JP2699023B2 - Color diffusion transfer photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a color diffusion transfer method, and in particular, to a color diffusion transfer method, in particular, a dye resistant to release a diffusible dye in response to a reaction in which silver halide is reduced to silver. The present invention relates to a color diffusion transfer method for forming a positive image by combining a diffusible compound (these compounds are referred to as a positive dye-donating compound) and an ordinary negative-working silver halide emulsion.

More specifically, the present invention relates to a color diffusion transfer method for forming a positive image as described above, which has a low minimum density and improved color reproducibility.

(Prior Art) As a method of directly forming a positive image by a color diffusion transfer method, A) a direct positive silver halide emulsion and a diffusible dye corresponding to a reaction in which silver halide is reduced to silver are used. B) a method using a combination of a compound having a diffusion-resistant property to be released (referred to as a negative dye-donating compound), and B) a normal silver halide emulsion (a silver halide emulsion having a negative-positive response) and silver halide reduced to silver A non-diffusible compound which becomes diffusible by itself in response to the reaction performed or a non-diffusible compound which releases a diffusible dye in response to the reaction in which silver halide is reduced to silver (this Is referred to as a positive dye-donating compound).

In the method A), for example, British Patent No. 1,330,524, JP-B-48-39,165, U.S. Patent Nos. 3,443,940, and 4,474,867
No. 4,483,914, etc., which have a diffusible dye as a leaving group and release a diffusible dye by a coupling reaction with an oxidized reducing agent (DDR
Coupler), U.S. Patent Nos. 3,928,312, 4,053,312,
A compound (DRR compound) which is reducible to silver halide and releases a diffusible dye when the silver halide is reduced, which is described in 4,055,428 and 4,336,322, etc., is used.

No. 3,134,764, US Pat. No. 3,362,819, US Pat.
No. 7,200, No. 3,544,545, No. 3,482,972, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked (the dye developer is diffusible in an alkaline environment, As described in U.S. Pat. No. 4,503,137, etc., it releases diffusible dyes in an alkaline environment, but loses its ability when reacted with silver halide, as described in US Pat. No. 4,503,137. Compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.No. 3,980,479 and the like, U.S. Pat.
No. 4,559,290, EP 220,746A2, U.S. Pat.No. 4,783,396, U.S. Pat. And the like, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye is used.

Among the above two methods, the method B) is preferable in that higher sensitivity is easily obtained. However, the method B) has a problem that it is difficult to lower the density of the lowest density portion, which is particularly important in image formation.

In the method B), the dye is released by the reaction between the reducible dye-donating compound and the electron donor, and the oxidation of the electron donor by the oxidized form of the electron transfer agent (generated by developing the photosensitive silver halide). The competition reaction determines the density of the lowest density part (corresponding to the high exposure part) of the positive image.

Therefore, in order to lower the minimum density, there is a need for a technique for controlling the development of the photosensitive silver halide to optimize the generation of the oxidized form of the electron transfer agent.

On the other hand, silver halide grains used in silver halide photographic light-sensitive materials are known in various forms, and silver chloride grains are known as one type of silver halide grains. In recent years,
Many patents have been disclosed for performing various development processes using high silver chloride silver halide grains. (See, for example,
95345, 59-232342, 60-19140, JP-A-1-23259
However, these methods are aimed at shortening the development processing time, and it has been almost known that high silver chloride silver halide grains are effective for improving the image quality of the color diffusion transfer method. Had not been.

Photothermographic materials using silver halide grains containing silver chloride are disclosed in JP-A-61-137147, JP-A-61-235831 and JP-A-1-25.
No. 0003, this is a patent relating to an image forming method using a developing method completely different from that of the present invention, and the effect is completely different from that of the present patent.

OBJECTS OF THE INVENTION It is an object of the present invention to create a color diffusion transfer process that produces a positive image with low minimum density and improved color reproduction.

(Means for Achieving the Object) The object of the present invention is to provide: (1) having, on a support, at least one photosensitive silver halide emulsion layer combined with a dye image-forming substance and an electron donor; PH = 12 with electron transfer agent after exposure
In a color diffusion transfer photosensitive material which forms an image by developing with the above alkaline developer, the dye image forming substance is represented by the following general formula (C-I). Silver halide grains comprising at least one kind of reducible dye-donating compound to be released, wherein the silver halide emulsion contained in at least one of the silver halide emulsion layers contains 60 mol% or more of silver chloride. A color diffusion transfer photosensitive material comprising: PWR- (Time) _t- Dye (2) In the color diffusion transfer photosensitive material described above, the silver halide emulsion contained in at least one of the silver halide emulsion layers is composed of silver halide grains containing 85 mol% or more of silver chloride. And a color diffusion transfer photosensitive material.

 Hereinafter, the present invention will be described in detail.

As the silver chloride-containing grains used in the present invention, those composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, being substantially free of silver iodide means that the silver iodide content is 1 mol% or less, preferably 0.5 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to equalize the properties of each grain. Regarding the distribution of silver halide inside the silver halide emulsion grains, any portion of the silver halide grains has a so-called uniform structure in which the composition is the same, or a core inside the silver halide grains and surrounds the core. A so-called laminated type particle having a different halogen composition from a shell (one or more layers) or
Particles having a structure having a different halogen composition in a non-layered manner inside or on the surface of the particle (in the case of being on the surface of the particle, a structure in which different composition portions are bonded on the edge, corner or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is advantageous to use one of the latter two types rather than particles having a uniform structure. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. Well,
Further, a structure which positively has a continuous structural change may be used.

The halogen composition of the silver chlorobromide emulsion used in the present invention must have a silver chloride ratio of 60 mol% or more. More preferably, it is 85 mol% or more.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the grain, on the edge, corner or plane of the grain surface. One preferable example is a layer epitaxially grown on the corner of the grain.

The method of producing the localized phase may be a halogen conversion method using a water-soluble bromide, or a method using a mixture with small-sized silver bromide particles as described in EP0273430, and is not limited to a specific method. Absent.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the photographing area of the grain, and the number average is taken) is from 0.20 μm to 2.0 μm. Is suitable, but 0.3 μm to 1.
5 μm is preferred.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle in terms of circle / thickness) of 2 or more, preferably 8 or more, exceed 50% of all grains as a photographed area can be preferably used.

The high silver chloride emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7 years), Photographic Emulsion Chemistry by GFDuffin
(Focal Press, 1966), M by VLZelikman et al
aking and Coating Photographic Emulsion (Focal Pre
ss, published in 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of the spectral sensitizing dye used at this time include, for example, Heterocyclic compoun by FM Harmer.
ds-Cyanine dyes and related compounds (John Wiley
& Sons [New York, London], 1964). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

Next, each component included in the present invention will be described.

(A) Support The support used in the present invention includes a transparent support, a white support and a black support which are usually used as a smooth photographic support. As the transparent support, polyethylene terephthalate, cellulose acetate, polycarbonate or the like having a thickness of 50 to 350 μm, preferably 70 to 210 μm is used. The transparent support may contain a minute amount of a pigment such as titanium dioxide or a small amount of a dye to prevent light piping.

The white support in the present invention refers to a support in which at least the side on which the dye image-receiving layer is coated is white, and any support having sufficient whiteness and smoothness can be used. For example, titanium oxide having a particle size of 0.1 to 5 μm,
Barium sulfate, polymer film whitened by the formation of microvoids by the addition or stretching of white pigments such as zinc oxide, such as polyethylene terephthalate film formed by ordinary sequential biaxial stretching, polystyrene, polypropylene films and synthetic paper, What laminated | stacked polyethylene, polyethylene terephthalate, polypropylene, etc. on both surfaces of paper is preferably used. A white pigment such as titanium white may be kneaded in the laminate layer.

The thickness of the support is 50 to 350 μm, preferably 70 to 210 μm
m, more preferably 80 to 150 μm. If necessary, a light-shielding layer may be provided on the support. For example, a support obtained by laminating polyethylene containing a light-shielding agent such as carbon black on the back of a white support is used.

As the black support, a thickness of 50 to 350 μm containing a light-shielding agent such as carbon black, preferably 70 to 210 μm polyethylene terephthalate, cellulose acetate, polycarbonate, polystyrene, polypropylene, etc.
Or a thickness of 50 including a light-blocking agent such as carbon black
A paper support having a thickness of 400 to 400 μm, preferably 70 to 250 μm, on both sides of which a polystyrene, polyethylene terephthalate, polypropylene or the like is laminated is preferably used.

As carbon black raw material, for example, Donnel Voest
Any method such as a channel method, a thermal method and a furnace method as described in "Carbon Black" Marcel Dekker, Inc. (1976) can be used. The particle size of the carbon black is not particularly limited, but is preferably 90 to 1800 °. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shaded,
An optical density of about 5 to 10 is desirable. When a black support is used or when the whiteness of the white support is insufficient, it is necessary to provide a white light reflecting layer between the support and the dye image-receiving layer. It is preferable to provide a layer containing a white pigment such as barium sulfate, zinc oxide or the like, or a hollow polymer latex.

(B) Layer having a neutralizing function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried in from the treatment composition, and if necessary, And a multilayer structure composed of layers such as a neutralization rate adjusting layer (timing layer) and an adhesion strengthening layer. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that gives such an acidic group by hydrolysis), and more preferably a higher acidic substance such as oleic acid described in US Pat. No. 2,983,606. Fatty acids, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 3,362,819; acrylic acid and acrylic as disclosed in French Patent 2,290,699 Acid ester copolymers; U.S. Pat. No. 4,139,383 and Research Disclosure No.
Examples include latex-type acidic polymers as disclosed in 16102 (1977).

Others, U.S. Pat.No. 4,088,493, JP-A-52-153,739
No. 53-1,023, No. 53-4,540, No. 53-4,541,
The acidic substances disclosed in JP-A-53-4,542 and the like can also be mentioned.

Specific examples of the acidic polymer include a copolymer of ethylene, vinyl acetate, a vinyl monomer such as vinyl methyl ether, and maleic anhydride and its n-butyl ester,
Copolymers of butyl acrylate and acrylic acid, cellulose acetate, hydrogen diphthalate, and the like.

The polymer acid may be used alone or in combination with a hydrophilic polymer. Examples of such a polymer include polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred.

Further, a polymer other than the hydrophilic polymer, such as cellulose acetate, may be mixed with the polymer acid.

The amount of the polymer acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymer acid to the alkali per unit area is preferably from 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye changes, or a stain occurs on a white background, and the hue changes even when the amount is too large.
Otherwise, inconveniences such as a decrease in light resistance occur. A more preferred equivalent ratio is 1.0 to 1.3. When mixed with a hydrophilic polymer, the amount of the hydrophilic polymer is too large or too small, and the quality of the photograph is deteriorated. The weight ratio of the hydrophilic polymer to the polymer acid is 0.1 to 10, preferably 0.3 to 3.0.

Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardeners well known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. In addition, if necessary, an antioxidant, a development inhibitor and a precursor thereof can be added.

(C) Neutralization timing layer The timing layer used in combination with the neutralization layer is, for example, an alkali such as gelatin, polyvinyl alcohol, a partially acetalized product of polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like. A polymer that lowers the permeability; a latex polymer that is made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer to increase the activation energy of alkali permeation;
A polymer having a lactone ring is useful.

Among them, JP-A-54-136328, U.S. Pat.
No. 4,009,030, 4,029,849, etc .; Timing layer using cellulose acetate;
128335, 56-69,629, 57-6,843, U.S. Patent
4,056,394, 4,061,496, 4,199,362, 4,25
Latex polymers prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid disclosed in U.S. Pat. Nos. 0,243, 4,256,827, and 4,268,604;
Lactone ring-containing polymer disclosed in JP-A-9,516; JP-A-56-25735, JP-A-56-97346, and JP-A-57-6842
No., European Patent (EP) No. 31,957A1, No. 37,724A1,
The polymers disclosed in JP-A-48,412A1 and the like are particularly useful.

 In addition, those described in the following documents can also be used.

U.S. Patent Nos. 3,421,893, 3,455,686, 3,575,701
Nos. 3,778,265, 3,785,815, 3,847,615,
4,088,493, 4,123,275, 4,148,653, 4,2
01,587, 4,288,523, 4,297,431, West German Patent Application (OLS) 1,622,936, 2,162,277, Research Disc
losure15,162 No.151 (1976).

JP-A-59-202463, U.S. Pat.Nos. 4,297,431 and 4,2
Nos. 88,523, 4,201,587, 4,229,516, JP-A-55-
121438, 56-166212, 55-41490, 55-543
No. 41, 56-102852, 57-141644, 57-173834
No. 57-179841, West German Patent Application Publication (OLS) 2,910,2
No. 71, European Patent Application Publication EP31957A1, Research Disclosu
re No. 18452 and the like.

 The neutralization timing layer may be a single layer or multiple layers.

In addition, for example, US Pat. No. 4,009,029 and West German Patent Application (OLS) 2,913,164
No. 3,014,672, JP-A-54-155837, and 55-13874
No. 5, etc., and a development inhibitor disclosed therein and / or a precursor thereof, or a hydroquinone precursor disclosed in U.S. Pat. No. 4,201,578, and other photographic useful additives or precursors thereof can also be incorporated. .

(D) Dye image receiving layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This is a single layer,
Further, it may have a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-252551. As the mordant, a polymer mordant is preferable.

The polymer mordant used in the present invention is a polymer having a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, and a polymer having a molecular weight of 5,000 or more, particularly preferably 10,000. That's all.

For example, U.S. Pat.Nos. 2,548,564, 2,474,430,
148,061, 3,756,814, etc .; vinylpyridine polymer and vinylpyridinium cationic polymer; U.S. Pat.No. 4,124,386, vinylimidazolium cationic polymer disclosed in U.S. Pat.No. 3,625,694, 3,859,096 U.S. Pat. No. 3,958,995; U.S. Pat. No. 3,958,995;
No. 2,721,852, No. 2,798,063, JP-A-54-115,228
Nos. 54-145,529, 54-126,027, 54-155,83
5, sol-type mordants disclosed in JP-A-5-17,352 and the like; water-insoluble mordants disclosed in U.S. Patent 3,898,088 and the like; U.S. Patent Nos. 4,168,976 and 4,20
Reactive mordants capable of forming a covalent bond with the dyes disclosed in 1,840 and the like; further, U.S. Pat. Nos. 3,709,690 and 3,7
No. 88,855, No. 3,642,482, No. 3,488,706, No. 3,
No. 557,066, No. 3,271,147, No. 3,271,148, JP-A-53-30328, JP-A-52-155528, JP-A-53-125, JP-A-53-125
Examples thereof include mordants disclosed in 1024, 53-107,835, British Patent 2,064,802 and the like.

Other examples include mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156.

Of these mordants, those that are unlikely to migrate from the mordant layer to another layer are preferred, for example, those that undergo a cross-linking reaction with a matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) -type mordants are preferred. . Particularly preferred is a latex dispersion mordant, having a particle size of 0.01 to
2μ, preferably 0.05-0.2μ.

The coating amount of the mordant varies depending on the type of the mordant, the content of the quaternary cation group, the type and amount of the dye to be morded, the kind of the binder to be used, etc., and is 0.5 to 10 g / m ² , preferably 1.0 to 10 g / m ² .
5.0 g / m ^2, particularly preferably 2 to 4 g / m ^2.

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferable.

An anti-fading agent may be used in the image receiving layer. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. These are substantially contained in the image receiving layer, but can be added to other layers if the effect is obtained.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of ultraviolet absorbers include benzotriazole-based compounds (US Pat. No. 3,533,794, etc.), 4-thiazolidone-based compounds (US Pat. No. 3,352,681, etc.), benzophenone-based compounds (JP-A-46-2784, etc.), and others. Showa 54
And compounds described in JP-A-48535, JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As metal complexes, U.S. Pat.Nos. 4,241,155 and 4,2
Nos. 45,018, columns 3-36, 4,254,195, columns 3-8, JP-A-62-174741 and JP-A-61-88256, pages (27) to (29),
There are compounds described in JP-A-1-75568 and JP-A-63-199248.

Examples of useful anti-fading agents are described in JP-A-62-215272 (125).
~ (137).

An anti-fading agent for preventing fading of the dye transferred to the image receiving element may be previously contained in the image receiving element,
You may make it supply to an image receiving element from outside, such as a photosensitive element or a processing composition.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent whitening agent may be used for the photosensitive element and the image receiving element.
In particular, it is preferable that the fluorescent whitening agent is incorporated in the image receiving element, or it is incorporated in the photosensitive element or the processing composition and supplied to the image receiving element during the processing step. For example, K.Veenkata
Raman, "The Chemistry of Synthetic Dyes", Vol. V, Chapter 8, JP-A-61-143752, and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

It can be used in combination with a fluorescent whitening agent and an anti-fading agent.

(E) Release Layer In the present invention, a release layer is provided, if necessary, to peel off the photosensitive element and the image receiving element after processing. Therefore, this release layer must be easily peelable after the treatment. Materials for this purpose include, for example, JP-A-47-8237 and JP-A-59-8237.
−220727, 59−229555, 49−4653, U.S. Pat.
5, 459518, JP-A-49-4334, 56-65133, 45-2
4075, U.S. Patents 3227550, 2759825, 4401746, 436
6227 and the like can be used. One specific example is water-soluble (or alkali-soluble)
And cellulose derivatives of For example, hydroxyethyl cellulose, cellulose acetate-phthalate,
Plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. As another example, various natural polymers such as alginic acid,
Pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Still another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, polybutyl methacrylate, or a copolymer thereof, or the like.

The release layer may be a single layer or, for example, disclosed in
It may be composed of a plurality of layers as described in 220727, 60-6042 and the like.

(F) Photosensitive layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is provided. The components will be described below.

(1) Dye image-forming substance The dye image-forming substance (hereinafter referred to as a reducible dye-donating compound) used in the present invention does not itself release a dye in connection with silver development, but when it is reduced, It releases pigment. Compounds of this type can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, for example, U.S. Patent Nos. 4,183,753, 4,142,891, and 4,278,7
50, 4,139,379, 4,218,368, JP-A-53-110827, U.S. Patents 4,278,750, 4,356,249, 4,358,525, and JP-A-5
3-110827, 54-130927, 56-164342, U.S. Pat.
No. 83,396, Gazette Technical Report 87-6199, European Patent Publication 220746A2, and the like.

The reducible dye-providing compound used in the present invention is a compound represented by the following general formula [CI].

PWR- (Time) _t -Dye General formula [CI] In the formula, PWR is reduced to-(Time) _t -D
Represents a group that releases ye.

Time represents a group that is released from the PWR as-(Time) _t- Dye and then releases Dye via a subsequent reaction.

 t represents an integer of 0 or 1.

 Dye represents a dye or its precursor.

 First, the PWR will be described in detail.

PWR is U.S. Pat.No. 4,139,389 or U.S. Pat.
No. 379, 4,564,577, JP-A-59-185333, 57-84
No. 453, which corresponds to a portion containing an electron accepting center and an intramolecular nucleophilic substitution reaction center in a compound which releases a photographic reagent by a nucleophilic substitution reaction in the molecule after being reduced as disclosed in No. 453. Or U.S. Patent 4,232,107
As disclosed in JP-A-59-101649, Research Disclosure (1984) IV, 24025 or JP-A-61-88257, a photographic reagent is eliminated from a molecule by an electron transfer reaction after reduction. It may correspond to an electron-accepting quinonoid center in the compound and a portion containing a carbon atom linking the quinonoid center to the photographic reagent.
JP-A-56-142530, U.S. Pat.Nos. 4,343,893, 4,6
No. 19,884, an aryl group substituted with an electron-withdrawing group in a compound that releases a photographic reagent after a single bond is cleaved after reduction as described in JP-A No. 19884, and an atom linking the photographic reagent to the aryl group (a sulfur atom or a carbon atom or (Nitrogen atom). U.S. Patent 4,450,22
As disclosed in No. 3, it may correspond to a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a moiety containing a carbon atom linking the nitro group and the photographic reagent, It may be a geminal dinitro moiety in a dinitro compound from which a photographic reagent is beta-eliminated after electron acceptance described in Japanese Patent No. 4,609,610 and a moiety containing a carbon atom linking it to the photographic reagent.

Further, SO _{2 is} contained in one molecule described in U.S. Pat.No.4,840,887.
-X (X represents any one of oxygen, sulfur and nitrogen) and a compound having an electron-withdrawing group, and a PO-X bond (X is the same as described above) in one molecule described in JP-A-63-271344. ) And a compound having an electron-withdrawing group, and a C-X 'bond (X' has the same meaning as X or -SO) in one molecule described in JP-A-63-271341.
_2- )) and a compound having an electron-withdrawing group.

In order to more sufficiently achieve the object of the present invention, among the compounds of the general formula [CI], those represented by the general formula [CII] are preferable.

General formula (C II) (Time _t Dye binds to at least one of R ¹⁰¹ , R ¹⁰² or EAG.

The part corresponding to the PWR in the general formula [C II] will be described.

X represents a group (—N (R ¹⁰³ ) —) containing an oxygen atom (—O—), a sulfur atom (—S—), and a nitrogen atom.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent a group other than a hydrogen atom or a mere bond.

Examples of groups other than the hydrogen atom represented by R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group, and a sulfamoyl group. These may have a substituent.

R ¹⁰¹ and R ¹⁰³ are preferably a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group and the like. R ₁₀₁ , and R
The number of carbon atoms of ¹⁰³ is preferably 1 to 40.

R ¹⁰² is preferably a substituted or unsubstituted acyl group or a sulfonyl group. Examples are the same as the acyl group and the sulfonyl group described for R ¹⁰¹ and R ¹⁰³ . The number of carbon atoms is preferably 1 to 40.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may combine with each other to form a 5- to 8-membered ring.

 X is particularly preferably oxygen.

 EAG will be described later.

In order to further achieve the object of the present invention, the general formula (CI
Among the compounds represented by I], those represented by the general formula [C III] are preferable.

General formula (C III) (Time _t Dye binds to at least one of R ₁₀₄ and EAG.

 X has the same meaning as described above.

R ¹⁰⁴ represents an atom group which is bonded to X and a nitrogen atom to form a 5- to 8-membered monocyclic or condensed heterocyclic ring including the nitrogen atom.

In the general formulas [C II] and [C III], EAG represents a group that receives an electron from a reducing substance and is bonded to a nitrogen atom. EAG is preferably a group represented by the following general formula [A].

General formula [A] In the general formula [A], Z ₁ is Represents

V _n represents an atomic group forming a three- to eight-membered aromatic group together with Z ₁ and Z ₂ , and n represents an integer of three or eight.

V ₃ ; −Z ₃ −, V ₄ ; −Z ₃ −Z ₄ −, V ₅ ; −Z ₃ −Z ₄ −Z ₅ −, V ₆ ;
−Z ₃ −Z ₄ −Z ₅ −Z ₆ −, V ₇ ; −Z ₃ −Z ₄ −Z ₅ −Z ₆ −Z ₇ −, V ₈ ;
−Z ₃ −Z ₄ −Z ₅ −Z ₆ −Z ₇ −Z ₈ −.

Z ₂ −Z ₈ —O—, —S—, or —SO ₂ —, and Sub represents a mere bond (a pi bond), a hydrogen atom, or a substituent described below. Sub may be the same as or different from each other, and may be bonded to each other to form a 3- to 8-membered saturated or unsaturated carbocyclic or heterocyclic ring.

In the general formula [A], Sub is selected such that the sum of Hammett's substituent constant sigma para of the substituent is +0.50 or more, more preferably +0.70 or more, and most preferably +0.85 or more.

EAG is preferably an aryl group or a heterocyclic group substituted by at least one electron-withdrawing group. Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire chemical. Examples of physical properties of the whole compound include, in addition to being able to adjust the ease of receiving electrons, for example, water solubility, oil solubility, diffusibility, sublimability, melting point, dispersibility in a binder such as gelatin, reactivity to a nucleophilic group, It can be used to adjust the reactive group for an electrophilic group.

Specific examples of EAG are described in U.S. Pat. No. 4,783,396 and EP 220746A2 Nos. 6-7.

Time is triggered by cleavage of nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bonds, followed by dye
Represents a group that releases

Various groups represented by Time are known, for example,
No. 147244, pp. (5)-(6), pp. 61-236549, (8)
Page- (14) and groups described in JP-A-62-215270.

The dye represented by Dye may be a pre-formed dye, or it may be a dye precursor that can be converted to a dye in a photographic or additional processing step, and the final image dye may or may not be metal chelated. Good. Representative dyes include metal-chelated or non-metal-chelated dyes such as azo dyes, azomethine dyes, anthraquinone dyes, and phthalocyanine dyes. Of these, azo cyan, magenta and yellow dyes are particularly useful.

Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, and 4,013,633
Nos. 4,245,028, 4,156,609, 4,139,383,
4,195,992, 4,148,641, 4,148,643, 433
No. 6322; JP-A-51-114930 and JP-A-56-71072;
rch Disclosure ”Nos. 17630 (1978) and 16475 (197
7) Items listed in item.

Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,544, 3,932,380
No. 3,931,144, No. 3,932,308, No. 3,954,476,
4,233,237, 4,255,509, 4,250,246, 4,1
42,891, 4,207,104 and 4,287,292;
No. 106,727, No. 52-106727, No. 53-23,628, No. 55-3
6,804, 56-73,057, 56-71060, 55-134
What is described in the issue.

Examples of cyan dyes: U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635
No. 4,268,625, No. 4,171,220, No. 4,242,435,
No. 4,142,891, No. 4,195,994, No. 4,147,544, No. 4,1
48,642; British Patent 1,551,138; JP-A-54-99431;
No. 52-8827, No. 53-47823, No. 53-143323, No. 54
-99431, 56-71061; European Patent (EPC) 53,
Nos. 037 and 53,040; Research Disclosure 17,630 (197
Nos. 8) and 16,475 (1977).

Further, as one kind of the dye precursor, a diffusion-resistant dye-providing substance to which a dye whose absorption spectrum has been temporarily shifted may be used during storage and exposure of the photosensitive material. The term “dye temporarily shifted in absorption spectrum” (hereinafter referred to as “temporarily shifted dye”) means a dye whose absorption spectrum has been changed from the original absorption spectrum when observed as an image. , The absorption spectrum may be changed to the original absorption spectrum at the same time as the dye is released from the diffusion-resistant dye-providing substance, or may be changed to the original absorption spectrum during development independently of the release. , The original absorption spectrum may be obtained.

The dyes used here include yellow, magenta, cyan, and black. These dyes can be structurally classified into nitro and nitroso dyes, azo dyes (benzene azo dyes, naphthalene azo dyes, heterocyclic azo dyes, and the like), and stilbene. Dye, carbium dye (diphenylmethane dye, triphenylmethane dye, xanthene dye,
Acridine dye), quinoline dye, methine dye (polymethine dye, azomethine dye, etc.), thiazole dye, quinone imine dye (azone dye, oxazine dye,
Thiazine dyes), lactone dyes, aminoketone dyes, hydroxyketone dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, and the like. And quinone imine dyes, and particularly preferred are azo dyes.

As a method for preparing a temporary shift dye which can be used in the present invention, a method in which a dye is converted into a two-electron reductant to shift the original absorption spectrum to a shallow color and then oxidized during or after development to obtain the original absorption spectrum (azo Dyes, anthraquinone dyes, methine dyes, quinone imine dyes, indigo dyes, etc.) and the auxiliary chromophores are chemically blocked to shift the original absorption spectrum to a shallower color. [Chemical blocking method] (azo dye, carbonium dye, methine dye, etc.), or a method of changing to a dye having a desired absorption spectrum by chelating with a metal ion after reaching the image receiving layer [ Chelation method] (azo dyes, methine dyes, phthalocyanine dyes, etc.). Blocking method and the post-chelate method is preferred. Regarding these methods, in the method in which the auxochrome is chemically blocked, examples of release and deblocking of a dye occurring independently are described in JP-A-57-158638 and JP-A-55-53.
No. 329, JP-A-55-53330 and the like, and examples more generally described as other block methods include U.S. Pat.Nos. 4,009,029, 4,310,612, and 3,300.
674,478, 3,932,480, 3,993,661, 4,335,2
No. 00, 4,363,865 and 4,410,618. A specific example of simultaneous release and deblocking of a dye is described in US Pat. No. 4,783,396. Further, in the method of changing to a dye having a desired absorption spectrum by chelating with a metal ion after reaching the image receiving layer, JP-A-58-209742 and JP-A-58-20
9741, 58-17438, 58-17437, 58-17436
No. 57-185039, No. 57-58149, U.S. Pat.
No. 93, 4,148,642, 4,147,544, JP-A-57-1586
No. 37, No. 58-123537, No. 57-181546, No. 60-57837
Nos. 57-182738, 59-208551, 60-37555
Nos. 59-15448, 59-149362 and 59-164553 describe examples thereof.

The compound represented by the general formula (C II) or (C III) needs to be immobile in the photographic layer itself,
For this purpose, the position of EAG, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁴ or X (particularly E
(Position of AG) preferably has a ballast group having 8 or more carbon atoms.

Hereinafter, typical specific examples of the reducible dye-providing compound used in the present invention will be listed, but the present invention is not limited to these.U.S. Pat.No. 4,783,396, European Patent Publication 220
Dye-donating compounds described in, for example, 746A2 and Published Technical Report 87-6199 can also be used.

Each of these compounds can be synthesized by the methods described in the patent specifications cited above. The amount of the reducible dye-donating compound used depends on the extinction coefficient of the dye, but is 0.05 to 5 mmol / m ² , preferably 0.1 to 3 mmol.
/ m ² . Dye-donating substances can be used alone or in combination of two or more. Further, in order to obtain an image of black or a different hue, for example, as described in JP-A-60-162251, for example, in a layer containing at least one type of each of the cyan, magenta and yellow dye-donor substances containing silver halide or Two or more dye-donating substances that release a mobile dye having a different hue, such as a mixture contained in an adjacent layer, can also be used.

(2) Electron Donor In the present invention, an electron donor (the electron donor in the present invention includes its precursor) is used. For details of these compounds, see US Pat. No. 4,783,396 and European Patent Publication 220746A2. And published technical report 87-6199. Particularly preferred electron donors are compounds represented by the following general formula [C] or [D].

In the color, A ₁₀₁ and A ₁₀₂ represent a hydrogen atom or a protecting group for a phenolic hydroxyl group which can be deprotected by a nucleophile, respectively.

 Here, the nucleophile is OH , RO (R; alkyl
Group, aryl group, etc.), hydroxamic acid anionic acid SO₃
²Anionic reagents and primary or secondary amines
, Hydrazine, hydroxylamines, alcohol
And compounds with lone pairs such as thiols
Can be

In the formula, when A ₁₀₁ and A ₁₀₂ represent a group that can be removed by an alkali (hereinafter, referred to as a precursor group), it is preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazolyl group, or a sulfonyl. A group that can be hydrolyzed such as a group, a precursor group of the type utilizing a reverse Michael reaction described in U.S. Pat.No. 4,009,029, and an anion generated after a ring cleavage reaction described in U.S. Pat. US Patent No. 3,67
4,478, 3,932,480 or 3,993,661, a precursor group in which an anion described in JP-A-3,993,661 causes an electron transfer via a conjugated system and thereby causes a cleavage reaction, U.S. Pat.
No. 0, a precursor group which causes a cleavage reaction by electron transfer of an anion reacted after ring opening or a precursor group utilizing an imidomethyl group described in U.S. Pat. Nos. 4,363,865 and 4,410,618.

A ₁₀₁ and A ₁₀₂ may combine with R ²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ to form a ring when possible. Also A
₁₀₁ and A ₁₀₂ may be the same or different.

R ²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ each represent a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amide group, and an imide. Group, carboxyl group, sulfonamide group and the like. These groups may have a substituent, if possible.

However, the total carbon number of R ^{201 to} R ²⁰⁴ is 8 or more. In the general formula [C], R ²⁰¹ and R ²⁰² and / or
R ²⁰³ and R ²⁰⁴ are represented by R ²⁰¹ and R ²⁰² , R in the general formula [D].
²⁰² and R ²⁰³ and / or R ²⁰³ and R ²⁰⁴ may combine with each other to form a saturated or unsaturated ring.

Among the electron donors represented by the general formula [C] or [D], those in which at least two of R ^{201 to} R ²⁰⁴ are substituents other than a hydrogen atom are preferable. Particularly preferred compounds are those in which at least one of R ²⁰¹ and R ²⁰² and at least one of R ²⁰³ and R ²⁰⁴ are substituents other than a hydrogen atom.

A plurality of electron donors may be used in combination, or an electron donor and a precursor thereof may be used in combination.

Specific examples of the electron donor are listed, but the present invention is not limited to these compounds.

The use amount of the electron donor has a wide range, but is preferably 0.01 mol to 50 mol per 1 mol of the positive dye-providing substance, particularly
A range of about 0.1 mol to 5 mol is a preferable range. The amount is 0.001 mol to 5 mol, preferably 0.01 mol to 1.5 mol, per 1 mol of silver halide.

(4) Addition Method In order to introduce the dye-donating substance, the electron donor or its precursor and other hydrophobic additives of the present invention into the hydrophilic colloid layer, a high-boiling organic solvent such as phthalic acid alkyl ester (dibutyl phthalate) is used. , Dioctyl phthalate, etc.), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, di-4 octyl butyl phosphate), citrate esters (eg, tributyl acetyl citrate), benzoic acid Acid esters (eg, octyl benzoate), alkyl amides (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (eg, tributyl trimesate), Carboxylic acids described in JP-A-63-85633;
9-83154, 59-178451, 59-178452, 59-
178453, 59-178454, 59-178455, 59-17
No. 2,322,027 using the compound described in No. 8457, or an organic solvent having a boiling point of about 30 ° C. to 160 ° C., for example, ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, After dissolving in secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid.
The above-mentioned high-boiling organic solvent and low-boiling organic solvent may be mixed and used. Further, after the dispersion, if necessary, the low-boiling organic solvent may be removed by ultrafiltration or the like before use. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used. Further, the amount is 5 g or less, preferably 2 g or less per 1 g of the diffusion-resistant reducing agent. Further, the amount of the high-boiling organic solvent is 1 g or less, preferably 0.5 g or less, more preferably 0.3 g or less per 1 g of the binder. Also, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can be used.
In addition, it can be directly dispersed in an emulsion, or can be dissolved in water or alcohols and then dispersed in gelatin or an emulsion.

In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. (For example, JP-A-59-174830, JP-A-53-102733,
Methods described in JP-A-63-271339) Various surfactants can be used when a hydrophobic substance is dispersed in a hydrophilic colloid. For example, JP-A-59-
The surfactants listed on pages (37) to (38) of 157636 can be used.

(5) Silver halide emulsion The silver halide which can be used in combination with the above emulsion of the present invention includes silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and chloroiodobromide. Any of silver may be used. The halogen composition in the grains may be uniform, or the grains may have a multiple structure having different compositions between the surface and the inside (Japanese Patent Application Laid-Open Nos. 57-154232 and 58-154232).
No. 108533, No. 59-48755, No. 59-52237, U.S. Pat.
4,433,048 and EP 100,984). Further, tabular grains having a grain thickness of 0.5 μm or less, a diameter of at least 0.6 μm and an average aspect ratio of 2 or more (US Pat. No. 4,414,310)
No. 4,435,499 and West German Open Patent (OLS) No. 3,241,
646A ₁ etc.) or monodisperse emulsions having a nearly uniform particle size distribution (JP-A-57-178235, JP-A-58-100846, JP-A-58-14).
829, WO 83 / 02338A ₁ issue, it may be a European Patent No. 64,412A ₃ and the second 83,377A _1, etc.).

Two or more silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like may be used in combination. Two or more single emulsions having different grain sizes may be mixed to adjust the gradation.

The grain size of the silver halide in the present invention, the average grain size is
It is preferably from 0.001 μm to 10 μm, more preferably from 0.001 μm to 5 μm.

These silver halide emulsions may be prepared by any of an acidic method, a neutral method, and an ammonia method. The reaction between the soluble silver salt and the soluble halide may be a one-sided mixing method, a simultaneous mixing method, May be used. A back-mixing method in which grains are formed in excess of silver ions or a controlled double-jet method in which pAg is kept constant can also be employed. Further, in order to accelerate the grain growth, the concentration, amount or rate of silver salt and halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-1581).
No. 24, U.S. Pat. No. 3,650,757).

Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, U.S. Pat. No. 4,094,6).
No. 84).

In the step of forming the silver halide grains used in the present invention, ammonia is used as a silver halide solvent,
No. 386, organic thioether derivatives described in
For example, a sulfur-containing compound described in JP-A-144319 can be used.

Cadmium salts, zinc salts, lead salts, thallium salts, and the like may coexist in the process of particle formation or physical ripening.

Further, a water-soluble iridium salt such as iridium chloride (III, IV) or ammonium hexachloroiridate, or a water-soluble rhodium salt such as rhodium chloride can be used for the purpose of improving high illuminance failure and low illuminance failure.

The soluble salts may be removed from the silver halide emulsion after the formation of the precipitate or after the physical ripening. Therefore, the silver halide emulsion can be subjected to the Nudel washing method or the sedimentation method.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or the like can be used alone or in combination for an emulsion for a normal photosensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526 and JP-A-58-215644).

The silver halide emulsion used in the present invention 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 a grain. It is also possible to use a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat. Nos. 2,592,250 and 3,761,276, JP-B-58-3534, and JP-A-57-136641. Preferred for combination in the present invention. Nucleating agents, U.S. Pat.Nos. 3,227,552, 4,245,037, 4,255,511, 4,2
Nos. 66,013, 4,276,364 and OLS 2,635,316.

As a method for forming the silver halide grains used in the present invention, a known single jet method or double jet method can be used, and in the latter method, further, a so-called control, in which the pAg in the reaction solution is kept constant. The de-double jet method can also be used. Further, a method of combining them may be used. In any of the silver halide emulsion forming methods described above, any of the known single-stage addition method or multi-stage addition method may be used, and the addition speed is as follows:
It may be a constant rate or a rate that changes stepwise or continuously (for example, by changing the addition flow rate of the solution while keeping the concentration of the soluble silver salt and / or halide constant). Alternatively, a method of changing the concentration of the soluble silver salt and / or halide in the addition solution while keeping the addition flow rate constant, or a method of a combination thereof) may be used. Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner.

The coating amount of the photosensitive silver halide of the present invention is 1 mg in terms of silver.
Or in the range of 10 g / m ² .

It is advantageous to use gelatin as a protective colloid used when preparing the emulsion of the present invention, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein;
Hydroxyethylcellulose, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin, Bull. Soc. Sci. Photo. Japan, No. 16, P30 (196
6) Enzyme-treated gelatin as described may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used.

In the present invention, various antifoggants or photographic stabilizers can be used. An example is RD1764
3 (1978), azoles and azaindenes described on pages 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in JP-A-59-168442, or mercapto compounds and their derivatives described in JP-A-59-111636. Metal salt, JP-A-62-87957
And the like.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, polopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, U.S. Pat.No. 4,617,257, JP-A-59-180
No. 550, No. 60-140335, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.

Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641). And those described in JP-A-63-23145).

These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or may be added to U.S. Pat.
No. 4,225,666, before and after nucleation of silver halide grains. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

(6) Composition of photosensitive layer To reproduce a natural color by the subtractive color method, the dye image-forming substance which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye. And a photosensitive layer composed of at least two of the following combinations. The emulsion and the dye image forming substance may be coated as separate layers, or may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred.
In this case, the layer of the reducible dye-donating compound is preferably located below the silver halide emulsion layer from the viewpoint of sensitivity.
The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming substance layer. A color image density can be increased by providing a partition layer described in JP-B-60-15267.
The reflective layer described in 4 can be provided to increase the sensitivity of the photosensitive element.

In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged from the exposure side.

When the present invention is used as a photographic material, an ultraviolet absorbing layer can be provided on the uppermost layer of the photosensitive layer.

Various ultraviolet absorbers generally used in the technical field, such as a benzotriazole compound, a 4-thiazolidone compound, and a benzophenone compound, can be used for the absorbing layer.

(G) Binder A hydrophilic binder is preferably used for the constituent layer of the photosensitive element or the image receiving element. An example is JP-A-62
No. 253159, pages (26) to (28). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a mixture of these vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. These binders can be used in combination of two or more kinds.

In the present invention, the coating amount of the binder is 1 m ² per 20g
The following is preferable, and particularly, it is suitably 10 g or less, more preferably 7 g or less.

Constituent layers of photosensitive element or image receiving element (including back layer)
For the purpose of improving the physical properties of the film, such as stabilization of dimensions, prevention of curl, prevention of adhesion, prevention of cracking of the film, and prevention of pressure increase / decrease, various polymer latexes can be contained. Specifically, JP-A Nos. 62-245258, 62-136648, 62-11
Any of the polymer latexes described in No. 0066 and the like can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, the image receiving layer can be prevented from cracking, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect can be reduced. can get.

(H) Hardener A hardener used in the constituent layers of the photosensitive element and the image receiving element is described in U.S. Pat. No. 4,678,739, column 41, JP-A-59-116655.
And hardening agents described in JP-A Nos. 62-245261 and 61-18942. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners Vinyl sulfone hardeners (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), N-methylol hardeners (such as dimethylol urea), or polymer hardeners (Japanese Patent Laid-Open No. Sho 62) -234157, etc.).

(I) Others In the constituent layers of the photosensitive element and the image receiving element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, antistatic, development acceleration and the like. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-183457.

The constituent layers of the photosensitive element and the image receiving element may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. As typical examples of the organic fluoro compound,
JP-B-57-9053, columns 8-17; JP-A-61-20944, 6
Fluorinated surfactants described in 2-135826 and the like,
Or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin.

A matting agent can be used for the photosensitive element and the image receiving element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate disclosed in JP-A-61-88256 (2.
In addition to the compounds described on page 9), there are compounds described in Japanese Patent Application Nos. 62-110064 and 62-110065, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.

In addition, the constituent layers of the photosensitive element and the image receiving element may contain an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256 (2.
It is described on pages 6) to (32).

In the present invention, an image formation accelerator can be used in the photosensitive element and / or the image receiving element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), surfactants, silver or silver ions. And compounds that interact with
However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects.
See U.S. Pat.No. 4,678,739 38-40 for details of these.
Column.

(J) Processing Composition The processing composition used in the present invention is developed uniformly on the photosensitive element after exposure of the photosensitive element, and develops the photosensitive layer with the components contained therein. For this purpose, the composition contains an alkali, a thickening agent, a light-blocking agent, an electron transfer agent (developer), and further, a development accelerator for controlling development, a development inhibitor, and a deterioration of the developer. Contains an antioxidant. If necessary, the composition may contain a light-shielding agent.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide) and alkali metal phosphates (eg, potassium phosphate). , Guanidines,
Examples include quaternary amine hydroxides (eg, tetramethylammonium hydroxide, etc.), and among them, potassium hydroxide and sodium hydroxide are preferable.

The thickener is necessary to develop the processing solution uniformly, to maintain the close contact between the photosensitive element and the image receiving element during development, and to prevent the processing solution component from remaining on the surface of the image receiving element during peeling. is there.

For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used.

When the image receiving element is a transparent support and does not have a light-shielding function, a light-shielding agent can be contained.

As the light-shielding agent, any dye or pigment can be used as long as the light-shielding agent does not diffuse to the dye image-receiving layer to produce stain, or a combination thereof. A typical example is carbon black, but a combination of titanium white and a dye is also used. The dye may be a temporary light-shielding dye that becomes colorless after a certain period of processing.

Preferred electron transfer agents cross-oxidize the electron donor,
Any material that does not substantially generate stain even when oxidized can be used. Such electron transfer agents may be used alone or in combination of two or more, and may be used in the form of a precursor. Specific compounds of these electron transfer agents include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain.

For example, 1-phenyl-3-pyrazolidinone, 1-p
-Tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-
4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolinone, and the like.

The treatment composition described above is disclosed in U.S. Pat.Nos. 2,543,181 and 2,642.
3,886, 2,653,732, 2,723,051, 3,056,491
No. 3,056,492, 3,152,515, etc., it is preferable to use it by filling it in a container which can be ruptured by pressure.

(K) Composition of photosensitive material A color diffusion transfer instant photosensitive material can be constituted by combining the above-mentioned elements.

The color diffusion transfer instant film unit is roughly classified into a release type and a release-free type. In the release type, a photosensitive layer and a dye image-receiving layer are coated on a separate support. The dye image transferred to the dye receiving layer is obtained by superimposing the image receiving element, developing the processing composition therebetween, and thereafter peeling off the dye image receiving element.

On the other hand, in the peeling-free type, the dye receiving layer and the photosensitive layer are coated between the transparent support and the other support, but the image receiving layer and the photosensitive layer are coated on the same transparent support. There is a form that is coated on another support.

In the former case, a white reflective layer is coated between the image receiving layer and the photosensitive layer, and in the latter case, a white pigment is applied to the processing composition developed between the image receiving layer and the silver halide emulsion layer. By containing the dye, the dye image transferred to the image receiving layer can be observed with reflected light.

In the release type, generally, the image receiving element and the photosensitive element are attached to different supports, and in addition to the dye image receiving layer as an image receiving material, a layer having a neutralizing function, a neutralization timing layer, and a release layer are provided as necessary. . As the support of the image receiving material, it is preferable to use a white support having a light shielding function. On the other hand, the light-sensitive material is provided with a layer having a neutralization function and a neutralization timing layer, if necessary, in addition to the light-sensitive layer. It is preferable to use a black support having a light-shielding function as the support for the photosensitive material. Regarding the film unit, JP-A-61-47956
What is mentioned in the item can be applied.

Further, as described in JP-A-01-198747 and JP-A-01-68749, a film unit provided in the same support in the order of dye image receiving layer / release layer / photosensitive layer is used as the release type. Can be.

When the photosensitive layer and the image receiving layer are provided on the same support, the release-free type uses a cover sheet material provided with a layer having a neutralization function and a neutralization timing layer on another transparent support. . Regarding the film unit,
No. 16356 and JP-A-50-13040 can be applied.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to this.

(Example-1) (1) Emulsion preparation method The emulsions shown in Tables 1-3 were prepared. First, emulsions A1 to A7
The method for preparing is described.

Preparation of silver halide emulsions A1 to A7 25 g of lime-processed gelatin was added to 800 ml of distilled water, dissolved at 40 ° C., and the pH was adjusted to 3.8 with sulfuric acid. In this aqueous solution,
Further, an aqueous solution (I) was prepared by dissolving 1.7 g of sodium chloride and 0.01 g of N, N'-dimethylethylenethiourea.
Next, an aqueous solution (II) was prepared by dissolving 125 g of silver nitrate in 500 ml of distilled water. Furthermore, 43 g of sodium chloride, 0.3 mg of yellow blood salt and 0.01 mg of dipotassium iridium hexachloride were added to 50 ml of distilled water.
The solution dissolved in 0 ml was used as an aqueous solution (III). Aqueous solution (II) and aqueous solution (III) in aqueous solution (I) kept at 60 ° C
Was added and mixed simultaneously for 45 minutes. After removing excess salts from the dispersion of silver halide grains obtained by the above operation by the coagulation sedimentation method, lime-processed gelatin 50
g was added and dispersed again. To this dispersion, the following spectral sensitizing dye (V-1) was added at 6.0 × 10 ^-4 mol per mol of silver halide for spectral sensitization, and further added onto silver chloride grains already formed by a halogen conversion method. While forming silver bromide
Sulfur sensitization was performed using N, N, N'-triethylthiourea.

As described above, the average grain size is 0.80 μm, and the silver chloride content is
A 99 mol% cubic silver chlorobromide emulsion A1 was prepared.

Further, emulsions A1 to A7 described in Table 1 were prepared in the same manner as in the above silver chlorobromide emulsion A1. The average grain size and silver chloride content of the silver halide grains as shown in Table 1 were adjusted by adjusting the aqueous solutions (I), (II) and (II) in the method for preparing Emulsion A1.
This was performed by changing the concentration of I), the time of the addition and mixing, the temperature of the addition and mixing, the stirring method during the addition and mixing, the control of pBr in the mixing vessel during the addition and mixing, and the degree of halogen conversion.

Preparation of silver halide emulsions B1 to B-5 The spectral sensitizing dye (V
-1) was replaced by the following spectral sensitizing dyes (V-2) and (V-3) each at 4.5 × 1 per mol of silver halide.
Silver halide emulsions B1 to B5 shown in Table 2 were prepared in the same manner as in emulsion A1, except that 0 to ⁴ mol and 9.5 × 10 ^-5 mol were used.

Preparation of silver halide emulsions C1 to C5 The spectral sensitizing dye (V
In the same manner as in Emulsion A1, except that the following spectral sensitizing dye (V-4) was used in an amount of 9.0 × 10 ^-5 mol per mol of silver halide instead of -1), the silver halide emulsions described in Table 3 were used. C1-C5
Was prepared.

Next, a method of preparing a gelatin dispersion of a dye-providing substance will be described.

18 g of the yellow dye-providing substance (1) ^* and 12 g of the high-boiling organic solvent (1) ^* were weighed, and 51 ml of ethyl acetate was added.
The solution was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 100 g of a 10% solution of lime-processed gelatin, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate were stirred and mixed, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is referred to as a yellow dye-providing substance dispersion.

Dispersions of magenta and cyan dye-donors were made using magenta dye-donors (2) ^* or cyan dye-donors (3) ^* , as well as yellow dye-donors.

Next, a method for preparing a gelatin dispersion of an electron donor will be described.

20.6 g of electron donor (1) ^* , high boiling organic solvent (1)
13.1 g of ^* was weighed, and 120 ml of ethyl acetate was added and dissolved by heating at about 60 ° C. to form a uniform solution. This solution, a 10% solution of a 10% solution of lime-processed gelatin, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called an electron donor dispersion.

Next, how to prepare a gelatin dispersion of a diffusion-resistant reducing agent for the intermediate layer will be described.

A diffusion-resistant reducing agent (1) ^* 23.5 g and a high-boiling organic solvent (1) ^* 8.5 g were dissolved in 120 ml of ethyl acetate at about 60 ° C. to form a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 15 ml of a 5% aqueous solution of surfactant (3) ^* and 0.2 g of dodecylbenzenesulfonic acid were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes.

This dispersion is referred to as a dispersion of the diffusion-resistant reducing agent for the intermediate layer.

Thus, a comparative photosensitive element (101) having the structure shown in Table 4 below was prepared.

Next, Samples 102 to 110 were prepared by changing the emulsions of the second, fifth and eighth layers to emulsions A to G shown in Table-5.

Matting agent (1) ^* Polymethyl methacrylate spherical latex (average particle size 4μ) Surfactant (1) ^* Aerosol OT High boiling organic solvent (1) ^* Tricyclohexyl phosphate Hardener (1) ^* 1,2-bis (vinylsulfonylacetamide) ethane The image receiving element was prepared as follows.

Paper support: 150 μ thick paper laminated with polyethylene on both sides at 30 μ each. To the polyethylene on the image receiving layer side, 10% by weight of titanium oxide based on polyethylene is dispersed and added.

Back side: (a) 4.0g / m ² carbon black, gelatin
2.0 g / m ² light-shielding layer.

(B) Titanium oxide 8.0 g / m ² , gelatin 1.0 g / m ²
White layer.

(C) A protective layer of 0.6 g / m ² of gelatin.

They are applied in the order of (a) to (c) and are hardened with a hardener.

Image receiving layer side: (1) A neutralization layer containing 22 g / m ^{2 of} an acrylic acid-butyl acrylate (molar ratio: 8: 2) copolymer having an average molecular weight of 50,000.

(2) Cellulose acetate having an oxidation degree of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of sample) and styrene-maleic anhydride having an average molecular weight of about 10,000 (molar ratio 1: 1) Combine 95 by weight
A second timing layer containing 4.5 g / m ² at a ratio of 5 to 5.

(3) An intermediate layer containing 0.4 g / m ^{2 of} poly-2-hydroxyethyl methacrylate.

(4) Styrene-butyl acrylate-acrylic acid-N-methylolacrylamide in a weight ratio of 49.7
Polymer latex emulsion polymerized at a ratio of /42.3/4/4,
A polymer latex obtained by emulsion polymerization of methyl methacrylate / acrylic acid / N-methylolacrylamide at a weight ratio of 93: 3: 4 is blended so that the solid fraction ratio is 6: 4, and the total solid fraction is 1.6 g / first timing layer comprising m ^2.

(5) As a coating aid A polymer mordant having the following repeating unit using 3.0 g / m ²
And an image receiving layer coated with gelatin 3.0 g / m ² .

(6) A protective layer coated with 0.6 g / m ² of gelatin.

The above (1) to (6) are applied in this order and hardened with a hardener.

 The treatment liquid formulation is shown below.

 0.8 g of a treatment liquid having the following composition was filled in a rupturable container.

1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g 1-phenyl-4-hydroxymethyl-4-methyl-
3-pyrrolizone 4.0 g Potassium sulfite (anhydrous) 4.0 g Hydroxyethyl cellulose 40 g Potassium hydroxide 64 g Benzyl alcohol 2.0 g Water 1 kg in total Addition of water 1 kg The photosensitive element was exposed from the emulsion layer side through a 101-110 gray color separation filter, and then received. The image receiving layer side of the element materials was superimposed, and the processing solution was spread between the two materials with the help of a pressure roller so as to have a thickness of 60 μm. The processing was performed at 25 ° C., and after 1.5 minutes, the light-sensitive material and the image-receiving element material were separated.

The reflection density transferred to each image receiving element was measured with a color densitometer.

The results are shown in Table-6. It was found that an image having a low minimum density and excellent color reproducibility was obtained by the present invention.

Claims (2)

(57) [Claims] A pH having at least one light-sensitive silver halide emulsion layer in combination with a dye image-forming substance and an electron donor on a support, and containing an electron transfer agent after exposure.
In a color diffusion transfer photosensitive material which forms an image by developing with an alkaline developer of 12 or more, the dye image forming substance is represented by the following general formula (CI). A silver halide emulsion comprising at least one kind of reducible dye-providing compound which releases the silver halide emulsion, and contained in at least one of the silver halide emulsion layers,
A color diffusion transfer photosensitive material comprising silver halide grains containing silver chloride as described above. General formula (C-1) PWR- (Time) _t -Dye 2. The color diffusion transfer light-sensitive material according to claim 1, wherein the silver halide emulsion contained in at least one of the silver halide emulsion layers contains silver chloride of 85 mol% or more. A color diffusion transfer photosensitive material comprising silver halide grains.