JPH0619565B2 - Photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive material having on a support a photosensitive layer containing a silver halide, a reducing agent, a polymerizable compound and a color image-forming substance (leuco dye).

BACKGROUND OF THE INVENTION A light-sensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is suitable for an image forming method in which a latent image of silver halide is formed and the polymerizable compound is polymerized. Can be used.

As an example of the image forming method, Japanese Patent Publication No. 45-11149.
No. 47-20741, No. 49-10697, JP-A Nos. 57-138632 and 58-169143. In these methods, when the exposed silver halide is developed using a developing solution, the reducing agent is oxidized and at the same time, the coexisting polymerizable compound (eg, vinyl compound) initiates the polymerization, resulting in high image quality. It forms a molecular compound. Therefore, the above method requires a developing treatment using a liquid, and the treatment requires a relatively long time.

Also, a patent has already been filed for a method capable of forming a polymer compound by dry treatment (Japanese Patent Laid-Open No. 61-69).
062). In this method, a recording material (photosensitive material) having a photosensitive layer composed of a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder supported on a support is imagewise exposed. To form a latent image, and then by heating, a polymer compound is formed on the portion of the photosensitive silver salt where the latent image is formed. That is, this image forming method is a method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is formed.

As one aspect of the image forming method, a light-sensitive material having a photosensitive layer containing a silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance on a support is imagewise exposed simultaneously or after the imagewise exposure. A patent has already been filed for an image recording method characterized by carrying out a developing treatment to polymerize and cure a polymerizable compound, thereby immobilizing a color image forming substance in a cured portion (Japanese Patent Laid-Open No. 61-73145). Issue).

A leuco dye is used as an example of the color image forming substance used in the color image forming method. The leuco dye is also called a reduction dye, and is a compound that exhibits a color reaction when brought into contact with an acidic substance (developing agent).

The leuco dye can easily obtain a color image by allowing the dye to coexist on a recording paper in a state of being separated from an acidic substance by using a method such as microencapsulation, and pressing and contacting both during use. As an image forming substance to be used, its usefulness has been found from early on for pressure sensitive paper.

By the way, as for the leuco dye exhibiting a black color, for example, JP-B-48-43296 and JP-A-55-265 is known.
Nos. 56-109251 and 58-7453. It is described that these leuco dyes exhibit excellent color forming properties when used in various recording materials such as the pressure sensitive recording paper and the heat sensitive recording paper.

The present inventors have studied a leuco dye (black) which is used in the above-mentioned light-sensitive material, exhibits a high color-forming property, and has high sensitivity and excellent image quality. As a result, it has been found that the leuco dye (black) described in each of the above publications may not always provide sufficient color developability when used in a light-sensitive material. That is, when a leuco dye is made to coexist with the above-mentioned constituents in the photosensitive layer of the photosensitive material, the leuco dye may be affected during the image forming (reaction) process and its color forming function may be impaired. .

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent light-sensitive material capable of obtaining a clear color image. In particular, the present invention aims to provide a light-sensitive material containing a black image-forming substance (leuco dye).

Another object of the present invention is to provide a light-sensitive material capable of obtaining a color image having a high contrast and a clear image quality.

The present invention resides in a light-sensitive material having, on a support, a light-sensitive layer containing a silver halide, a reducing agent, a polymerizable compound, and a leuco dye represented by the following general formula [I] as a black image forming substance.

[Wherein R ¹ and R ² and R ³ and R ⁴ may be the same or different from each other and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R ¹ , R ² and R ³ And R ⁴ may combine with an adjacent nitrogen atom to form a 5- or 6-membered ring,
⁵ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group, R ⁶ represents a hydrogen atom, a halogen atom, a nitro group, or a group represented by —NHCOR ⁷ (R ⁷ represents an alkyl group or an aryl group. Represents a group), and the above-mentioned substituents may be further substituted with other substituents.] [Effect of the Invention] The above-mentioned general formula [I]
By using the leuco dye represented by (black image forming substance), the maximum density is high and the minimum density is low,
That is, an image with high contrast can be obtained. Therefore,
When an image is formed using the light-sensitive material of the present invention, an extremely clear black image can be obtained.

Further, in the light-sensitive material of the present invention containing the above leuco dye, for example, another leuco dye having a different hue (yellow,
Magenta or cyan image forming substance) is used alone or in appropriate combination of two kinds, whereby a color image can be recognized as a clearer image according to each hue. That is, a plurality of bright color images can be obtained.

In particular, for a full-color image, for example, leuco dyes having different hues (yellow, magenta, or cyan image forming substances) are contained in three types of microcapsules having different photosensitivity, respectively, and these are allowed to coexist in the photosensitive layer. Although it can be easily obtained by using the light-sensitive material of the aspect, by containing the leuco dye according to the present invention in the light-sensitive layer contained in a microcapsule different from the three types of microcapsules at that time, It is possible to obtain a clearer full-color image with higher contrast.

[Detailed Description of the Invention] The leuco dye used in the light-sensitive material of the present invention is a compound represented by the following general formula [I].

In the general formula [I], the alkyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ has 1 to 22 carbon atoms (more preferably,
1 to 12) is preferable. Further, these may have a straight-chain structure or have a branch, and may be substituted with a substituent such as a halogen atom, a cyano group, an alkoxy group or a hydroxy group.

Examples of the cycloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a cyclopentyl group, a cycloheptyl group, a cyclooctyl group and the like.

Examples of the aralkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a benzyl group and a phenethyl group, and a halogen atom, a nitro group, a cyano group, a lower alkyl group (having 1 carbon atom). To 4), and a lower alkoxy group (having 1 to 4 carbon atoms).

Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include a phenyl group, which may be substituted with the substituents mentioned as the substituents of the above aralkyl group.

R ¹ and R ² and R ³ and R ⁴ together with the nitrogen atom to which they are bonded may form a 5- or 6-membered ring.

The halogen atom represented by R ⁵ and R ⁶ is C
, Or Br.

The alkyl group portion of the alkoxy group and the alkylthio group represented by R ⁵ preferably has 1 to 12 carbon atoms. It may be substituted with a halogen atom, a cyano group, an alkoxy group, a hydroxy group, or the like.

The alkyl group and aryl group represented by R ⁷ have the same meanings as R ^{1 to} R ⁴ described above.

The leuco dye of the general formula [I] of the present invention is
The compound represented by [II] is preferable.

[However, R ¹ and R ² are the same and represent an alkyl group,
R ⁵ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group, Z represents a hydrogen atom or an alkyl group, and Y represents OCH ₃ , CH.
₃ , Cl, COCH ₃ or CF ₃ ] That is, in the above general formula [II], the alkyl groups represented by R ¹ , R ² , R ⁵ and Z are
It is preferable that the carbon number is 1 to 8. Moreover, these may have a linear structure or may have a branch.

The halogen atom represented by R ⁵ is preferably a chlorine atom or a bromine atom. Further, the alkylthio group represented by R ⁵ and the alkyl portion of the alkoxy group preferably have 1 to 8 carbon atoms. Y is OC, which is advantageous from the viewpoint of manufacturing.
It is selected from H ₃ , CH ₃ , Cl, COCH ₃ and CF ₃ .

Next, typical examples of leuco dyes that can be used in the light-sensitive material of the present invention are shown.

(1) (2) (3) (4) (5) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) The leuco dye of the general formula [I] can be easily synthesized by the following method.

[Synthesis Example 1] Synthesis of leuco dye (1) 6.2 g of 2- (2-hydroxy-4-diethylamino) benzoylbenzoic acid, 4.4 g of 3-chloro-4-anilinophenol, and 15 m of concentrated sulfuric acid were mixed. , 40 ° C
And stirred for 8 hours. After completion of the reaction, the mixture was neutralized with sodium hydroxide, extracted with ethyl acetate, and then purified with a silica gel column (yield: 6.3 g). Melting point is 179-180 ° C
Met.

The leuco dye represented by the general formula [I] according to the present invention can be easily synthesized by the same procedure as in Synthesis Example 1.

Incidentally, some of the leuco dyes of the general formula [I] are already known, for example, JP-A-56-109251.
It is described in the official gazette.

The leuco dyes described above may be used alone,
You may mix and use it suitably. Further, the leuco dye of the general formula [I] (black image forming substance) according to the present invention can be used together with other known leuco dyes (yellow, magenta and cyan image forming substances) having different hues of color development.
In this case, known leuco dyes (yellow, magenta, cyan) may be used alone (for example, yellow only), or two or more kinds (for example, yellow) having different hues of color development (for example,
You may mix and use yellow and magenta). As a result, the obtained hue (color image) can be made clearer.

In particular, the leuco dye of the general formula [I] (black image-forming substance) according to the present invention functions advantageously when a clear full-color image having high contrast is obtained. This is because when the leuco dye of the general formula [I] is used in a light-sensitive material, the resulting black image forms three colors (blue, green,
All of them show high absorption at the peak wavelength of (red), which means that excellent saturation (brightness of color) can be obtained. Therefore, by using this together with other known leuco dyes having different hues, the hues possessed by the respective leuco dyes are promoted more vividly, especially in full-color images. As the embodiment of the light-sensitive material capable of obtaining a full-color image, at least three kinds (blue, green, and red) of silver halide emulsions (the silver halide emulsion will be described later) having sensitivity in different spectral regions, and corresponding to these The three types of microcapsules containing the three types of leuco dyes having different hues (yellow, magenta, and cyan), respectively, and a silver halide emulsion having a higher sensitivity than the silver halide emulsion and a leuco compound represented by the general formula [I]. It is preferable that the microcapsules containing the dye are in a coexisting state in the photosensitive layer. When a single color image is desired, it goes without saying that one or two of the above capsules may be appropriately selected.

In the light-sensitive layer of the light-sensitive material of the present invention, the leuco dye of the general formula [I] is preferably used in an amount in the range of 0.5 to 50% by weight based on the polymerizable compound, and particularly 2 to 20.
Preference is given to using amounts in the range by weight.

The light-sensitive material containing the leuco dye (black) of the general formula [I] of the present invention is used by bringing the leuco dye into contact with an acidic developer described later at the time of image formation. For example, a color image can be obtained on an image receiving material by containing an acidic developer in the image receiving layer of the image receiving material and superimposing the light sensitive material of the present invention on the image receiving material to cause a color forming reaction. .

In the above color development reaction, the leuco dye and the developer may be brought into contact with each other under heating conditions. By heating, the above color development reaction can be remarkably accelerated.

The heating temperature is generally 50 ° C to 200 ° C, preferably 50 ° C to 150 ° C. The heating time is generally 1
Seconds to 1 minute, preferably 1 second to 10 seconds.

The acidic developer may be present in the light-sensitive material of the present invention as an optional component in the light-sensitive layer. It is also possible to form a color image on the light-sensitive material by accommodating the leuco dye together with the polymerizable compound in the microcapsule in the light-sensitive layer of the light-sensitive material and allowing the acidic developer to exist outside the microcapsule. As for the light-sensitive material capable of obtaining a color image without using the image receiving material as described above, Japanese Patent Application No. 61-5
No. 3881 specification. In addition, acidic developer
It may be contained in a microcapsule different from the microcapsule containing the leuco dye and may be present in the photosensitive layer.

However, in terms of sensitivity and sharpness of the obtained color image, in order to form an image using the light-sensitive material of the present invention,
As described above, the embodiment in which the image receiving material containing an acidic developer in the image receiving layer (these will be described later) is the most preferable embodiment as the method for coloring the leuco dye according to the present invention. It is needless to say that other known leuco dyes having different hues which are used together with the leuco dye according to the present invention may be used in the above-described mode.

Examples of the acidic developer described above include acidic clay-based developer (clay), phenol-formaldehyde resin (eg, p-phenylphenol-formaldehyde resin), and metal salt of salicylic acid (eg, 3,5-dicarboxylic acid). -Α-methylbenzyl salicylate), phenol-salicylic acid-formaldehyde resin (eg, p-octylphenol-zinc salicylate-formaldehyde resin), zinc rhodan, zinc xanthate and the like.

Among these acidic developers, the developers that can be used in the present invention are preferably metal salts of salicylic acids, and more preferably zinc salicylate developers. That is, according to the study by the present inventor, it has been clarified that the coloring reaction of the leuco dye proceeds rapidly and efficiently in the presence of the zinc salicylate-based color developer. For the description of metal salts of salicylic acids, for example, Japanese Patent Publication No. 52-1327 and the like have details. The oil-soluble zinc salt of salicylic acid is described in US Pat. Nos. 3,864,146 and 4046.
No. 941 is described in each specification and the like.

The acidic developer as described above is a leuco dye,
It is preferably used in the range of 50 to 5000% by weight, more preferably 100 to 3000% by weight.

The silver halide, the reducing agent, the polymerizable compound, and the support which compose the light-sensitive material of the present invention will be sequentially described below.

Photosensitive materials include silver chloride, silver bromide,
Any grain of silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used.

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having multiple structures having different compositions on the surface and inside, JP-A-57-154232 and 58-10853 are known.
3, 59-48755, 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 1.
No. 00984 is described in each specification. Also, Japanese Patent Application Sho 61
A silver halide grain having a high proportion of silver iodide in the shell portion may be used as in the light-sensitive material described in Japanese Patent No. 25576.

There is also no particular limitation on the crystal habit of the silver halide grains. For example, tabular grains having an aspect ratio of 3 or more as in the light-sensitive material described in Japanese Patent Application No. 61-55509 may be used.

As the silver halide grains, Japanese Patent Application No. 61-2
It is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in 14580 specification.

Two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination with the silver halide used in the light-sensitive material.

The grain size distribution of silver halide grains is not particularly limited. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used, as in the light-sensitive material described in Japanese Patent Application No. 61-55508.

In the light-sensitive material, the average grain size of silver halide grains is preferably 0.001 to 5 μm,
More preferably, it is 001 to 2 μm.

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

The reducing agent that can be used in the light-sensitive material has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-
Birazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols,
2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines, etc. There is. By adjusting the type and amount of the reducing agent, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. In addition, in a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized, it is particularly preferable to use 1-phenyl-3-pyrazoline as a reducing agent.

Regarding various reducing agents having the above functions, JP-A Nos. 61-183640 and 61-188535, and Japanese Patent Application Nos. 60-68874 and 60-210.
No. 657, No. 60-226084, No. 60-2275.
No. 27, No. 60-227528, No. 61-42746.
In each specification (including those described as a developing agent or a hydrazine derivative). Regarding the reducing agent, see "The Theory of the Photographic Pro" by T. James.
cess ", 4th edition, pages 291-334 (1977), Research Disclosure Vol.170, June 170, No.17029 (pages 9-15), and Vol.17.
6, 17643, December 1978 (22-31
Page). Further, as in the light-sensitive material described in Japanese Patent Application No. 61-55505, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base is used instead of the reducing agent. Good. The reducing agent and the reducing agent precursor described in the above-mentioned respective specifications and references can be effectively used for the light-sensitive material in the present specification. Therefore, the “reducing agent” in the present specification includes the reducing agents and reducing agent precursors described in the above-mentioned publications, specifications and literatures.

These reducing agents may be used alone, or as described in each of the above specifications, two or more reducing agents may be mixed and used. When two or more reducing agents are used in combination, the reducing agents may interact with each other by first promoting the reduction of silver halide (and / or organic silver salt) by so-called superadditivity. To cause polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent in which the oxidant of the first reducing agent generated by reduction of silver halide (and / or organic silver salt) coexists (Or suppressing the polymerization) is considered. However, in actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 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-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- (3,5-dichlorobenzoyl) -2-phenylhydrazine, 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) butylamido} phenyl]
Hydrazine, 1-trityl-2-[{2,6-dichloro-4- (N, N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine, 1- (methoxycarbonylbenzohydryl) -2- (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-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4-dibutylcarbamoylbenzoyl) -2-tritylhydrazine, 1- (1-naphthoyl) -2-tritylhydrazine, etc. Can be mentioned.

In the light-sensitive material, the reducing agent is preferably used in the range of 0.1 to 1500 mol% with respect to 1 mol of silver (including the above-described silver halide and an organic silver salt which is an optional component).

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and known polymerizable compounds can be used. As a method of using the light-sensitive material, when a heat development process is planned, a high boiling point (for example, a boiling point of 80
It is preferable to use compounds of (° C. or higher). Further, in the embodiment in which the photosensitive layer contains a color image forming substance as an optional component described later, the color image forming substance is immobilized by polymerizing and curing the polymerizable compound. A crosslinkable compound having a polymerizable functional group is preferable. Further, as described later, when a transfer image is formed using an image receiving material, Japanese Patent Application No. 61-15007
It is preferable to use a highly viscous substance as the polymerizable compound, as in the light-sensitive material described in No. 9.

The polymerizable compounds that can be used in the light-sensitive material are described in the application specifications for a series of light-sensitive materials described above and below.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable.

Compounds having an ethylenically unsaturated group that can be used in the light-sensitive material include acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydride. Acids, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers,
There are allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the light-sensitive material include acrylic acid esters such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, dicyclohexyl. Oxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate,
Examples thereof include polyoxyethylenated bisphenol A diacrylate, hydroxypolyether polyacrylate, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetramethacrylate. Methacrylate and dimethacrylate of polyoxyalkylenated bisphenol A and the like can be mentioned.

The polymerizable compounds may be used alone or in combination of two or more. The light-sensitive material containing two or more polymerizable compounds in combination is described in Japanese Patent Application No. 61-55504. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the above-mentioned reducing agent or an optional component described later, which is a color image forming substance, can also be used as the polymerizable compound. Needless to say, use of a substance that serves as both a reducing agent and a polymerizable compound or a color image forming substance and a polymerizable compound as described above is also included in the embodiment of the light-sensitive material.

In the light-sensitive material, the polymerizable compound is preferably used in the range of 50,000 to 120,000 parts by weight with respect to 1 part by weight of silver halide. A more preferable range of use is 10 to 10,000 parts by weight.

The light-sensitive material comprises a support and a light-sensitive layer containing the components described above. The support is not particularly limited, but when heat development processing is planned as a method of using the light-sensitive material, it is preferable to use a material that can withstand the processing temperature of the development processing. Examples of materials that can be used for the support include glass, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene. Examples thereof include films such as terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

When the support is made of a porous material such as paper, the support used in the photosensitive material described in Japanese Patent Application No. 61-52996 has a certain degree of smoothness according to a prescribed method due to waviness. It is preferable to have When a paper support is used, a paper support having a low water absorption such as the light-sensitive material described in Japanese Patent Application No. 61-183050 and a light-sensitive material described in Japanese Patent Application No. 61-191273 are used. Paper support having a certain Beck's smoothness, Japanese Patent Application No. 61-
A paper support having a low shrinkage ratio such as the light-sensitive material described in JP-A-227766, and a paper support having a low air permeability such as a light-sensitive material described in Japanese Patent Application No. 227768/1987.
It is also possible to use a paper support having a pH value of 5 to 9 like the light-sensitive material described in US Pat.

Hereinafter, various aspects of the light-sensitive material of the present invention, optional components that can be contained in the light-sensitive layer, and auxiliary layers that can be optionally provided in the light-sensitive material of the present invention will be sequentially described.

In the photosensitive material, the polymerizable compound is preferably dispersed in the photosensitive layer in the form of oil droplets. For an example of a photosensitive material in which a polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets, see Japanese Patent Application No.
It is described in the specification of 0-218603. Other components in the photosensitive layer such as silver halide, a reducing agent, and a color image forming substance may be contained in the oil droplets. Regarding a light-sensitive material containing silver halide in oil droplets, Japanese Patent Application No. 60-
Nos. 261888 and 61-5571,
For the light-sensitive material further containing a reducing agent in the oil droplets,
Each of them is described in the specification of Japanese Patent Application No. 61-25577. When silver halide is included in oil droplets,
As described in Japanese Patent Application No. 61-160592, it is preferable that the number of silver halide grains contained in the oil droplet is 5 or more.

The oil droplets of the polymerizable compound are more preferably in the form of microcapsules. Various known techniques can be applied to the microcapsules without particular limitation. An example of a light-sensitive material in which oil droplets of a polymerizable compound are in a microcapsule state is disclosed in Japanese Patent Application No. 60-11.
7089 specification.

There is no particular limitation on the wall material that constitutes the outer shell of the microcapsule. Regarding a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application No. 61-53871 discloses a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application No. 61-53872 for a light-sensitive material using the above, and Japanese Patent Application No. 61-538 for a light-sensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin.
Japanese Patent Application No. 61-538 discloses a photosensitive material using microcapsules having an outer shell made of gelatin.
Japanese Patent Application No. 61-741 discloses a light-sensitive material using microcapsules having an outer shell made of an epoxy resin.
-53875 describes a photosensitive material using microcapsules having a composite resin outer shell containing a polyamide resin and a polyurea resin, see Japanese Patent Application No. 61-53877, which describes a composite resin containing a polyurethane resin and a polyester resin. The light-sensitive materials using microcapsules having shells are described in Japanese Patent Application No. 61-53878.

When aldehyde-based microcapsules are used, it is preferable that the amount of residual aldehyde is not more than a certain value, as in the light-sensitive material described in Japanese Patent Application No. 61-176415 by the present applicant.

When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. Regarding the photosensitive material containing silver halide in the wall material of the microcapsule, Japanese Patent Application No. 61-61
It is described in the specification of -11556.

Further, two or more microcapsules in which at least one of the components contained in the microcapsules such as silver halide, a reducing agent, a polymerizable compound, and a color image forming substance are different may be used in combination. In particular, in the case of forming a full-color image, it is preferable to use together three or more types of microcapsules in which the color hue of the color image forming substance contained is different. The light-sensitive material in which two or more kinds of microcapsules are used in combination is described in Japanese Patent Application No. 61-42747.

The average particle size of the microcapsules is preferably 3 to 20 μm. The particle size distribution of the microcapsules is preferably uniform over a certain value, as in the light-sensitive material described in Japanese Patent Application No. 61-150080. The film thickness of the microcapsules is Japanese Patent Application No. 61-
As in the light-sensitive material described in No. 227767, it is preferable that the particle diameter is within a certain range.

When accommodating silver halide in microcapsules, the average grain size of the silver halide grains described above is preferably one-fifth or less, and preferably one-tenth or less, of the average size of microcapsules. Is more preferable. By setting the average grain size of silver halide grains to be 1/5 or less of the average size of microcapsules,
It is possible to obtain a uniform and smooth image.

The optional components that can be contained in the photosensitive layer of the photosensitive material include color image-forming substances other than the above-mentioned acidic developers and leuco dyes according to the present invention, sensitizing dyes, organic silver salts, radical generators, various Image forming accelerator (eg, base, base precursor, oil, surfactant, compound having fog-preventing function and / or development-accelerating function, thermal solvent, compound having oxygen removing function, etc.), thermal polymerization inhibitor, heat Polymerization initiators, development terminators, fluorescent whitening agents, anti-fading agents, halation or irradiation prevention dyes or pigments,
Examples thereof include a dye having a property of decolorizing by heating or light irradiation, a matting agent, an anti-smudge agent, a plasticizer, a water releasing agent, a binder, a photopolymerization initiator, a solvent for a polymerizable compound, and a water-soluble vinyl polymer.

The light-sensitive material of the present invention contains a leuco dye represented by the above general formula [I] as a color image forming substance. However, a color image forming substance other than the leuco dye represented by the general formula [I] is optionally used in combination. It may be as described above. The general light-sensitive material using a color image forming substance is described in Japanese Patent Application No. 61-73145 mentioned above. Further, Japanese Patent Application No. 61-29987 discloses a photosensitive material using a dye or pigment as a color image forming substance, and Japanese Patent Application No. 61-53876 discloses a photosensitive material using a leuco dye, and a triazene compound. Japanese Patent Application No. 61-96339 for a light-sensitive material using the same, and Japanese Patent Application Nos. 61-133091 and 61-13 for a light-sensitive material using a yellow color-forming leuco dye.
No. 3092 describes a light-sensitive material using a cyan color-forming leuco dye, and each is described in Japanese Patent Application No. 61-197963.

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and a silver halide sensitizing dye known in the photographic art can be used. The sensitizing dye, methine dye, cyanine dye, merocyanine dye, complex cyanine dye, holopolar cyanine dye, hemicyanine dye,
Examples include styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. In particular, for the purpose of supersensitization, it is common to use a combination of sensitizing dyes. Further, together with the sensitizing dye, a dye which does not have a spectral sensitizing effect itself, or a substance which does not substantially absorb visible light but exhibits supersensitization may be used together. The amount of the sensitizing dye added is generally 10 ^{-8 to} 10 ^-2 per mol of silver halide.
It is about molar.

The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. Regarding a light-sensitive material obtained by adding a sensitizing dye in the step of forming silver halide grains, Japanese Patent Application No. 60-139746 discloses a silver halide emulsion after the formation of silver halide grains. The light-sensitive materials obtained by adding them in the preparation stage are described in Japanese Patent Application No. 61-55510. Further, specific examples of sensitizing dyes that can be used in the light-sensitive material are described in the above-mentioned Japanese Patent Application Nos. 60-139746 and 61-55510. Further, as in the light-sensitive material described in Japanese Patent Application No. 61-20878, an infrared-sensitive sensitizing dye may be used in combination.

Addition of an organic silver salt to a light-sensitive material is particularly effective in heat development processing. That is, when heated to a temperature of 80 ° C. or higher, the organic silver salt is considered to participate 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 contact with or in close proximity to each other. 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. Among them, benzotriazole is particularly preferable. The above organic silver salt is generally used in an amount of 0.01 to 10 mol, preferably 0.0 mol, per mol of silver halide.
Use 1 to 1 mole. Instead of the organic silver salt, an organic compound (for example, benzotriazole) that constitutes it
The same effect can be obtained by adding to the photosensitive layer. A light-sensitive material using an organic silver salt is described in Japanese Patent Application No. 60-141799.

The above-mentioned radical generator which participates in the polymerization acceleration (or polymerization suppression) reaction of the reducing agent may be added to the photosensitive layer.
Japanese Patent Application No. 61-38510 discloses a photosensitive material using silver triazene as the above-mentioned radical generator, and Japanese Patent Application No. 61-38510 discloses a photosensitive material using silver diazotate.
No. 38511 and Japanese Patent Application No. 61-38512 describe the light-sensitive material using an azo compound.

Various image formation accelerators can be used in the light-sensitive material. The image forming accelerator includes a silver halide (and / or an organic silver salt) and a reducing agent for promoting the redox reaction between the redox agent and the photosensitive material to the image receiving material or image receiving layer (these will be described later). It has the function of promoting the movement of image forming substances. The image formation accelerator is a base, a base precursor, an oil, a surfactant, a
It is further classified into a compound having an antifoggant function and / or a development promoting function, a hot solvent, a compound having an oxygen removing function, and the like. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Therefore, the above classification is convenient, and in fact, one compound often has a plurality of functions.

Examples of image forming accelerators include bases, base precursors, oils, surfactants, compounds having an antifoggant function and / or development promoting function, thermal solvents, and compounds having an oxygen removing function.

Examples of preferable bases include alkali metal or alkaline earth metal hydroxides as inorganic bases; alkali metal or alkaline earth metal tertiary phosphates, borates,
Carbonates, metaborates; combinations of zinc hydroxide or zinc oxide with chelating agents such as sodium picolinate;
Ammonium hydroxides; quaternary alkyl ammonium hydroxides; hydroxides of other metals, and the like, and organic bases include aliphatic amines (trialkylamines,
Hydroxylamines, aliphatic polyamines); Aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis [p-
(Dialkylamino) phenyl] methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and the like, with a pKa of 7 or more being particularly preferable.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heating, compounds that release amines by reactions such as intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Compounds that release and generate a base by electrolysis are preferably used. Specific examples of the chloride precursor include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, phenylsulfonylacetic acid guanidine, 4-chlorophenylsulfonylacetic acid guanidine, and 4-methylsulfonylsulfonyl. Examples thereof include guanidine phenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

The base or base precursor can be used in a wide range of amount in the light-sensitive material of the present invention. The base or the base precursor is suitably used in an amount of 100% by weight or less in terms of weight of the coating film of the photosensitive layer, and more preferably 0.
A range of 1% to 40% by weight is useful. In the present invention, the base and / or base precursor may be used alone or as a mixture of two or more kinds.

A light-sensitive material using a base or a base precursor is described in Japanese Patent Application No. 60-227528. Further, regarding a light-sensitive material using a tertiary amine as a base or a base precursor, Japanese Patent Application No. 61-131
No. 81 discloses a light-sensitive material using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C., which has a solubility of 0.1% in Japanese Patent Application No. 61-52992.
Japanese Patent Application No. 61-215637 discloses a light-sensitive material using the following guanidine derivative, and Japanese Patent Application No. 61-96341 discloses a light-sensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal. There is a description in each book.

Further, regarding a light-sensitive material using an acetylide compound as a base precursor, Japanese Patent Application No. 61-167558 discloses that acetylene carboxylate is used as a base precursor, and silver, copper, a silver compound or a copper compound is subjected to a base formation reaction. Japanese Patent Application No. 61-191000 for a light-sensitive material containing the catalyst as a catalyst, and Japanese Patent Application No. 61-191000 for a light-sensitive material containing the acetylene carboxylate salt and the silver, copper, a silver compound or a copper compound separated from each other. 61
No. 227,769 discloses a photosensitive material containing the above-mentioned acetylene carboxylate salt and the above-mentioned silver, copper, a silver compound or a copper compound and a ligand in a free state. 243555 uses acetylene carboxylate as a base precursor,
Further, regarding a light-sensitive material containing a heat-meltable compound as a reaction accelerator for a base-forming reaction, Japanese Patent Application No. 61-191001 discloses that a sulfonylacetate is used as a base precursor, and a heat-meltable compound is used in a reaction for a base-forming reaction. Regarding the light-sensitive material containing the accelerator, Japanese Patent Application No. 61-1933.
Japanese Patent Application No. 61-1675 discloses a photosensitive material using a compound in which an isocyanate or isothiocyanate is bound to an organic base as a base precursor.
No. 58 has a description.

When a base or a base precursor is used in the light-sensitive material of the present invention, silver halide in the microcapsules described above,
It is preferable that a reducing agent, a polymerizable compound and a triazene compound are contained, and a base or a base precursor is present in the photosensitive layer outside the microcapsules. Alternatively, a base or a base precursor may be contained in another microcapsule as in the light-sensitive material described in Japanese Patent Application No. 61-52988. In addition to the above specification, a light-sensitive material containing microcapsules containing a base or a base precursor is a light-sensitive material containing a base or a base precursor dissolved or dispersed in an aqueous solution of a water retention agent in microcapsules. No. 529299 discloses a photosensitive material in which solid fine particles carrying a base or a base precursor are contained in microcapsules. Japanese Patent Application No. 61-52995 discloses a light-sensitive material having a melting point of 70 ° C. to 21 ° C.
For the photosensitive material using microcapsules containing a base compound at 0 ° C., see Japanese Patent Application No. 61-212149.
Each is listed. In place of the microcapsules containing the above base or base precursor, Japanese Patent Application No.
Particles containing a base or a base precursor in a compatible state with a hydrophobic substance may be used as in the light-sensitive material described in US Pat. No. 4,243,556.

The base or base precursor is described in Japanese Patent Application No. 61-9.
It may be added to an auxiliary layer (a layer containing a base or a base precursor described later) other than the photosensitive layer as described in the specification of 6340. Furthermore, Japanese Patent Application No. 61-1
As described in Japanese Patent No. 76417, the above-mentioned support may be made porous, and a base or a base precursor may be contained in this porous support.

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

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

The compound having the fog-preventing function and / or the development-accelerating function can be used for the purpose of obtaining a clear image (high-contrast image) having a high maximum density and a low minimum density. For a light-sensitive material using an antifoggant as a compound having an antifoggant function and / or a development promoting function, Japanese Patent Application No. 60-294337 is available.
Japanese Patent Application No. 60-294338 describes a photosensitive material using a compound having a cyclic amide structure, and Japanese Patent Application No. 60-294339 discloses a photosensitive material using a thioether compound. Regarding the light-sensitive material using a glycol derivative, Japanese Patent Application No. 60-
No. 294340, and Japanese Patent Application No. 60-294341 describes a photosensitive material using a thiol derivative.
Japanese Patent Application No. Sho 6 for a photosensitive material using an acetylene compound.
1-20438, a photosensitive material using a sulfonamide derivative is described in Japanese Patent Application No. 61-25578, and a photosensitive material using a quaternary ammonium salt is described in Japanese Patent Application No. 61-238871. , Each has a description.

As the hot solvent, a compound which can be a solvent for the reducing agent, a compound which is a substance having a high dielectric constant and is known to accelerate the physical development of the silver salt, and the like are useful. As a useful thermal solvent,
Polyethylene glycols described in U.S. Pat. No. 3,347,675, derivatives of polyethylene oxide such as oleic acid ester, beeswax, monostearin and -SO.
High dielectric constant compounds having _2- and / or --CO-- groups, polar substances described in US Pat. No. 3,667,959, 1,10-decanediol described in Research Disclosure, December 1976, pages 26-28. , Methyl anisate, biphenyl suberate and the like are preferably used. The photosensitive material using a hot solvent is described in the specification of Japanese Patent Application No. 60-227527.

The compound having a function of removing oxygen can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting action). Examples of the compound having an oxygen removing function include compounds having two or more mercapto groups. The photosensitive material using a compound having two or more mercapto groups is described in Japanese Patent Application No. 61-53880.

The thermal polymerization initiator that can be used in the light-sensitive material is generally a compound that thermally decomposes under heating to generate a polymerization initiation species (particularly a radical), and is usually used as an initiator of radical polymerization. The thermal polymerization initiator is described on pages 6 to 18 and the like of "Addition Polymerization / Ring-Opening Polymerization", edited by Editorial Committee for Polymer Experiments, Polymer Society of Japan, 1983, Kyoritsu Shuppan). Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 2,2-azobis ( 2-Methyl butyronitrile), azo compounds such as azobisdimethylvaleronitrile, organic peroxides such as benzoyl peroxide, di-t-peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. Compounds, hydrogen peroxide, inorganic peroxides such as potassium persulfate and ammonium persulfate, and sodium p-toluenesulfinate. The thermal polymerization initiator is preferably used in the range of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In the system in which the polymerizable compound in the portion where the latent image of silver halide is not formed is polymerized, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Further, a light-sensitive material using a thermal polymerization initiator is described in Japanese Patent Application No. 60-210657.

A development terminator that can be used in a light-sensitive material is a compound that interacts with a compound or silver and a silver salt that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop development after proper development. Is a compound that suppresses development. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, a nitrogen-containing heterocyclic compound, and a mercapto compound. Examples of acid precursors include JP-A-60-1
Examples thereof include oxime esters described in each of Nos. 08837 and 60-192939, and compounds that release an acid by the Rossen rearrangement described in JP-A-60-230133. Further, as an example of the electrophilic compound which causes a substitution reaction with a base upon heating, there is disclosed in JP-A-60-230.
Examples thereof include compounds described in JP-A-134.

Dyes or pigments may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. For the purpose of preventing halation or irradiation, a white pigment is added to the photosensitive layer to describe a light-sensitive material in Japanese Patent Application No. 61-174402.

When the light-sensitive layer of the light-sensitive material is a mode in which the above-mentioned microcapsules are used, the microcapsules may contain a dye having a property of decoloring by heating or light irradiation. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. Regarding the light-sensitive material using the dye having the property of being decolorized by heating or light irradiation as described above, Japanese Patent Application No.
It is described in the specification of No. 1-243551.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. As a specific example, British Patent No. 1
Starch particles described in US Pat. No. 2,322,347, fine polymer powders described in US Pat. No. 3,625,736, microcapsule particles containing no color-developing agent described in British Patent No. 12359991, US Pat. No. 2,711,375. Examples thereof include the finely divided cellulose powder, talc, kaolin, bentonite, pyrophyllite, zinc oxide, titanium oxide, and inorganic particles such as alumina. The average particle size of the particles is 3 to 50 μm in volume average diameter.
Is preferable, and a range of 5 to 40 μm is more preferable. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules.

The binder that can be used in the light-sensitive material and the image-receiving material described later can be contained in the light-sensitive layer or the image-receiving layer (described later) alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and examples thereof include gelatin, gelatin derivatives,
It includes natural substances such as cellulose derivatives, starch, arabic gum and the like, and synthetic polymer substances such as water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone and acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latices, which increase the dimensional stability of photographic materials in particular. Regarding the light-sensitive material using a binder, see Japanese Patent Application Laid-Open No. 61-6906.
It is described in Japanese Patent No. 2 publication. Regarding the photosensitive material using a binder together with microcapsules, Japanese Patent Application No.
-52994 specification.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing the unpolymerized polymerizable compound after image transfer. A light-sensitive material using a photopolymerization initiator is described in Japanese Patent Application No. 61-3025.

When a solvent for a polymerizable compound is used in the light-sensitive material, it is preferably used by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound. Regarding a photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules, see Japanese Patent Application No. 61-5299.
There is a description in No. 3 specification.

A water-soluble vinyl polymer may be adsorbed on the above-described silver halide grains for use. Regarding the light-sensitive material using the water-soluble vinyl polymer as described above, Japanese Patent Application No. 61-2388
No. 70 specification.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and the usage thereof are also described in the application specification regarding the series of photosensitive materials described above, and Research Disclosure Vol. 170, June 1978. The 17th
No. 029 (pages 9 to 15).

The photosensitive layer of the photosensitive material comprising the components described above preferably has a pH value of 7 or less as in the photosensitive material described in Japanese Patent Application No. 61-104226.

Examples of layers that can be optionally provided in the light-sensitive material include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer,
Examples thereof include a cover sheet or a protective layer, a layer containing a base or a base precursor, a base barrier layer, and an antihalation layer (colored layer).

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

For the photosensitive material using the heating element layer, Japanese Patent Application No.
-135568, Japanese Patent Application No. 61-55507 for a photosensitive material provided with a cover sheet or a protective layer, and Japanese Patent Application No. 61-96340 for a photosensitive material provided with a layer containing a base or a base precursor. Japanese Patent Application No. 61-246901 describes a light-sensitive material provided with a coloring layer as an antihalation layer. Further, a light-sensitive material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application No. 61-96340. Furthermore, examples of other auxiliary layers and their usages are also described in the specification of the above-mentioned series of photosensitive materials.

The method for producing the photosensitive material will be described below.

Although various methods can be used as a method for producing a light-sensitive material, a general production method is to prepare a coating solution by dissolving, emulsifying or dispersing the components of the photosensitive layer in an appropriate solvent, and applying the solution. It comprises a step of obtaining a light-sensitive material by applying the liquid to the support as described above and drying.

Generally, each coating solution is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared for each component, or may be prepared to contain a plurality of components. A part of the components of the photosensitive layer may be added and used at the stage of preparing the liquid composition or the coating solution or after the preparation. Furthermore, as described below, an oily (or aqueous) composition containing one or more components is
Further, a method of preparing a secondary composition by emulsifying in an aqueous (or oily) solvent can also be used.

With respect to the main components contained in the photosensitive layer, a method for preparing a liquid composition and a coating liquid is shown below.

In the production of a light-sensitive material, silver halide is preferably prepared as a silver halide emulsion. There are various methods known in the photographic art for the preparation of silver halide emulsions,
There are no particular restrictions on the production of the photosensitive material. The silver halide emulsion can be prepared by any of the acidic method, the neutral method and the ammonia method. As the reaction mode of the soluble silver salt and the soluble halogen salt, a one-sided mixing method,
Either a double jet method or a combination thereof may be used. Back mixing method and pA for mixing particles under silver ion excess conditions
A controlled double jet method that keeps g constant can also be adopted. Further, the silver halide emulsion may be a surface latent image type in which a latent image is mainly formed on the surface of a grain, 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.

In the preparation of a silver halide emulsion used for producing a light-sensitive material, a hydrophilic colloid (eg gelatin) can be used as a protective colloid. Further, a water-soluble vinyl polymer may be added to the silver halide emulsion in place of or in combination with gelatin. The light-sensitive material in which the water-soluble vinyl polymer compound is in contact with the silver halide emulsion grains is described in Japanese Patent Application No. 61-238870.

The silver halide emulsion contains ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (see JP-A-53-144319) as a silver halide emulsion in the step of forming silver halide grains.
Etc. can be used. Further, in the process of grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt or the like may be allowed to coexist. Further, iridium chloride (III value or IV value) is used for the purpose of improving high illumination failure and low illumination failure.
Value), a water-soluble iridium salt such as ammonium hexachloroiridium salt, or a water-soluble rhodium salt such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after formation of a precipitate or after physical ripening. In this case, it can be carried out according to the Nudel washing method or the sedimentation method. The silver halide emulsion may be used without ripening, but it is usually chemically sensitized before use. In the conventional emulsion for a sensitive material, the known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination.

When a sensitizing dye is added to the silver halide emulsion,
The aforementioned Japanese Patent Application Nos. 60-139746 and 61-5.
It is preferably added at the stage of preparing a silver halide emulsion as in the light-sensitive material of No. 5510. When a nitrogen-containing heterocyclic compound is added as the compound having the fog-preventing function and / or the development-accelerating function, it should be added in the step of forming silver halide grains or the ripening step in the preparation of a silver halide emulsion. Is preferred. The method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added in the step of forming silver halide grains or the step of ripening is described in Japanese Patent Application No. 61-3024.

When the above-mentioned organic silver salt is contained in the photosensitive layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion.

In the production of a light-sensitive material, the polymerizable compound can be used as a medium for preparing the composition of other components in the light-sensitive layer. For example, a silver halide (including a silver halide emulsion), a reducing agent, a color image-forming substance and the like can be dissolved, emulsified or dispersed in a polymerizable compound and used for producing a light-sensitive material. In particular, the leuco dye represented by the general formula [I] is preferably contained in the polymerizable compound.
When oil droplets of the polymerizable compound are microencapsulated, components such as wall material necessary for microencapsulation may be included in the polymerizable compound.

The photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition to the silver halide emulsion, a silver halide powder prepared by freeze-drying or the like can be used for the preparation of the photosensitive composition. The photosensitive composition containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrer.

In addition, it is preferable to dissolve a copolymer composed of a hydrophilic repeating unit and a hydrophobic repeating unit in the polymerizable compound used for preparing the photosensitive composition. For a photosensitive composition containing the above copolymer, Japanese Patent Application No.
-261887 specification.

Further, instead of using the above copolymer, microcapsules containing a silver halide emulsion as a core substance may be dispersed in a polymerizable compound to prepare a photosensitive composition. The photosensitive composition containing the microcapsules containing the silver halide emulsion as a core substance is described in Japanese Patent Application No. 61-5750.

The polymerizable compound (including those containing other constituents such as the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. Also, Japanese Patent Application Sho 60
When the oil droplets of the polymerizable compound are microencapsulated as in the light-sensitive material described in JP-A-117089, the wall material necessary for microencapsulation is added to the emulsion, and the microcapsules are removed. The shell-forming treatment can also be carried out at this emulsion stage. Further, a reducing agent or any other component may be added at the stage of the above emulsion.

As an example of the microencapsulation method, a method utilizing coacervation of the hydrophilic wall-forming material described in US Pat. Nos. 2,800,457 and 2,800,458; US Pat. No. 3,287,154 and British Patent No. 990443. Each specification and Japanese Patent Publication No. 38-1957
No. 4, 42-446 and 42-771; interfacial polymerization method; method by polymer precipitation described in US Pat. Nos. 3,418,250 and 3,660,304; US Pat. No. 3,796,669. Method using the described isocyanate-polyol wall material; Method using the isocyanate wall material described in US Pat. No. 3,914,511; US Pat. Nos. 4,001,140, 4;
No. 087376 and No. 4089802, the method of using the urea-formaldehyde-based or urea-formaldehyde-resilicinol-based wall forming material; the walls of melamine-formaldehyde resin, hydroxypropyl cellulose, etc. described in US Pat. No. 4,025,455. In situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079; polymerization dispersion cooling described in British Patents 927807 and 965074. Law; U.S. Pat. No. 3,111,407 and British Patent No. 930422.
The spray drying method described in each specification can be used. The method of microencapsulating the oil droplets of the polymerizable compound is not limited to the above, but a method of forming a polymer film as a microcapsule wall after emulsifying the core substance is particularly preferable.

Regarding the photosensitive microcapsules that can be used for producing the photosensitive material, Japanese Patent Application No. 61-11556,
No. 61-11557, No. 61-53871, No. 61
-53872, 61-53873, 61-53
874, 61-53875, 61-53877.
No. 61-53878.

When the polymerizable compound is a photosensitive composition containing silver halide in the emulsion of the polymerizable compound (including the microcapsule liquid subjected to the microencapsulation treatment) described above, the coating liquid for the photosensitive material is used as it is. Can be used as Emulsions other than the above can be mixed with the composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. Other components may be added at the stage of this coating solution as in the case of the above emulsion.

A photosensitive material is manufactured by coating the support with the coating solution for the photosensitive layer prepared as described above and drying. The coating of the coating liquid on the support can be easily carried out according to known techniques.

The method of using the photosensitive material will be described below.

The light-sensitive material may be imagewise exposed at the same time or after imagewise exposure.
It is used after being developed.

Although various exposing means can be used as the exposing method, a latent image of silver halide is generally obtained by imagewise exposure of radiation including visible light. The type of light source and the amount of exposure are
Sensitive wavelength of silver halide (when dye sensitization is performed,
It can be selected according to the sensitized wavelength) and the sensitivity. The original image may be a monochrome image or a color image.

The light-sensitive material is subjected to development processing at the same time as or after the above-described increase exposure. The photosensitive material is Japanese Patent Publication No. 45-111.
You may perform the development process using the developing solution of Unexamined-Japanese-Patent No. 49 grade. As described above, the method described in Japanese Patent Application Laid-Open No. 61-69062, which carries out heat development processing, has the advantage that the operation is simple and the processing can be performed in a short time because it is a dry processing. Therefore, the development process of the photosensitive material is
The latter is especially good.

As a heating method in the heat development treatment, various conventionally known methods can be used. Further, as in the light-sensitive material described in Japanese Patent Application No. 60-135568, the light-sensitive material may be provided with a heating element layer and used as a heating means. Further, as in the image forming method described in Japanese Patent Application No. 61-55506, the heat development treatment may be carried out while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 80 ° C to 200 ° C, preferably 100 ° C to 160 ° C. The heating time is generally 1 second to 5 seconds.
Minutes, preferably 5 seconds to 1 minute.

Instead of incorporating the above-mentioned base or base precursor into the light-sensitive material, development processing may be carried out while adding the base or base precursor to the light-sensitive layer or immediately after the addition. As a method for adding a base or a base precursor, a method using a sheet containing a base or a base precursor (base sheet) is the easiest and preferable. An image forming method using the above-mentioned base sheet is described in Japanese Patent Application No. 61-176417.

The light-sensitive material can be subjected to the heat development treatment as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. Incidentally, in the light-sensitive material, the polymerizable compound in the portion where the latent image of silver halide is formed is generally polymerized in the heat development treatment described above.
It is also possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed by adjusting the kind and amount of the reducing agent as in the light-sensitive material described in the specification of 210657.

As described above, the photosensitive material can obtain a polymer image on the photosensitive layer.

When the light-sensitive material is constituted like the light-sensitive material described in Japanese Patent Application No. 61-53881, the developed light-sensitive material is pressurized to destroy the microcapsules containing the leuco dye of the present invention. Then, a color image can be formed on the photosensitive material by bringing the leuco dye and the acidic developer into contact with each other.

However, as described above, in the image forming method using the light-sensitive material of the present invention, it is preferable to form an image on the image receiving material by using the image receiving material.

The image receiving material will be described below. An image forming method using an image receiving material or an image receiving layer is generally described in Japanese Patent Application No. 60-112284.

As the support for the image receiving material, in addition to the support that can be used for the light-sensitive material described above, variator paper can be used. When a porous material such as paper is used as the support of the image receiving material, it preferably has a certain smoothness like the image receiving material described in Japanese Patent Application No. 61-52990. . An image receiving material using a transparent support is described in Japanese Patent Application No. 61-52991.

The image receiving material generally has an image receiving layer provided on a support. When an acidic developer is added to the light-sensitive layer of the light-sensitive material of the present invention to develop color before or simultaneously with the transfer to the image-receiving material, the image-receiving material may be composed of only the above support. Good.

The image receiving layer preferably contains a polymer as a binder. As the binder, the binder that can be used in the photosensitive layer of the photosensitive material described above can be used. A polymer having low oxygen permeability may be used as a binder, such as the image receiving material described in Japanese Patent Application No. 61-53879.

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation. The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from publicly known plastic resins (plastics) and waxes. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or lower. Regarding the image receiving material having the image receiving layer containing the above-mentioned thermoplastic compound fine particles, Japanese Patent Application No. 61-12
Nos. 4952 and 61-124953 are described.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator for the purpose of smoothly proceeding the curing treatment (fixing treatment) of the unpolymerized polymerizable compound. Regarding the image receiving material having an image receiving layer containing a photopolymerization initiator, Japanese Patent Application No. 61-
No. 3025 describes an image receiving material having an image receiving layer containing a thermal polymerization initiator, and each is described in Japanese Patent Application No. 61-55502.

The dye or pigment may be contained in the image receiving layer for the purpose of writing characters, symbols, frames, etc. on the image receiving layer or for the purpose of making the background of the image a specific color. Further, a dye or a pigment may be included in the image receiving layer for the purpose of facilitating the front / back discrimination of the image receiving material. As the dye or pigment, various known substances including dyes or pigments that can be used in image formation can be used, but the dye or pigment may impair the image formed in the image receiving layer. In some cases, it is preferable to lower the dyeing density of the dye or pigment (for example, the reflection density is 1 or less), or to use the dye or pigment having the property of being decolorized by heating or light irradiation.
An image receiving material having an image receiving layer containing a dye or pigment having a property of being decolorized by heating or light irradiation is described in Japanese Patent Application No. 61-96339.

Further, when a white pigment such as titanium dioxide or barium sulfate is added to the image receiving layer, the image receiving layer can function as a white reflective layer. When the image receiving layer is made to function as a white reflective layer, the white pigment is 10 g per 1 g of the thermoplastic compound.
It is preferably used in the range of 100 to 100 g.

When the dye or pigment as described above is contained in the image receiving layer, it may be uniformly contained or may be partially distributed. For example, a support described below is made of a material having a light-transmitting property, and a part of the reflection image can be a projection image by including the white pigment in a part of the image receiving layer. By doing so, unnecessary image information in the projected image can be written as a reflected image in the image receiving layer portion containing the white pigment.

The image receiving layer may be composed of two or more layers depending on the functions as described above. The thickness of the image receiving layer is 1 to 1
The thickness is preferably 00 μm, more preferably 1 to 20 μm.

A protective layer may be further provided on the image receiving layer. Further, a layer made of an aggregate of fine particles of a thermoplastic compound may be further provided on the image receiving layer. An image receiving material having a layer comprising an aggregate of fine particles of a thermoplastic compound provided on the image receiving layer is described in Japanese Patent Application No. 61-55503.

Further, a layer containing an adhesive or an adhesive and release paper may be sequentially laminated on the surface of the support opposite to the surface on which the image receiving layer is provided. Regarding the sticker-shaped image receiving material having the above structure, Japanese Patent Application No. 61-16926 of the present applicant
There is a description in No. 4 specification.

The photosensitive material is subjected to development processing as described above, and by pressing the image receiving material in a state of being superposed, the unpolymerized polymerizable compound is transferred to the image receiving material, and a polymer image can be obtained on the image receiving material. it can. Regarding the pressing means,
Various conventionally known methods can be used.

After the image is formed on the image receiving material as described above, the image receiving material may be heated as in the image forming method described in Japanese Patent Application No. 61-55501. The above method also has an advantage that the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized and the storability of the obtained image is improved.

Photosensitive materials include black and white or color photographing and printing sensitive materials, printing sensitive materials, printing plates, X-ray sensitive materials, medical sensitive materials (for example, ultrasonic diagnostic machine CRT photographing sensitive materials), computer graphic hard copy sensitive materials, There are many applications such as sensitive materials for copiers.

The present invention will be described more specifically by the following examples. However, the present invention is not limited to this.

[Example 1] [Preparation of light-sensitive material] Preparation of silver halide emulsion (A) 21 g of sodium chloride was added to a stirring gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 m of water and kept at 75 ° C). And an aqueous solution containing 600 g of potassium bromide and 600 g of silver nitrate (water of 600 m
4) simultaneously dissolving 0.59 mol of silver nitrate)
Added at equal flow rate over 0 minutes. Thus, a monodisperse cubic silver bromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

The above emulsion was washed with water and desalted, and then 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7 were added.
-Tetrazaindene (20 mg) was added and chemical sensitization was performed at 60 ° C. The yield of emulsion was 600 g.

Preparation of benzotriazole silver emulsion (A) 28 g of gelatin and 13.2 g of benzotriazole were added to 3 parts of water.
It was melted in 000m. The solution was stirred while maintaining the temperature at 40 ° C., and a solution prepared by dissolving 17 g of silver nitrate in 100 m of water was added over 2 minutes. Excess salt was precipitated and removed by adjusting the pH of the obtained emulsion. Then, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion. The yield of emulsion was 400 g.

Preparation of Photosensitive Composition (A) 100 g of trimethylolpropane triacrylate and 0.40 g of the following copolymer and the following leuco dye (5)
8.0 g and 2 g of Emalex NP-8 (manufactured by Nippon Emulsion Co., Ltd.) were dissolved. The above solution 18.00
To g, a solution prepared by dissolving 0.16 g of the following hydrazine derivative (reducing agent) and 1.22 g of the following developing agent (reducing agent) in 1.80 g of methylene chloride was added. Further, 3.50 g of the silver halide emulsion (A) prepared as described above and 3.35 g of the benzotriazole silver emulsion (A) were added,
Using a homogenizer, the mixture was stirred at 15,000 rpm for 5 minutes to obtain a photosensitive composition (A).

(Copolymer) Leuco dye (5) (Hydrazine derivative) (Developer) Preparation of microcapsule liquid (A) 18.6% aqueous solution of isoban (manufactured by Kuraray Co., Ltd.) 10.
51 g and 48.56 g of a 2.89% aqueous solution of pectin were added, and the photosensitive composition (A) was added to an aqueous solution whose pH was adjusted to 4.0 with 10% sulfuric acid, and the mixture was rotated at 7,000 rpm using a homogenizer. The resulting photosensitive composition was emulsified in an aqueous solvent.

Urea 40% aqueous solution 8.32 was added to 72.5 g of this aqueous emulsion.
g, resorcin 11.3% aqueous solution 2.82 g, formalin 37% aqueous solution 8.56 g, ammonium sulfate 8.76
% Aqueous solution 2.74 g was sequentially added, and heating was continued at 60 ° C. for 2 hours while stirring. Thereafter, the pH was adjusted to 7.0 using a 10% aqueous sodium hydroxide solution, and 3.62 g of a 30.9% aqueous sodium hydrogen sulfite solution was added to prepare a microcapsule solution (A).

Preparation of photosensitive material (101) Microcapsule liquid (A) 1 prepared as described above
To 0.0 g, 1% aqueous solution of the following anionic surfactant 1.
0 g, 1.0 g of 10% guanidine trichloroacetate (water / ethanol = 50/50 volume ratio) solution was added,
A light-sensitive material (101) according to the present invention was prepared by coating on polyethylene terephthalate having a thickness of μm using a # 40 coating rod and drying at about 40 ° C.

(Anionic surfactant) Preparation of Photosensitive Compositions (BF) In preparation of the above-mentioned photosensitive composition (A), the following leuco dyes (6), (7) and (1) are used instead of the leuco dye (5).
5), (16) and (17) are used, and the same operations as those for the photosensitive composition (A) are performed to obtain the corresponding photosensitive compositions (B), (C),
(D), (E) and (F) were prepared.

Leuco dye (6) Leuco dye (7) Leuco dye (15) Leuco dye (16) Leuco dye (17) Preparation of Microcapsule Liquid (BF) In preparation of the microcapsule liquid (A), the photosensitive composition (B) obtained above was used instead of the photosensitive composition (A).
-F), microcapsule liquids (BF) were obtained by performing the same operation as the above-mentioned microcapsule liquid (A).

Preparation of photosensitive materials (102) to (106) In the preparation of photosensitive material (101), instead of microcapsule liquid (A), microcapsule liquid B obtained above,
Except that C, D, E and F are used, the light-sensitive material (1
By performing the same operation as in (01), the corresponding photosensitive materials (102), (103), (1) of the present invention
04), (105) and (106) were created.

Preparation of image receiving material To 125 g of water, 11 g of 40% sodium hexametaphosphate aqueous solution was added, and further 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed and roughly dispersed by a mixer. The liquid was dispersed with a Dynamill disperser, and to 200 g of the obtained liquid, 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added and uniformly mixed. This mixed solution was uniformly applied onto an art paper having a weight of 43 g / m ² to give a wet film thickness of 30 μm, and then dried to prepare an image receiving material.

[Evaluation of Photosensitive Material] Each of the photosensitive materials (101 to 106) obtained above was imagewise exposed to 200 lux for 1 second using a tungsten bulb, and then heated on a hot plate heated to 125 ° C. for 30 seconds. . Then, stack each light-sensitive material with the above image-receiving material and pass through a 350 kg / cm ² pressure roller,
The maximum density of the positive color image (black image) obtained on the image receiving material was measured with a reflection densitometer. The maximum density D was measured at the peak wavelength of each hue [blue (B), green (G), red (R)].

Table 1 shows the above measurement results.

As is clear from the results in Table 1, the light-sensitive materials (101 to 106) containing the leuco dye according to the present invention have high maximum densities in all three hues (blue, green, red), and The concentration was well balanced. Also,
It was also confirmed that the image had high contrast. Therefore, it was confirmed that the leuco dye according to the present invention can be used as an excellent black image forming substance in a light-sensitive material.

[Example 2] [Preparation of light-sensitive material] Preparation of silver halide emulsion (G) Brominated with stirring gelatin aqueous solution (containing 20 g of gelatin and 1 g of potassium bromide in 1000 m of water and kept at 70 ° C). 600m aqueous solution containing 70g potassium
And an aqueous solution of silver nitrate (a solution of 0.59 mol of silver nitrate dissolved in 600 m of water) were added simultaneously at the same flow rate for 50 minutes. Five minutes after this was completed, 100 m of an aqueous solution containing 1.7 g of potassium iodide and an aqueous solution of silver nitrate (a solution of 0.01 mol of silver nitrate dissolved in 100 m of water) were simultaneously added at the same flow rate for 5 minutes. Thus, the monodisperse particles 14 having an average particle size of 0.20 μm
A surfaced silver iodobromide emulsion was prepared.

The above emulsion was washed with water and desalted, and then 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7 were added.
-Tetrazaindene (20 mg) was added and chemical sensitization was performed at 60 ° C. Further, the following sensitizing dye (a) was added to this emulsion.
75% of 1% methanol solution of
g of blue-sensitive silver halide emulsion (G) was obtained.

(Sensitizing dye a) Preparation of Photosensitive Composition (G) In 100 g of trimethylolpropane triacrylate, 0.2 g of the copolymer used in Example 1 above, 12 g of the following yellow image-forming substance (a), and Emarex NP.
2 g of -8 (manufactured by Nippon Emulsion Co., Ltd.) was dissolved.
To 18 g of the above solution, 0.5 g of the following reducing agent (I) and 0.6 g of the developer used in Example 1 above were added to 1.Methylene chloride.
A solution dissolved in 8 g was added. Further, 2 g of the silver halide emulsion (G) prepared above and 1 g of the benzotriazole silver emulsion (A) used in the above-mentioned Example 1 were added, and the mixture was stirred for 5 minutes at 15,000 rpm with a homogenizer to obtain a photosensitive composition. A composition (G) was obtained.

Yellow image-forming substance a (Reducing agent I) Preparation of microcapsule liquid (G) 18.6% aqueous solution of isoban (manufactured by Kuraray Co., Ltd.)
To 51 g, 48.56 g of a 2.89% aqueous solution of pectin was added, and the photosensitive composition (G) was added to an aqueous solution whose pH was adjusted to 4.0 with 10% sulfuric acid. The photosensitive composition was emulsified in an aqueous solvent by stirring for 2 minutes.

Urea 40% aqueous solution 8.32 was added to 72.5 g of this aqueous emulsion.
g, resorcin 11.3% aqueous solution 2.82 g, formalin 37% aqueous solution 8.56 g, ammonium sulfate 8.76
% Aqueous solution 2.74 g was sequentially added, and heating was continued at 60 ° C. for 2 hours while stirring. After that, the pH was adjusted to 7.0 with a 10% aqueous sodium hydroxide solution, 3.62 g of a 30.9% aqueous sodium hydrogen sulfite solution was added, and a microscopic mixture containing a blue-sensitive silver halide emulsion and a yellow image-forming substance was added. A microcapsule liquid (G) for dispersing the capsules was prepared.

Preparation of Silver Halide Emulsion (H) In the preparation of silver halide emulsion (G) above, sensitizing dye (a) was replaced by sensitizing dye (b) shown below, A green-sensitive silver halide emulsion (H) was prepared by performing the same operation as for the silver emulsion (G).

(Sensitizing dye b) Preparation of Photosensitive Composition (H) In preparation of the above-mentioned photosensitive composition (G), the silver halide emulsion (H) prepared as described above is used instead of the silver halide emulsion (G), The photosensitive composition (G) was prepared in the same manner as in the above-mentioned photosensitive composition (G) except that 12 g of the following magenta image-forming material (b) was used in place of 12 g of the yellow image-forming material (a). (H) was prepared.

Magenta image forming substance (b) Preparation of Microcapsule Liquid (H) In the above preparation of microcapsule liquid (G), the photosensitive composition (H) prepared as described above is used in place of the photosensitive composition (G). A microcapsule solution (H) in which microcapsules containing a green-sensitive silver halide emulsion and a magenta image forming substance were dispersed was prepared by performing the same operation as the above-mentioned microcapsule solution (G).

Preparation of Silver Halide Emulsion (I) The silver halide emulsion (I) above, except that the sensitizing dye (c) shown below is used in place of the sensitizing dye (a) in the preparation of the above silver halide emulsion (G). A red-sensitive silver halide emulsion (I) was prepared by performing the same operation as for the emulsion (G).

(Sensitizing dye c) Preparation of Photosensitive Composition (I) In preparation of the above-mentioned photosensitive composition (G), the silver halide emulsion (I) prepared as described above is used in place of the silver halide emulsion (G), Further, a photosensitive composition is obtained by performing the same operation as the above-mentioned photosensitive composition (G) except that 12 g of the following cyan image forming material (C) is used instead of 12 g of the yellow image forming material (a). The product (I) was prepared.

Cyan image forming substance (C) Preparation of Microcapsule Liquid (I) In the preparation of the above microcapsule liquid (G), the photosensitive composition (I) prepared as described above is used instead of the photosensitive composition (G). The microcapsule solution (I) in which the microcapsules containing the red-sensitive silver halide emulsion and the cyan image forming substance are dispersed by performing the same operation as the above-mentioned microcapsule solution (G).
Was prepared.

Preparation of Silver Halide Emulsion (J) In the above preparation of silver halide emulsion (G), three kinds of sensitizing dyes (a), (b) and (c) were used instead of sensitizing dye (a). Monodisperse tetradecahedral particles having an average grain size of 0.35 μm were obtained by the same operation as in the above silver halide emulsion (G) except that they were mixed and added in equal amounts and the reaction temperature or reaction time was adjusted. A silver iodobromide emulsion was prepared.

Preparation of Photosensitive Composition (J) In the preparation of the above-mentioned photosensitive composition (G), the silver halide emulsion (J) prepared as described above is used instead of the silver halide emulsion (G), Further, the same operation as in the above-mentioned photosensitive composition (G) is performed except that 6 g of the black image forming substance (leuco dye 7) used in Example 1 is used in place of 12 g of the yellow image forming substance (a). Thus, a photosensitive composition (J) was prepared.

Preparation of Microcapsule Liquid (J) In the above preparation of microcapsule liquid (G), except that the photosensitive composition (J) prepared as described above is used instead of the photosensitive composition (G). By performing the same operation as the above-mentioned microcapsule liquid (G), a microcapsule liquid (J) in which microcapsules containing the black leuco dye according to the present invention were dispersed was prepared.

Preparation of Photosensitive Material (201) In the preparation of the photosensitive material (101) of Example 1, instead of 10.0 g of the microcapsule solution (A), each microcapsule solution (G) prepared as described above, ( H) and (I) are each used in an amount of 3 g, and 1 g of the microcapsule liquid (J) containing the black leuco dye according to the present invention is used.
A light-sensitive material (201) according to the present invention containing a black image-forming substance according to the present invention and capable of obtaining a full-color image was prepared.

[Comparative Example] In the above-described preparation of the light-sensitive material (201), the same operation as in the light-sensitive material (201) was performed except that the microcapsule liquid (J) containing the black leuco dye according to the present invention was not used. A light-sensitive material (202) was prepared for comparison to obtain a full-color image containing no black image-forming substance.

[Evaluation of Photosensitive Material] The photosensitive materials (201) and (202) prepared as described above were exposed through a full-color transparent positive image including a black background using a tungsten bulb, and then exposed on a hot plate heated to 125 ° C. Heated for seconds. Then
350kg /
The positive color image obtained on the image receiving material was evaluated by passing through a pressure roller of cm ² .

As a result, the light-sensitive material (201) containing the leuco dye exhibiting a black color according to the present invention is compared with the light-sensitive material (202) containing no leuco dye exhibiting a black color,
A clear, full-color image with a high density of black background and high contrast in general was shown.

Claims (9)

[Claims] 1. A silver halide, a reducing agent, a polymerizable compound, and the following general formula [I] on a support: [Wherein R ¹ and R ² and R ³ and R ⁴ may be the same or different from each other and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R ¹ , R ² and R ³ And R ⁴ may combine with an adjacent nitrogen atom to form a 5- or 6-membered ring,
⁵ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group, R ⁶ represents a hydrogen atom, a halogen atom, a nitro group, or a group represented by —NHCOR ⁷ (R ⁷ represents an alkyl group or an aryl group. Which represents a group), wherein the above-mentioned substituents may be further substituted with other substituents], and a light-sensitive material having a light-sensitive layer containing a leuco dye represented by the above formula as a black image-forming substance. 2. The above leuco dye is represented by the following general formula [II]: [However, R ¹ and R ² are the same and represent an alkyl group,
R ⁵ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group, Z represents a hydrogen atom or an alkyl group, and Y represents OCH ₃ , CH.
₃ , Cl, COCH ₃ or CF ₃ ]. The photosensitive material according to claim 1. 3. The photosensitive layer according to claim 1, wherein the silver halide, the reducing agent, the polymerizable compound and the leuco dye represented by the above general formula [I] are contained in the photosensitive layer in a state of being housed in microcapsules. The light-sensitive material described. 4. A microcapsule in which the photosensitive layer contains silver halide, a reducing agent, a polymerizable compound and a leuco dye represented by the general formula [I], and a red-sensitive silver halide, a reducing agent, and a polymerization. The light-sensitive material according to claim 1, which contains at least both of a photosensitive compound and a microcapsule containing a cyan image-forming substance. 5. A microcapsule in which the photosensitive layer contains silver halide, a reducing agent, a polymerizable compound and a leuco dye represented by the above general formula [I], and a green-sensitive silver halide, a reducing agent, and a polymerization. 2. The light-sensitive material according to claim 1, which contains at least both a photosensitive compound and a microcapsule containing a magenta image-forming substance. 6. A microcapsule in which the photosensitive layer contains silver halide, a reducing agent, a polymerizable compound and a leuco dye represented by the above general formula [I], and a blue-sensitive silver halide, a reducing agent, and a polymerization. 2. The light-sensitive material according to claim 1, which contains at least both a photosensitive compound and a microcapsule containing a yellow image-forming substance. 7. A light-sensitive layer contains silver halide, a reducing agent, a polymerizable compound and microcapsules containing a leuco dye represented by the above formula [I], and further, red-sensitive silver halide and reduction. Agent, polymerizable compound and cyan color image forming substance-containing microcapsule, green-sensitive silver halide, reducing agent, polymerizable compound and magenta color image-forming substance-containing microcapsule, and blue-sensitive halogenated substance The light-sensitive material according to claim 1, comprising at least two types of microcapsules selected from three types of microcapsules containing silver, a reducing agent, a polymerizable compound, and a yellow color image-forming substance. 8. A microcapsule containing a silver halide, a reducing agent, a polymerizable compound and a leuco dye represented by the above general formula [I], a red-sensitive silver halide, a reducing agent, and a polymerizable layer. Microcapsules containing compound and cyan image-forming substance, green-sensitive silver halide, reducing agent, microcapsules containing polymerizable compound and magenta image-forming substance, and blue-sensitive silver halide, reducing agent The light-sensitive material according to claim 1, which comprises four types of microcapsules containing a polymerizable compound and a yellow image-forming substance. 9. The method according to claim 1, wherein the photosensitive layer contains the leuco dye represented by the general formula [I] in an amount of 0.5 to 50% by weight based on the polymerizable compound. Photosensitive material.