example, a method of bringing the surface of the photosensitive material into close contact with a heated object is preferred. The heating temperature is 80-200°C, more preferably 10
It is in the range of 0-150°C. The heating time is 1-1
80 seconds, more preferably 5-60 seconds.

The present invention will be explained in more detail with reference to the following examples. However, the present invention is not limited to these.

[Example 1] Precursor - Powder 2 of the following base precursor (mostly insoluble in water)
00g was dispersed in 800g of a 3% by weight aqueous solution of polyvinyl alcohol using a Dynomyl disperser. The particle size of the base precursor was less than O.S.mu.m.

100 g of this dispersion was mixed with 200 g of water and concentrated using a centrifuge to obtain a base precursor concentration of 64% by weight.
An aqueous dispersion was obtained.

(Base precursor) Halogen $ 1, 1 Stirring aqueous gelatin solution (containing 16 g of gelatin and 0.5 g of sodium chloride in 1500 ml of water, IN < 7) Tep sulfate H3, 2, 1 liter, kept warm at 50°C 300 mJ of an aqueous solution containing 71 g of potassium bromide!
and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 300 ml of water) were simultaneously added at equal flow rates over 50 minutes. One minute after this is finished, the following sensitizing dye (A
) was added, and 15 minutes after addition of the sensitizing dye, 100 ml of an aqueous solution containing 2.9 g of potassium iodide was added! and a silver nitrate aqueous 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(imbutylene-monosodium co-maleate) was added and precipitated, washed with water and salted, 12 g of gelatin was added and dissolved, and further 0.5 mg of sodium thiosulfate was added.
Chemical sensitization was carried out at 0°C for 15 minutes, and the average particle size was 0.
22 μm monodispersed tetradecahedral silver iodobromide emulsion (A) 1000
g was prepared.

(Sensitizing dye (A)) A stirring gelatin aqueous solution (containing 20 g of gelatin and 0.5 g of sodium chloride in 1,600 mf of water, purified with IN sulfuric acid)
200 ml of an aqueous solution containing 71 g of potassium bromide (adjusted to H3.2 and kept at 42°C)! and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 200 mf of water) were simultaneously added at equal flow rates over 30 minutes. One minute after this was completed, 48 ml of a 1% methanol solution of the following sensitizing dye (B) was added, and 10 minutes after addition of the sensitizing dye, 10 minutes of an aqueous solution containing 2.9 g of potassium iodide was added.
0m1! and silver nitrate aqueous solution (silver nitrate 0.0.
018 mol dissolved) was added simultaneously over a period of 5 minutes. To this emulsion, 1.2 g of poly(imbutylene-monosodium co-maleate) was added and precipitated, washed with water to desilver, then 18 g of gelatin was added and dissolved, and further 0.7 mg of sodium thiosulfate was added and the mixture was heated at 60°C. So 15
Chemical sensitization was carried out for 1 minute to prepare 1000 g of a monodispersed tetradecahedral silver iodobromide emulsion (B) having an average grain size of 0.12 μm.

(Sensitizing dye (B)) A gelatin aqueous solution (containing 20 g of gelatin and 0.5 g of sodium chloride in 1,600 mJ of water, adjusted to pH 3.5 with 1N sulfuric acid, and kept at 45°C) has an odor. 200 mJl of an aqueous solution containing 71 g of potassium chloride and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in 200 mff1 of water) were simultaneously added at equal flow rates over 30 minutes. 1 minute after this is finished, 0 of the following sensitizing dye <C>
．． 48 m2 of a 5% methanol solution was added, and 15 minutes after addition of the sensitizing dye, a 100 mM aqueous solution containing 3.65 g of potassium iodide and an aqueous silver nitrate solution (0.022 mol of silver nitrate dissolved in 100 ml of water) were simultaneously added for 5 minutes. It was added over a period of time. 1.2 g of poly(imbutylene-63 sodium comaleate) was added to this emulsion and precipitated.
After washing with water and desalting, add 10g of gelatin and dissolve.
Further, 0.45 mg of sodium thiosulfate was added and chemical sensitization was carried out at 55°C for 20 minutes to obtain an average particle size of o, i.
1000g of 3μm monodispersed 14-hedral silver iodobromide emulsion (C)
was created.

(Sensitizing dye (C)) In 100 g of trimethylolpropane triacrylate (polymerizable compound), the following yellow image forming substance 15
g was dissolved to obtain an oil phase.

Into 60 g of this oil phase, 1.8 g of the following Copo Blade Mer was dissolved. To this was added 16.6 g of the aqueous base precursor dispersion prepared as described above, and the mixture was stirred using a homogenizer at 7,000 revolutions per minute for 60 minutes to emulsify the base precursor aqueous dispersion into the oil phase. Note that during this stirring, most of the water in the aqueous dispersion evaporated, but some water remained.

To 59 g of this emulsion, 3.9 g of the following hydrazine compound (reducing agent), 3.3 g of the following developer (reducing agent), 0.05 g of the following mercapto compound precursor, 0.01 g of the following mercapto compound, and the following interface Activator 0.5
g was dissolved.

Furthermore, in the obtained emulsion, 8 g of the silver halide emulsion (A) described above and 1.3 g of a 10% aqueous solution of potassium bromide were added.
A mixed solution was added thereto and stirred using a homogenizer at 40° C. and 10,000 revolutions per minute for 10 minutes to prepare a photosensitive composition in an oil phase state.

(Yellow color image forming substance) (Copolymer) (Hydrazine compound) (Developer) (Mercapto compound precursor) (Mercapto compound) (Magenta color image forming substance) (Surfactant) (n m a, 5l PIl, B In addition to the above photosensitive composition (A), an electrophotosensitive composition (B) was prepared in the same manner as above except for some changes as shown below.
was created.

Instead of the yellow image forming substance, 124 g of the magenta image forming material shown below, 0.015 g of the mercapto compound instead of 0.01-, and 1 silver halide [□Agent (A)'
Silver halide emulsion (B) 8g'? 'Use.

″ □ □The photosensitive composition (A
), a photosensitive composition (0) was prepared in the same manner as in Example 1, except for some changes as described below. ...In place of the yellow white image forming material, 19'g of the following cyan image forming substance, 0.0.075 g in place of 0.01 g'' of the mercapto compound, and in place of the silver halide emulsion (A), 8 g of silver halide emulsion (C) is used.

′　　　　□.

(Cyan color image forming substance) In the photosensitive group Ij, th'' (1:) described above, an isosite compound (takenite D''116'□N'wtB':lI' product□ (manufactured by Kogyo ■) was dissolved and dissolved. Add the solution from above to 3 g of a 10% ice solution of sodium salt of polystyrene sulfosic acid (product p'VergaTL502, manufactured by National Starch), and add it to 3 g of a 10% ice solution at 40°C using a hodgenizer. The photosensitive composition was emulsified in an aqueous solvent by stirring for 30 seconds at a rotation speed of 9,000 min.

While stirring the supernatant aqueous emulsion at 25°C and 1200 revolutions per minute, add melamine-formaldehyde prepolymer (34.5 g of melamine to 186 g of water and 57 g of formalin).
32 g of the saliva obtained by stirring at 60° C. for 30 minutes at 600 revolutions per minute were added, and the pH was adjusted to 6. Heat this solution to 60℃ for 1 minute 12
After stirring at 0.00 rpm for 90 minutes, the pH was adjusted to 7.0, and a late solution (A) of Ji II photosensitive microcapsules was prepared.

h & □ Microcapsules B Photosensitized in the same manner except that the photosensitive microcapsule dispersion liquid (A) is replaced by the photosensitive □ composition (B) instead of the photosensitive composition (A). A microcapsule dispersion (B→) was prepared.

14-' Microcapsules □ ゛ The same process is carried out except that the photosensitive composition (C) is placed in the capsule dispersion (A) and the photosensitive composition (C) is used instead of the photosensitive composition (A). A photosensitive microcapsule dispersion (C) was prepared.

``Minsuyama'' 111 ``''□ 20 parts of LBSP and LB were beaten with P2O to 290cc of Canadian Freeness (C3F) using a refinery, and alkyl ketene dimer (Accobel 12, Dick Bercules Co., Ltd.) was added as a neutral sizing agent. ) 0.3 part, polyamide polyamine epichlorohydrin (
Kaimen 557, manufactured by Dick Vercules Co., Ltd.) 0.5 part, and cation-modified polyacrylamide (trade name: Polystron 705, manufactured by Arayo Kagaku ■) as a paper strength agent 0
．． 5 parts were added in each case based on the absolute dry weight ratio of the pulp. Next, the above paper stock was made into a base paper having a weight of 60 g/ba and a thickness of 66 μm using a Fourdrinier paper machine.

A coating liquid for forming a moisture-proof layer made of polyvinylidene chloride resin, 100 parts of SBR latex (product name: 5N-304, manufactured by Sumitomo Naugatack ■), and polyacrylic were applied to the surface (felt surface) of the base paper produced as described above. 1 part sodium acid (trade name: Nearon T40, manufactured by Toagosei Chemical Industry ■), clay (trade name: UW-90, manufactured by Engelhard)
200 parts, and petroleum resin (trade name - Carbomul R,
A moisture-proof layer forming coating solution having a composition of 100 parts (manufactured by Dick Vercules) was prepared, and the coating solution was sequentially coated with an air knife coater until the weight was 16 g/m''.
, 5 g/rr1'' coating amount to prepare a paper support.

Photosensitive microcapsule dispersions (A), (B) and (
A coating solution for a photosensitive layer was prepared by adding 10 g of C), 2 g of a 5% aqueous solution of the surfactant, 2.5 g of a 40% aqueous solution of urea, and 40 g of water.

This coating solution was applied onto the paper support to a dry film thickness of approximately 10 μm.
A full-color photosensitive material was prepared by coating and drying so as to give m.

11 and to fraud 1 2.5 g of sodium hexametaphosphate to 123 g of water
22 g of zinc 3.5-di-α-methylbenzylsalicylate and 53 g of 55% calcium carbonate slurry were further mixed therewith and dispersed using a Dynamyl disperser. To 40 g of the obtained liquid were added 10 g of an 8% polyvinyl alcohol aqueous solution, 4 g of a 10% gelatin aqueous solution, 1.6 g of zinc chloride, and 34 g of water and mixed uniformly.

Spread this mixture onto art paper with a basis weight of 43 g/♂ to a thickness of 90 μm.
After coating to a wet film thickness of , it was dried to produce an image receiving material.

11 and skin 51 The photosensitive material obtained as above was imagewise exposed for 1 second at an illuminance of 2000 lux using a halogen lamp through a step wedge, and then the photosensitive material was placed on a hot plate heated to 155°C. were brought into close contact and heat developed. Next, the photosensitive material was layered with the above-mentioned image-receiving material, and in that state it was weighed at 500 kg.
/ crn'' pressure roller, a positive image was obtained on the image-receiving material for a black original (wedge). Heating required to obtain an image with a minimum density of 0.1 or less The time was about 7 seconds.

[Comparative Example 1] 15 g of the yellow image forming substance of Example 1 was dissolved in 10 og of trimethylolpropane triacrylate to obtain an oil phase. In 49 g of this oil phase, the following were used in Example 1:
Copolymer 1.8g, hydrazine compound 3.9g, developer 3.3g, mercapto compound precursor 0.05
g, 0.01 g of mercapto compound and 0.01 g of surfactant.
5g was dissolved. Furthermore, 8 g of the silver halide emulsion (A) of Example 1 and a 10% aqueous solution of potassium bromide!
, add 3g of the mixture and use a homogenizer to
A photosensitive composition (A) was prepared by stirring at 10,000 revolutions per minute at a temperature of 10,000 rpm for 10 minutes.

It&B It& A photosensitive composition (B) was prepared in the same manner as the photosensitive composition (A) except for changing some parts as described below.

24 g of the magenta color image forming material of Example 1 instead of the yellow image forming material, 0.015 g of the mercapto compound instead of 0.01 g, and instead of the silver halide emulsion (A),
8 g of the silver halide emulsion (B) of Example 1 is used.

CM A photosensitive composition (C) was prepared in the same manner as the photosensitive composition (A), except for some changes as described below.

In place of the yellow imaging material, the cyan color of Example 1 □
19 g of the image forming substance, 0.0075 g of the mercapto compound instead of 0.01 g, and 8 g of the silver halide emulsion (C) of Example 1 instead of the silver halide emulsion (A) were used.

A photosensitive microcapsule dispersion (
A), (B) and (C) were prepared respectively.

Base precancer powder 200 used in Example 1 of Breaker
g was dispersed in 800 g of a 3% by weight aqueous solution of polyvinyl alcohol using a Dynomyl disperser to obtain an aqueous base precursor dispersion/dispersion.

10 g of each of the photosensitive microcapsule dispersions (A), (B) and (C) prepared as above, and 7 g of the aqueous dispersion of the base precursor used in Example 1. A coating solution for the photosensitive layer was prepared by adding 2 g of a 5% aqueous solution of a surfactant, 2.5 g of a 40% aqueous solution of urea, and 33 g of water.

This coating solution is coated on the paper support used in Example 1 to a dry film thickness of about 10 μm and dried to produce a photosensitive material containing a base precursor in the photosensitive layer outside the photosensitive microcapsules. was created.

When an image was formed on an image-receiving material using the photosensitive material obtained as described above in the same manner as in Example 1, the heating time required to obtain an image with a minimum density of 0.1 or less was approximately 17 It was seconds.

[Comparative Example 2] 15 g of the yellow image forming substance of Example 1 was dissolved in 100 g of trimethylolpropane triacrylate to obtain an oil phase. Into 85 g of this oil phase, 15 g of powder of the base precursor (mostly insoluble in the oil phase) used in Example 1 was dispersed using a Dyno Mill disperser. The particle size of the base precursor was 0.5 μm or less.

59 g of the oil phase in which the base precursor was dispersed in this way
1.8 g of Copo Limer used in Example 1,
Hydrazine compound 3.9g, developer 3.3g, mercapto compound precursor 0.05g, mercapto compound 0
．． 01 g and 0.5 g of surfactant were dissolved. Further, a mixture of 8 g of the silver halide emulsion (A) of Example 1 and 1.3 g of a 10% potassium bromide aqueous solution was added thereto, and the mixture was stirred for 10 minutes at 40° C. and 10,000 revolutions per minute using a homogenizer. A photosensitive composition (A) was prepared.

A photosensitive composition (B) was prepared in the same manner as the above photosensitive composition (A) except for changing some parts as follows.
Manufactured. □24g of the mazezota color image-forming material of Example 1 instead of the yellow image-forming material
, 0.015 mercapto□ compound instead of 0.01 g
g, silver halide emulsion (A゛) □Instead, Example 1
□ Using 8 g of silver halide emulsion (B)'.

A photosensitive composition (C) was prepared in the same manner as in the photosensitive composition (A) except that a part of the photosensitive composition (A) was changed to ``as in 1''. ′ □: I □ Erotic image composition i ``In exchange for quality, □ Actual: cyan image of bowl 1''
19 g of the □-form acid substance, 0.0075 g of the mercapto-containing pot □ material instead of 0.01 g, and 8 g of the silver halide emulsion (C) of Example 1 were used instead of the silver halide emulsion (A).

A photosensitive microcapsule dispersion (
A), (B) and (C) were each produced separately.

11 A photosensitive material was prepared in the same manner as in Example 1 except that the photosensitive microcapsule dispersion prepared as described above was used.

When an image was formed on an image-receiving material using the photosensitive material obtained as described above in the same manner as in Example 1, the minimum density of the image was 3.
Even after heating for 0 seconds, the value was 0.7, and virtually no image was 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 fast development rate 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.

10 g of photosensitive composition (A) was added to 50 g of 10% aqueous polyvinyl alcohol using a homogenizer.
The mixture was emulsified by stirring at 000 rpm for 5 minutes to prepare a photosensitive emulsion (A). Similarly, photosensitive compositions (B) and (C) were respectively emulsified to create photosensitive emulsions (B) and (C).

1 each of photosensitive emulsions (A), (B) and (C)
Example!0g and 40g of water mixed together! A full-color photosensitive material was prepared by coating the mixture on a paper support to a dry film thickness of approximately 10 μm and drying.

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

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

In preparing the photosensitive composition (B) of Example 1, except for the emulsification step of the mixture of the silver halide emulsion and the potassium bromide aqueous solution, the process was carried out in exactly the same manner as above, and a composition containing no silver halide was prepared. (B) was created.

Next, 10 g of the above composition was added to 50 g of a 10% aqueous solution of polyvinyl alcohol using a homogenizer.
The mixture was emulsified by stirring at 00 rpm for 5 minutes to prepare an emulsion (B).

30 g of the above emulsion (B), 0 of the above silver halide emulsion
．． 5 g and 40 g of water were mixed, coated on the paper support of Example 1 to a dry film thickness of about 10 μm, and dried to prepare a photosensitive material.

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

[Brief explanation of the drawing]

1 to 5 are schematic cross-sectional views showing various aspects of photosensitive materials 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 Patent applicant
Fuji Photo Film Co., Ltd. Representative Patent Attorney Yasushi Yanagawa Figure 1 Figure 2 Figure 3 Figure 4 Figure 5

Claims (1)

[Claims] 1. A method for producing a photosensitive material, in which a photosensitive layer containing a photosensitive silver halide, a reducing agent, a base precursor, and a polymerizable compound is provided on a support, in an oil-based medium containing 0.1 to 100% by weight of the polymerizable compound. A method for producing a photosensitive material, comprising the step of emulsifying an aqueous dispersion of a base precursor.