JP2000112096A - Color diffusion transfer photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color diffusion transfer photosensitive material in which a high image density and excellent color reproducibility can be obtd. even at a low temp., an image can be obtd. in a short time, and the completed image shows little changes in density. SOLUTION: This photosensitive material has, on a supporting body, at least two photosensitive silver halide emulsion layers combined with a non-diffusive dye image forming compd. which forms or releases diffusive dyes (or precursors) on silver development or combined with a dye image forming compd. whose own diffusion property changes. In this material, a color mixing preventing layer is interposed between the emulsion layers. The color mixing preventing layer is formed by applying a dispersion material prepared by dispersing particles which are the integrated body of a non- diffusive reducing agent and a single polymer or copolymer, where the dispersion medium is a hydrophilic org. colloid. The polymer or copolymer has a repeating unit having a -C(=O)-O- bond in the main chain or side chains and is insoluble in water but soluble in a low-boiling point org. solvent. The average size of the particles is 0.1 to 0.3 μm. The content of a low boiling point org. solvent is 0.2 to 4 wt.%. The weight ratio of the polymer to the hydrophilic org. colloid is 0.2 to 1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color diffusion transfer photosensitive material. More specifically, the present invention relates to a color diffusion transfer photosensitive material having high image density and excellent color reproducibility even at a low temperature. Also, the present invention relates to a color diffusion transfer photosensitive material in which the appearance of an image is fast and the density fluctuation after completion of the image is small.

[0002]

2. Description of the Related Art A color diffusion transfer photographing method using an azo dye image-forming compound which gives an azo dye having a diffusibility different from that of the image forming compound itself as a result of development under basic conditions is known. As the compound, compounds described in U.S. Pat. No. 3,928,312 and the like are well known.

[0003] Conventional color diffusion transfer photosensitive materials are roughly classified into a peeling type and a peeling-free type. In the release type, the photosensitive layer and the dye receiving layer are coated on different supports, and after image exposure, the photosensitive element and the image receiving element are overlapped, a processing solution is developed during that time, and then the dye receiving element is peeled off. Thus, a dye image transferred to a dye receiving element is obtained. However, when the toner is peeled after a predetermined time (image completion time), the dye contained in the photosensitive element is further transferred to cause a problem such that the color balance is lost and a white background is stained.

On the other hand, with respect to the peeling-free type, a dye-receiving layer and a silver halide emulsion layer are coated between the transparent support and the other support on the same transparent support, and a different support is used. There is a form that is applied to the body. In the former case, a white reflective layer is coated between the image receiving layer and the silver halide emulsion layer, and in the latter case, the processing liquid composition developed between the image receiving layer and the silver halide emulsion layer is used. By containing a white pigment, the dye image transferred to the image receiving layer can be observed with reflected light. However, since it takes time for the dye to be released from the silver halide emulsion layer and fixed to the image receiving layer, there is a problem that the density changes with time after processing are large.

As described above, the above-mentioned problem is remarkable especially at a low temperature in any of the peeling type and the peeling-free type color diffusion transfer photosensitive material, and an improvement has been desired. Further, further improvement in color reproducibility has been desired. Further, it is preferable that the time required to complete an image after processing is preferable as soon as possible in any of the peeling-type and peeling-free type color diffusion transfer photosensitive materials. In this regard, further improvement is desired.

Various attempts have been made to improve the above problems. Attempts to improve by improving the transferability of the released dyes have been disclosed in US Pat. No. 5,665,52.
9, JP-A-7-120901, JP-A-8-2863
No. 44 discloses a magenta dye image-forming substance having a specific structure,
JP-A-6-332131 discloses a yellow dye image-forming substance. However, although the transferability of the dye is improved and the formation of the dye image and the change in density after completion of the image are improved, they are still insufficient, and little improvement has been made in image formation at low temperatures.

[0007] In addition, capturing unnecessary dyes after completion of the image,
US Pat. No. 5,419,9 attempts to suppress concentration fluctuations.
No. 96, No. 5,447,818, No. 5,607,
No. 812 and the like are disclosed, and although there is an effect of suppressing the density fluctuation with respect to a specific dye, it is still insufficient and has a problem that the effect at a low temperature is small.

On the other hand, in an attempt to improve the above problem by increasing the efficiency of dye release, a method containing a diffusion-resistant sulfonamide compound is disclosed in US Pat. No. 5,418,1.
No. 11, No. 5,447,818, No. 5,496,6
No. 80, JP-A-8-292,536 and JP-A-8-292,
No. 538 and the like. However, although it has the effect of hastening the completion of an image and suppressing the density fluctuation after completion, when used in a large amount, the stain on a white background is deteriorated, and the storage stability of the photosensitive material before processing is deteriorated. Has problems.

The color diffusion transfer light-sensitive material has at least three layers of light-sensitive silver halide comprising a yellow dye image-forming substance, a magenta dye image-forming substance, and a cyan dye image-forming substance, each of which is combined with a silver halide emulsion having a different photosensitive wavelength. An emulsion layer is laminated. Therefore, it is desirable that the oxidized developer generated in a specific layer reacts with the dye image-forming substance in the layer, and the oxidized developer is diffused into another layer and reacted with the dye image-forming substance in another layer. In this case, color turbidity occurs, and color reproducibility is impaired. In order to prevent this, an intermediate layer is provided for the purpose of isolating each silver halide emulsion layer (for this purpose, it is called a color mixture prevention layer). It is known that the color mixture prevention layer contains a non-diffusible reducing agent for reducing an oxidized developer. For example, it is necessary to provide a layer containing a color mixture inhibitor such as a hydroquinone derivative in Research Disclosure, Vol. 152, No. 1
5162 (issued in November 1976).

On the other hand, since the non-diffusible reducing agent used in the color mixture preventing layer reduces and consumes the oxidized developer as described above, the effect of preventing color mixture is large when a large amount of the non-diffusible reducing agent is used. Although it becomes larger, the reaction between the oxidized developer and the dye image forming substance which should originally react decreases, resulting in a decrease in the maximum dye image density. Therefore, the design of the color mixture prevention layer is a problem to achieve such contradictory performance, and various studies have been made.

Specific examples of the non-diffusible reducing agent include non-diffusible hydroquinone, sulfonamidophenol, and sulfonamidonaphthol. More specifically, Japanese Patent Application Laid-Open Nos. 50-21249 and 50-23813
Nos. 49-106329 and 49-129535
Nos. 2,336,327 and 2,36
No. 0,290, No. 2,403,721, No. 2,5
No. 44,640, No. 2,732,300, No. 2,
No. 782,659, No. 2,937086, No. 3,
Nos. 637,393 and 3,700,453, British Patent 557,750, JP-A-57-24949, and JP-A-58-2112249 are disclosed.

In order to solve the above contradictory problems, a dispersing method has been studied. A method of co-emulsifying a hydroquinone derivative mixture having a freezing point of 100 ° C. or less with a specific polymer is disclosed in Japanese Patent Application Laid-Open No. 60-238831 and Japanese Patent Publication No. 60
Although it is disclosed in JP-A-18978, it is effective in improving color reproducibility and increasing the maximum density of a dye image, but the diffusion of the oily hydroquinone derivative into another layer cannot be completely solved, so that the pre-treatment is not possible. There is a disadvantage that the storage stability of the photosensitive material is impaired. Further, the color reproducibility at low temperatures is insufficient, and further improvement has been desired. Although various studies have been made as described above, image densities at low temperatures, color reproducibility, the speed of image appearance, density fluctuations after image completion are still insufficient, and further improvements have been desired.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color diffusion transfer photosensitive material and a color diffusion transfer film unit having high image density and excellent color reproducibility even at a low temperature. Another object of the present invention is to provide a color diffusion transfer photosensitive material and a color diffusion transfer film unit capable of quickly obtaining an image and having a small density fluctuation after completion of the image.

[0014]

It has been found that the above problem can be solved by the following constitution. (1) a non-diffusible dye image-forming compound which forms or releases a diffusible dye or a precursor thereof in association with silver development, or a dye image-forming compound which is a compound which changes the diffusivity of itself; In a color diffusion transfer light-sensitive material having at least two photosensitive silver halide emulsion layers combined, at least one non-diffusible reducing agent and at least one- C
Hydrophilic organic colloid as individual particles as a unit with a water-insoluble and low boiling point organic solvent-soluble homopolymer or copolymer having a repeating unit having a (有 す る O) —O— bond in the main chain or side chain A dispersion dispersed therein, wherein the average size of the particles is 0.1 μm or more and 0.3 μm or less, and the content of the low boiling point organic solvent in the dispersion is 0.2 wt% or more and 4 wt% or less, and A color mixture preventing layer formed by applying a dispersion in which the weight ratio of the polymer to the hydrophilic organic colloid (solid content) in the dispersion is from 0.2 to 1.5. Color diffusion transfer photosensitive material.

(2) The particles are characterized in that the non-diffusible reducing agent of the particles is a hydroquinone derivative, and the particles are formed in combination with a high-boiling organic solvent represented by the following general formula (1). The color diffusion transfer photosensitive material according to the above (1).

[0016]

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In the formula (1), R represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and has 15 to 50 carbon atoms in total.

(3) On a transparent support, an image receiving layer, a white reflective layer, a light-shielding layer, at least two photosensitive silver halide emulsion layers combined with the dye image-forming compound, and the photosensitive silver halide emulsion layers A photosensitive sheet (1) having the above-described color mixture preventing layer therebetween, a transparent cover sheet (2) having at least a neutralization layer and a neutralization timing layer on a transparent support, and the photosensitive sheet (1) and the transparent cover sheet The color diffusion transfer photosensitive material according to the above (1), which is a color diffusion film unit comprising a light-shielding alkali treatment composition (3) arranged so as to be developed between (2). .

(4) An image receiving sheet (1) comprising at least a neutralization layer, a neutralization timing layer, an image receiving layer and a release layer on a support, and a dye-image forming compound in combination with a light-shielding support. A photosensitive sheet (2) having the at least two silver halide emulsion layers and the color mixture preventing layer between the photosensitive silver halide emulsion layers, and the image receiving sheet (1) and the photosensitive sheet (2). The color diffusion transfer photosensitive material according to the above (1), which is a color diffusion transfer film unit composed of an alkali treatment composition (3) arranged so as to be spread therebetween.

In the present invention, the non-diffusible reducing agent and the water-insoluble and low-boiling organic solvent-soluble homopolymer or copolymer are integrated to form individual particles in the dispersion. Means that within the particles of the dispersion,
It is considered that both are in a solid solution.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The non-diffusible reducing agent used in the color mixture prevention layer is preferably selected from non-diffusible hydroquinone derivatives, sulfonamidophenol derivatives, and sulfonamidonaphthol derivatives as described above. Particularly, a non-diffusible hydroquinone derivative is preferable. Further, dialkyl hydroquinone derivatives are preferred. Here, the alkyl group includes a substituted or unsubstituted alkyl group, and the substituent is not particularly limited as long as it does not inhibit “non-diffusion” of the compound. Specific examples include an aryl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. The total carbon number of the “dialkyl group” is 12
Or more is preferable, and 16 or more is more preferable.

As specific compounds, the compounds described in the above-mentioned patents can be used. Specific compounds are described below, but are not limited thereto.

[0023]

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[0024]

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In the present invention, a water-insoluble and low-boiling organic solvent-soluble single polymer having a repeating unit having a —C (＝ O) —O— bond in a main chain or a side chain used together with a non-diffusible reducing agent in the present invention. As a union or copolymer,
Homopolymers and copolymers described in Japanese Patent Application No. 0-18978 and polymers described in Japanese Patent Application No. 9-143891 can be used.

Specific compounds include polyvinyl acetate, polyvinyl propionate, vinyl acetate-vinyl alcohol copolymer (90:10), polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate. , Polyisobutyl methacrylate, polyisopropyl methacrylate, polyoctyl acrylate, poly-t-butyl methacrylamide, butyl acrylate
Acrylamide copolymer (95: 5), stearyl methacrylate-acrylic acid copolymer (90:10), 1,
Examples include, but are not limited to, 4-butanediol-adipate polyester, ethylene glycol-sebacate polyester, polycaprolactone, polypropiolactone, polydimethylpropiolactone, and the like. These polymers can be used alone or in combination.

The low-boiling organic solvent used in the present invention can be used as long as it can dissolve the non-diffusible reducing agent and the polymer to be used, and is usually used for emulsification and dispersion. Specifically, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone and the like having a boiling point of less than about 140 ° C. can be used. These low-boiling organic solvents can be used alone or in combination.

According to the present invention, the hydrophilic organic colloid in which the mixture of the non-diffusible reducing agent and the polymer is dispersed is, for example, gelatin (acid-treated gelatin, alkali-treated gelatin, demineralized gelatin), allylating agent Such as gelatin derivatives (acylated gelatin, phthalated gelatin, etc.), gelatin grafted with a vinyl polymer, proteins such as casein, albumin; hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl cellulose,
Cellulose derivatives such as; polyvinyl alcohol, polyacrylamide, polyvinyl ethers, polymer non-electrolyte such as polymethyl ether, polyacrylic acid,
An anionic synthetic polymer such as a partial hydrolyzate of polyacrylamide can be used. These hydrophilic organic colloids can be used alone or in combination.

In a desirable step of preparing a dispersion of individual particles in which the non-diffusible reducing agent and the polymer of the present invention are integrated, the non-diffusible reducing agent and the polymer are dissolved in a low boiling organic solvent. Then, an aqueous solution of a hydrophilic organic colloid is added thereto, and an emulsion is prepared using an emulsifying and dispersing machine such as a homogenizer. The dispersion is significantly aided by using a surfactant as an emulsifying aid. Useful surfactants are described, for example, in the above-mentioned patent specification and JP-B-39-4.
923, U.S. Pat. No. 3,676,141.

The above-mentioned dispersion in which the non-diffusible reducing agent and the polymer of the present invention are integrated is emulsified and dispersed so that the content of the low-boiling organic solvent is from 0.2 wt% to 4 wt%. It is necessary to remove low boiling organic solvents. In order to remove the low-boiling organic solvent, a method of removing the low-boiling organic solvent by heating and reducing the pressure of the emulsified dispersion, adding water to the emulsified dispersion and concentrating the mixture with an ultrafiltration membrane to obtain a water-soluble organic solvent There are a method of removing the low boiling point organic solvent together with water, a method of cooling the emulsified dispersion, noodleling the gelled composition, and washing and removing it. Although any method can achieve the object of the present invention, the above-mentioned heating / decompression method and ultrafiltration method are preferable.

As a result of various studies, the present inventors have found that the average particle size of the emulsified dispersion particles in which the non-diffusible reducing agent and the polymer are integrated is not less than 0.1 μm and not more than 0.3 μm, and that the low boiling organic solvent A color in which a dispersion having a content of 0.2 wt% to 4 wt% and a weight ratio of a polymer to a hydrophilic organic colloid (solid content) in the dispersion of 0.2 to 1.5 is used for a color mixture prevention layer. The present inventors have found that an image having a high image density at a low temperature and excellent color reproducibility can be rapidly obtained by the diffusion transfer photosensitive material, and that the density fluctuation after completion of the image is small.

This effect is a surprising effect which cannot be expected from the function of the color mixture prevention layer. When the average size of the emulsified dispersion of the color mixture preventing layer is reduced, the activity of the non-diffusible reducing agent is increased by increasing the specific surface area. In order to solve this, it is common to reduce the amount of application. However, while ordinary photographic photosensitive materials are developed at a constant temperature, color diffusion transfer photosensitive materials are developed at various temperatures depending on the user's conditions. Since the length becomes longer, the total amount of the oxidized developer generated until a certain image density is obtained increases, and the non-diffusible reducing agent in the color mixture prevention layer becomes insufficient, and the color mixture becomes worse. Therefore, the average size of the emulsified dispersion of the color mixture preventing layer conventionally used in the color diffusion transfer photosensitive material is 0.4 μm or more.
It had a large size of 0.8 μm.

The present inventors not only reduced the average size of the emulsified dispersion, but also reduced the content of the low-boiling organic solvent to 4 wt% or less, and reduced the weight of the polymer relative to the hydrophilic organic colloid of the color mixture preventing layer. It has been found that the above effects can be obtained by setting the ratio to 0.2 or more and 1.5 or less.

When the size of the emulsified dispersion is set to 0.1 μm or less, the activity of the emulsified product is so high that it is difficult to balance with the ability to prevent color mixing. When the content of the low-boiling organic solvent exceeds 4% by weight, the activity of the emulsified dispersion is reduced, and the color turbidity is deteriorated at the same coating amount. On the other hand, if the content of the low boiling point organic solvent is less than 0.2% by weight, it is not preferable because a large amount of energy needs to be input and the stability of the emulsified dispersion itself is significantly impaired.

When the weight ratio of the polymer to the hydrophilic organic colloid exceeds 1.5, the color mixture preventing layer becomes hydrophobic, so that the transfer of the image forming dye is inhibited and the density is reduced. If it is less than 0.2, the non-diffusible reducing agent cannot be fixed to the color mixture preventing layer and diffuses into other layers to lower the maximum density, contaminate the white background, and impair the storage stability of the photosensitive material before processing.

In the present invention, the non-diffusible reducing agent is preferably a non-diffusible hydroquinone derivative as described above. Further, when the hydroquinone derivative is used in combination with the high boiling point organic solvent represented by the general formula (1), color turbidity is further improved. The high boiling point organic solvent of the formula (1) preferably has a boiling point of about 140 ° C. or higher, particularly about 160 ° C. or higher. Specific examples of the high-boiling organic solvent represented by the formula (1) are listed below.

[0037]

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In the color diffusion transfer photosensitive material, a small amount of a hydrophilic organic colloid in the photosensitive material is used as much as possible in order to ensure the transferability of the image forming dye. For this reason, generally used high-boiling organic solvents cannot be retained in the hydrophilic organic colloid when used in large amounts, and cause various problems. For this reason, the amount used was limited. However, as a result of various studies, the present inventors have found that when the non-diffusible hydroquinone derivative is used in combination with the high-boiling organic solvent of the general formula (1), the mobility of the hydroquinone derivative and the high-boiling organic solvent is suppressed rather than the above. It has further been found that no problem occurs, the image density at low temperatures is high, and the color reproducibility is excellent. This was a surprising thing that could not be predicted from conventional knowledge. The weight ratio of the compound of the general formula (1) to the non-diffusible hydroquinone derivative is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.0.

Next, the color diffusion transfer photosensitive element of the present invention will be described. In a typical form of the color diffusion transfer film unit, the image receiving element and the photosensitive element are laminated on one transparent support, and after the transfer image is completed, there is no need to peel the photosensitive element from the image receiving element. It is a form. More specifically, the image receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a blue-sensitive emulsion layer, a combination of a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer, A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound, magenta The dye image-forming compound and the cyan dye image-forming compound are respectively combined (herein, the term “infrared-sensitive emulsion layer” means 700 nm or more, especially 74 nm).
An emulsion layer having a spectral sensitivity maximum with respect to light of 0 nm or more). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the developing process can be completed in a light place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example,
67840 and Canadian Patent 674,082.

As another embodiment of a laminate type, which is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, a white support described in JP-A-63-226649. (C) a release layer, (d) a light-sensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming compound, an alkali treatment composition containing a light-shielding agent, and a transparent cover sheet, the emulsion layer comprising: There is a color diffusion transfer photographic film unit having a layer having a light-shielding function on the side opposite to the side where the processing composition is spread.

In another embodiment in which no peeling is required, the above-described photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
An image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,71.
No. 8 is described.

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peeling type, and the other is a peeling-free type. is there. More specifically, in a preferred embodiment of the peelable film unit, at least one image-receiving layer is coated on one support, and the photosensitive element is coated on a support having a light-shielding layer. Before the end of the exposure, the coated surface of the photosensitive layer and the coated surface of the mordant layer do not face each other, but after the end of the exposure (for example, during the developing process), the coated surface of the photosensitive layer is inverted in the image forming apparatus and is in contact with the coated surface of the image receiving layer. It is devised as follows. After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element.

In a preferred embodiment of the film unit which does not require peeling, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. Thus, the photosensitive layer application surface and the mordant layer application surface face each other and are superposed.

A pressure-rupturable container (processing element) further containing an alkaline processing liquid may be combined with the above-described embodiment. In particular, in a peeling-free film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains one or both of a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the film unit of the color diffusion transfer system, it is preferable that a neutralization timing mechanism composed of a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

Hereinafter, each component which can be used in the light-sensitive material of the present invention will be described in more detail.

I. Photosensitive Sheet A) Support The support of the photosensitive sheet used in the present invention may be any smooth transparent support usually used for photographic photosensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping. The thickness of the support is 5
It is 0 to 350 μm, preferably 70 to 210 μm, and more preferably 80 to 150 μm. If necessary, a layer for curl balance or an oxygen barrier layer described in JP-A-56-78833 may be provided on the back side of the support.

B) Image receiving layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer containing secondary and tertiary amino groups, a polymer containing a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. Things. The coating amount of the mordant is generally 0.5
10 to 10 g / m ^2, preferably 1.0 to 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, polyvinyl pyrrolidone and the like are used, and gelatin is preferred. In the image receiving layer, JP-A-62-30620
No. 62-30621, JP-A-62-215272.
The anti-fading agent described in (1) can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. As white pigments for the white reflective layer, barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. These may be used alone or as a mixture as long as the desired reflectance is obtained. A particularly useful white pigment is titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of the pigment, the mixing ratio of the pigment and the binder, and the amount of the pigment applied, but the light reflectance is desirably 70% or more. In general, as the amount of the pigment applied increases, the whiteness improves.However, when the image forming dye diffuses through this layer, the pigment becomes resistant to the diffusion of the dye. Is desirable. 5 to 40 g of titanium dioxide /
m ² , preferably 10 to 25 g / m ² , and a white reflective layer having a light reflectance of 78 to 85% with light having a wavelength of 540 nm is preferred. Titanium dioxide can be selected from various commercially available brands. Among them, it is particularly preferable to use rutile type titanium dioxide. Many of the commercially available products are surface-treated with alumina, silica, zinc oxide, or the like.
The above is desirable. Commercially available titanium dioxide includes, for example, those described in Research Disclosure No. 15162 in addition to Ti-pure R931 manufactured by DuPont.

As the binder for the white reflective layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose can be used. A particularly desirable binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1/1 to 2
0/1 (weight ratio), preferably 5/1 to 10/1 (weight ratio). In the white reflective layer, JP-B-62-3062
It is preferable to incorporate an anti-fading agent such as No. 0 or No. 62-30621.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light-shielding agent, any material having a light-shielding function is used, and carbon black is preferably used. U.S. Pat.
Degradable dyes described in US Pat. No. 5,966 or the like may be used.
As the binder for coating the light-blocking agent, any binder capable of dispersing carbon black may be used, and gelatin is preferred. As a carbon black raw material, for example, D
onnel Voet "Carbon Black" MarcelDekker, Inc. (1
Any production method such as a channel method, a thermal method and a furnace method described in 976) 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 shielded from light, but is preferably about 5 to 10 in optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming compound is provided above the light-shielding layer. The components will be described below.

(1) Dye image forming compound Specific examples of the dye image forming compound are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,453,453
No. 107, No. 3,544,545, No. 3,932,3
No. 80, No. 3,931,144, No. 3,932,30
No. 8, 3,954, 476, 4, 233, 237
Nos. 4,255,509 and 4,250,246
Nos. 4,142,891, 4,207,104
No. 4,287,292, JP-A-52-10672.
No. 7, No. 53-23628, No. 55-36804,
No. 56-73057, No. 56-71060, No. 55
-134, JP-A-7-120901 and 8-286
No. 343, No. 8-286344, No. 8-292535
What is described in the issue.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 3,929,760, No. 4,013,63
No. 5, 4,268,625, 4,171,220
Nos. 4,242,435 and 4,142,891
Nos. 4,195,994 and 4,147,544
No. 4,148,642; British Patent 1,551,1
No. 38; JP-A-54-99431, JP-A-52-8827.
No. 53-47823, No. 53-143323,
Nos. 54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Research Disclosure 17,630 (1978) and 16,475 (1977).

Dye image forming compounds which form a dye by coupling can also be used. For example, JP-A-8-28634
No. 0, No. 9-152705, Japanese Patent Application No. 8-357190
And Nos. 8-357191 and 9-117529. Also, a positive dye image forming compound can be used. In this case, a negative emulsion may be used as the silver halide emulsion. An example of this is disclosed in Japanese Patent Laid-Open No. 4-156542.
Nos. 4-155332, 4-172344, 4-172450, 4-318844, and 356
046, 5-45824, 5-45825,
5-53279, 5-107710, 5-2
No. 41302, No. 5-107708, No. 5-2326
No. 59, U.S. Pat. No. 5,192,649.

These compounds are disclosed in JP-A-62-2152.
No. 72, pages 144 to 146. These dispersions are described in JP-A-62-2152.
No. 72, pages 137 to 144 may be included. Specific examples of these dye-forming compounds include the following compounds. Dye in the following compounds represents a dye group, a temporarily shortened dye group, or a dye precursor group.

[0060]

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[0061]

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[0062]

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(2) Silver halide emulsion The silver halide emulsion used in the present invention may be a negative emulsion which mainly forms a latent image on the surface of silver halide grains,
An internal latent image type direct positive emulsion which forms a latent image inside silver halide grains may be used.

The internal latent image type direct positive emulsion may be, for example, a so-called “conversion type” emulsion which is prepared by utilizing the difference in solubility of silver halide, or may be doped with metal ions.
Or a "core / shell" emulsion in which at least the photosensitive sites of the silver halide inner nucleus (core) grains subjected to chemical sensitization or both are coated with an outer shell of silver halide. These are described in U.S. Pat. Nos. 2,592,250 and 3,206,313, British Patent 1,027,146, and U.S. Pat.
Nos. 6, 3,935,014 and 3,447,927
No. 2,297,875, No. 2,563,785
Nos. 3,551,662 and 4,395,478
No. 2,728,108, US Patent 4,43.
1,730 and the like.

When an internal latent image type direct positive emulsion is used, it is necessary to give a surface fog nucleus using light or a nucleating agent after image exposure. As a nucleating agent for that,
U.S. Pat. Nos. 2,563,785 and 2,588,982
Hydrazines described in US Pat. No. 3,227,5
No. 52, hydrazines and hydrazones described in British Patent No. 1,283,835, JP-A-52-69613.
No. 3,615,615 and 3,719,4
Nos. 94, 3,734, 738 and 4,094,68
Heterocycle 4 described in No. 3, No. 4, 115, 122, etc.
Grade salt compounds, sensitizing dyes having a nucleating substituent described in US Pat. No. 3,718,470 in dye molecules, US Pat. Nos. 4,030,925 and 4,031,1
No. 27, No. 4, 245, 037, No. 4, 255, 51
No. 1, 4,266,013, 4,276,364
Thiourea-linked acylhydrazine-based compounds described in US Pat. No. 2,012,443 and the like, and US Pat. Nos. 4,080,270 and 4,278,748, British Patent 2,011,391B and the like An acylhydrazine-based compound in which a heterocyclic group such as a thioamide ring or a triazole or a tetrazole described in (1) is bonded as an adsorptive group is used.

In the present invention, spectral sensitizing dyes can be used in combination with these negative emulsions and internal latent image type direct positive emulsions. For a specific example thereof, see JP-A-59-18.
Nos. 0550 and 60-140335, Research Disclosure (RD) 17029, U.S. Pat.
No. 6,300, No. 2,078,233, No. 2,08
9,129, 2,165,338, 2,23
No. 1,658, No. 2,917,516, No. 3,35
No. 2,857, No. 3,411,916, No. 2,29
5,276, 2,481,698, 2,68
8,545, 2,921,067, 3,28
2,933, 3,397,060, 3,66
No. 103, No. 3,335,010, No. 3,35
2,680, 3,384,486, 3,62
No. 3,881, No. 3,718,470, No. 4,02
5,349 and the like.

(3) Composition of the photosensitive layer In order to reproduce a natural color by the subtractive color method, the above-mentioned dye which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above-mentioned spectral sensitizing dye is used. A photosensitive layer comprising at least two of the combination with the image forming compound is used. The emulsion and the dye image-forming compound 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.
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 compound layer. For example, JP-A-60-1735
No. 41, a layer containing a nucleation development accelerator,
The color image density can be increased by providing a partition layer described in JP-A No. 0-15267, or the sensitivity of the photosensitive element can be increased by providing a reflective layer.

The reflective layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide ^{0.1g / m 2 ~8g / m 2} , and preferably from ^{0.2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354.

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. Arbitrary layers can be provided between the emulsion layer units as needed. In particular, it is preferable to provide an intermediate layer in order to prevent an unfavorable effect of the development effect of one emulsion layer on other emulsion layer units. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer, and the like are provided as needed.

F) Peeling Layer In the present invention, a peeling layer can be provided, if necessary, for peeling off the photosensitive sheet in the unit at an arbitrary place after processing. Therefore, this release layer must be easily peelable after the treatment.

As a material for this, for example, Japanese Unexamined Patent Publication No.
Nos. 7-8237, 59-220727 and 59-2
No. 29555, No. 49-4653, U.S. Pat.
20,835 and 4,359,518,
No.-4334, No.56-65133, No.45-240
No. 75, U.S. Pat. Nos. 3,227,550 and 2,75
9,825, 4,401,746, 4,36
No. 6,227 or the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like.
Other examples include 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. Further, another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate,
Polybutyl methacrylate or a copolymer thereof. The release layer can be a single layer or, for example,
It may be composed of a plurality of layers as described in JP-A-59-220727 and JP-A-60-60642.

The color diffusion transfer photosensitive material of the present invention preferably has a neutralizing function between the support and the photosensitive layer, between the support and the image receiving layer, or on the cover sheet.

G) Support The support of the cover sheet used in the present invention may be any smooth transparent support usually used for photographic light-sensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. ,
It is preferable to provide an undercoat layer. The support preferably contains a trace amount of a dye to prevent light piping.

H) Layer Having 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 introduced from the treatment composition. Accordingly, a multilayer structure including layers such as a neutralization rate control layer (timing layer) and an adhesion strengthening layer may be used. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that provides such an acidic group by hydrolysis), and more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in US Pat. Ester copolymers;
No. 4,139,383 and Research Disclosure No. 16102 (19
And latex-type acidic polymers as disclosed in (77). In addition, U.S. Pat.
8,493, JP-A-52-153739, and JP-A-53-15339.
No. 1023, No. 53-4540, No. 53-4541
And the acidic substances disclosed in JP-A-53-4542 and the like.

Specific examples of the acidic polymer include ethylene,
Copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, acetate hydrogendiene phthalate and the like.

The above-mentioned polymer acid can be used by mixing with a hydrophilic polymer. Such polymers include:
Examples include polyacrylamide, polymethylpyrrolidone, 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 in the polymer acid,
For example, cellulose acetate or the like may be mixed.

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 is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.0 to 1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The weight ratio of the hydrophilic polymer to the polymer acid is from 0.1 to 10, preferably from 0.1 to 10.
3 to 3.0.

In the layer having a neutralizing function of the present invention, additives can be incorporated 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. Other, if necessary,
An antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof can also be added.

The timing layer used in combination with the neutralizing layer has a low alkali permeability such as, for example, gelatin, polyvinyl alcohol, a partially acetalized product of polyvinyl alcohol, cellulose acetate, and partially hydrolyzed polyvinyl acetate. Polymers made by copolymerizing small amounts of hydrophilic comonomers such as acrylic acid monomers,
Latex polymers that increase the activation energy of alkali permeation; polymers having a lactone ring are useful.

In particular, JP-A-54-136328,
U.S. Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849 and the like, a timing layer using cellulose acetate;
No. 335, No. 56-69629, No. 57-6843
No. 4,056,394 and 4,061,4
Nos. 96, 4,199,362, 4,250,24
No. 3, 4,256, 827, 4,268,604
A latex polymer prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; a polymer having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346 and 57-6842, European Patent (EP) 31,957A1, 37,72
The polymers disclosed in Nos. 4A1, 48,412 A1, and the like are particularly useful.

In addition, those described in the following documents can also be used. U.S. Pat. Nos. 3,421,893 and 3,455
686, 3,575,701, 3,778,2
No. 65, No. 3,785,815, No. 3,847,61
No. 5, 4,088, 493, 4, 123, 275
No. 4,148,653, 4,201,587
No. 4,288,523 and 4,297,431
No., West German Patent Application (OLS) 1,622,936, 2,162,277, Research Disclosure 1516
2, No. 151 (1976). The timing layer using these materials can be used as a single layer or as a combination of two or more layers.

In addition, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, and US Pat.
No. 72, JP-A Nos. 54-155837 and 55-138.
No. 745, and the like, and a development inhibitor and / or a precursor thereof disclosed in US Pat.
Hydroquinone precursor disclosed in No. 78,
It is also possible to incorporate other useful photographic additives or precursors thereof. Further, as a layer having a neutralization function, JP-A-63-168648 and JP-A-63-168648
Providing an auxiliary neutralizing layer as described in JP-B-168649 is effective in that a change in transfer density with time after processing is reduced.

I) Others In addition to a layer having a neutralizing function, a back layer, a protective layer, a filter dye layer and the like may be provided as a layer having an auxiliary function. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used for preventing adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are overlapped. The sensitivity of the photosensitive layer can be adjusted by adding a dye to the cover sheet. The filter dye is directly in the support of the cover sheet or a layer having a neutralizing function, and further the back layer,
You may add to a protective layer, a capture mordant layer, etc., and may provide a single layer.

II. Alkali processing composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is disposed on the back of the support or on the side opposite to the processing solution of the photosensitive layer to form a pair with the light shielding layer. Thus, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the contained components. For this purpose, the composition contains an alkali, a thickener, a light-blocking agent, a developer, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developer. Etc. A light-shielding agent is always contained in the composition for light-shielding.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes a hydroxide of an alkali metal (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable.

The thickener is used in order to spread the treatment liquid uniformly.
Also, it is necessary to maintain the close contact between the photosensitive layer and the cover sheet. 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. 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.

As the preferable developing agent, any one can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially generate stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor form. These developing agents may be contained in an appropriate layer of the photosensitive sheet or in an alkaline processing solution. Specific examples of the compound 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-pyrazolidinone, and the like.

Either a photosensitive sheet, a cover sheet or an alkali treatment composition, a development accelerator described in JP-A-62-215272, pages 72 to 91, a hardener described in pages 146 to 155, a hardener described in pages 201 to 210 Surfactant, 210
Fluorine-containing compounds described on pages 223 to 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 23
It may contain a polymer latex described on pages 0 to 239, a matting agent described on page 240, and the like. Also, Japanese Patent Laid-Open No. 6-2
73907, JP-A-7-134386, JP-A-7-134386
No. 175193 and JP-A-7-287372.
A graded amine latex can be included.

Further, these alkali liquid compositions have a developed thickness (amount of the processing liquid per m ² after transferring the processing liquid) of 20 μm to ² μm.
It is desirable that the image is spread on the photosensitive element at a thickness of 00 μm. The processing temperature when processing the photographic material is preferably from 0 to 50C, more preferably from 0 to 40C.

The details of the heat-developable color light-sensitive material (dye-fixing element) in which the dye image forming compound of the present invention is used, and the exposure / heating method and apparatus to be applied are described in, for example, JP-A-7-219180, [0128]. From [01
59].

[0091]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 First, a method for preparing a silver halide emulsion will be described. The following eight kinds of silver halide emulsion grains (emulsion-A to emulsion-F) and emulsion-T,
U was prepared.

Preparation of Emulsion-A (octahedral internal latent image type direct positive emulsion): 0.05 M potassium bromide, 1 g of 3,6-dithia-1,8-octanediol, 0.034 mg of lead acetate
And deionized gelatin 60 having a Ca content of 100 ppm or less
g in 1000 ml of an aqueous gelatin solution containing
While maintaining the temperature at 5 ° C., a 0.4 M aqueous solution of silver nitrate and a 0.4 M aqueous solution of potassium bromide were controlled by the double jet method while controlling the addition rate of the aqueous solution of potassium bromide so that the pBr was 1.60. Was added over 40 minutes. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having an average particle size (equivalent sphere size) of about 0.7 μm and a uniform particle size were produced.

Next, core chemical sensitization was performed under the following conditions. 1. Tank: hemispherical bottom with metal surface made of Teflon coated with a thickness of 120 μm by fluoro resin FEP developed by Du Pont. 2. Stirring impeller: Seamless, integral type, propeller type with Teflon coated metal surface.

Sodium thiosulfate 1
mg, potassium tetrachloroaurate 90 mg and potassium bromide 1.
3 g of an aqueous solution of 2 g dissolved in 1000 ml of water is added,
Chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes. 0.1% was added to the emulsion solution thus chemically sensitized.
After the addition of 5 M potassium bromide, a 0.9 M aqueous solution of silver nitrate and a 0.9 M aqueous solution of potassium bromide are added to the aqueous solution of 0.9 M potassium bromide in a controlled double jet method while maintaining the temperature at 75 ° C., as in the preparation of the core particles. The silver nitrate aqueous solution 6
70 ml was added over 70 minutes. The emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added to make the average particle size (equivalent sphere size) about 1.2 μm. Octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) were obtained.

Next, 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to the internal latent image type core / shell emulsion.
Was added to 1000 ml of water and 3 ml of an aqueous solution was added.
After addition of mg of poly (N-vinylpyrrolidone) and aging at 60 ° C., 0.005 M potassium bromide was added to prepare an octahedral internal latent image type direct positive emulsion.

Preparation of emulsions BF (octahedral internal latent image type direct positive emulsion): In the preparation method of emulsion-A, the addition time of silver nitrate aqueous solution and potassium bromide aqueous solution was changed, and the amount of added chemicals was further changed. Was carried out to obtain an octahedral internal latent image type direct positive silver halide emulsion having an average particle size (equivalent sphere diameter) shown in Table 1 having a uniform particle size.

[0098]

[Table 1]

Preparation of Emulsion-T (hexagonal flat internal latent image type direct positive emulsion): In 1.2 liter of gelatin aqueous solution containing 0.05 M potassium bromide and 0.7% by weight of gelatin having an average molecular weight of 100,000 or less. And 1.4 containing the aforementioned gelatin.
33 ml of each of the M aqueous silver nitrate solution and the 2 M aqueous potassium bromide solution were simultaneously mixed for 1 minute by the double jet method with vigorous stirring. During this time, the gelatin aqueous solution was kept at 30 ° C. Further, 300 ml of a gelatin solution containing 10% by weight of deionized gelatin having a Ca content of 100 ppm or less was added, and the temperature was raised to 75 ° C. Next, 40 ml of 0.9 M silver nitrate aqueous solution
Was added over 3 minutes, and a 25% by weight aqueous ammonia solution was added, followed by aging at 75 ° C. After the ripening, ammonia was neutralized, and then 5 mg of lead acetate (added as an aqueous solution) was added, and an accelerated flow rate of 1 M silver nitrate aqueous solution and 1 M potassium bromide aqueous solution while maintaining pBr at 2.5 (at the end of the aging) (The flow rate was 6 times the flow rate at the start) and added by the double jet method (the amount of the used silver nitrate aqueous solution was 500 ml).

The particles thus formed (hereinafter referred to as core particles) were washed with water by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto, and 750 g of a hexagonal flat plate was added. Core particles were obtained. The obtained hexagonal flat core particles have an average projected area circle equivalent diameter of 0.9 μm and an average thickness of 0.20.
μm, and 95% of the total projected area was occupied by hexagonal tabular grains.

Next, core chemical sensitization was performed under the following conditions. 1. Tank: Fluororesin material F developed by DuPont for metal surface
Hemisphere bottom shape with Teflon coating with thickness 120μm by EP. 2. Stirring impeller: Seamless, integral type, propeller type with Teflon coated metal surface.

The hexagonal tabular core emulsion 200 g was added to water 13
00ml, potassium bromide 0.11M and deionized gelatin 4
After adding 0 g and raising the temperature to 75 ° C, 3,6-dithia-
2.4 g of an aqueous solution obtained by dissolving 0.3 g of 1,8-octanediol, 10 mg of sodium benzenethiosulfate, 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (added as an aqueous solution) And heated at 75 ° C. for 180 minutes to perform a chemical sensitization treatment. In the same manner as in the preparation of the core particles, the chemically sensitized core particles were mixed with a 2M aqueous solution of silver nitrate.
The double jet method was carried out at an accelerated flow rate (the flow rate at the end was 3 times the flow rate at the start) while adjusting the addition rate of the aqueous solution of potassium bromide to adjust the pBr to 2.2. (The amount of the used aqueous silver nitrate solution was 810 ml).

After adding 0.3 M potassium bromide, the emulsion was washed with water by a conventional flocculation method, and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains have an average projected area equivalent circle diameter of 2.0 μm, an average thickness of 0.38 μm, an average volume size of 1.3 (μm) ³ and 88% of the total projected area are hexagonal tabular grains. Occupied by particles. Next, 100 mg of sodium thiosulfate and 4 parts of sodium tetraborate were added to the hexagonal tabular internal latent image type core / shell emulsion.
15 mg of an aqueous solution in which 0 mg was dissolved in 1000 ml of water was added, and 20 mg of poly (N-vinylpyrrolidone) was further added.
By heating at 100 ° C. for 100 minutes, the grain surface was chemically sensitized to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-U (hexagonal tabular internal latent image type direct positive emulsion): When forming the outer shell of Emulsion-T, 0.15 mol% of iodine was uniformly contained, and the amount of outer shell was further reduced. By increasing, the average projected area circle equivalent diameter becomes 2.5
μm, the average grain thickness was 0.45 μm, the average volume size was 1.7 (μm) ³ , and 88% of the total projected area was occupied by hexagonal tabular grains. Next, AgI corresponding to 0.04 mol% of the silver amount required for grain formation at the start of shell chemical sensitization of the hexagonal tabular internal latent image type core / shell emulsion was used.
After adding the fine grain emulsion-X, the same shell chemical sensitization as in the emulsion-T was performed to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-X (AgI fine grain emulsion) 0.5 g of potassium iodide and 26 g of gelatin were added to water, and 80 ml of an aqueous silver nitrate solution containing 40 g of silver nitrate and 39 g of iodine were stirred into a solution kept at 35 ° C. while stirring. 80 cc of an aqueous solution containing potassium iodide was added over 5 minutes. At this time, the addition flow rates of the silver nitrate aqueous solution and the potassium iodide aqueous solution were each 8 ml / min at the start of the addition, and the addition flow rates were linearly accelerated so that the addition of 80 ml was completed in 5 minutes. After the formation of the particles was completed, the soluble salts were removed by settling at 35 ° C. Next, the temperature was raised to 40 ° C., and 10.5 g of gelatin and 2.56 g of phenoxyethanol were added, and the pH was adjusted to 6.8 with sodium hydroxide. The obtained emulsion had a finished amount of 73.
Monodispersed AgI fine particles having an average diameter of 0.015 μm were obtained at 0 g.

Using the emulsions AF, T, and U as described below, comparative photosensitive elements (sample 101) having the constitutions shown in Tables 2 to 5 below were prepared. At the end of the shell chemical sensitization, the sensitizing dye was added at the dye type, dispersion form, addition temperature and amount shown in Table 6 below.

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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A method for preparing an emulsified dispersion used for the color mixture preventing layer will be described. Method for Preparing Emulsion (1) Used in Color Mixing Prevention Layer of Photosensitive Material 101 Nondiffusible Hydroquinone Derivative (Specific Example A) 92.
8 g and 100 g of polymethyl methacrylate were dissolved in 160 cc of ethyl acetate at 60 ° C., and 100 g of alkali-treated gelatin and 4.8 of surfactant (5) were prepared.
g and 780 cc of water, and a solution dissolved at 40 ° C. was added, followed by emulsification and dispersion with a homogenizer. The emulsified dispersion 20 for an anti-color mixture layer having an average particle size of 0.6 μm was thus obtained.
00 g was prepared.

Preparation of Emulsion (2) An emulsion having an average size of 0.25 μm was prepared in the same manner as in Emulsion (1) except that the emulsification conditions in the homogenizer were changed.
(2) 2000 g was prepared.

Preparation of Emulsion (3) Emulsion (2) was immediately added with water and concentrated by ultrafiltration to give emulsion (3) having an ethyl acetate concentration of 1%.
0 g was prepared. Emulsions (4) to (19) in the same manner as described below.
Was prepared. Table 7 summarizes the results.

[0128]

[Table 7]

Next, except that the ninth layer and the fifteenth layer were changed using the above-mentioned emulsion for a color mixture preventing layer, the photosensitive element 101 was completely changed.
In the same manner as in the above, photosensitive elements 102 to 119 were prepared. As described above, the activity of the color mixture preventing layer differs depending on the content of the emulsion.
Therefore, the application amount of the hydroquinone derivative was changed so that the maximum concentration of the standard treatment at 25 ° C. became close. Table 8 summarizes the contents of the photosensitive elements 101 to 119.

[0130]

[Table 8]

Preparation of Cover Sheet A transparent cover having a thickness of 75 μm was applied in a layer constitution as shown in Table 9 to prepare a cover sheet.

[0132]

[Table 9]

The chemical structural formulas and the like of the compounds used in the cover sheet are shown below.

[0134]

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[0135]

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The formula of the alkali treatment composition is shown below. Silver nitrate 0.10 g Carbon black (manufactured by Dainichi Seika Co., Ltd.) 160 g Additive (22) 8.60 g Carboxymethyl cellulose Na salt 58.0 g Benzyl alcohol 2.50 g Additive (23) 2.10 g Potassium sulfite (anhydrous ) 1.90 g 5-methylbenzotriazole 2.50 g 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 7.00 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10 0.06 g Potassium hydroxide 56.0 g Aluminum nitrate 0.60 g Zinc nitrate 0.60 g Additive (24) 6.60 g Additive (14) 1.80 g 1,2-Benzisothiazolin-3-one 0.003 g

[0137]

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Next, after exposing the photosensitive elements 101 to 119 from the emulsion layer side through a gray continuous wedge, the photosensitive elements 101 to 119 were superposed on the cover sheet, and the alkali treatment composition was applied between both materials so as to have a thickness of 62 μm. It was deployed using a pressure roller. The treatment is performed at 15 ° C and 25 ° C,
Two hours later, the transfer density was measured with a color densitometer, and the maximum density and the minimum density of each color of yellow, magenta, and cyan in gray exposure were measured and evaluated. The density of the sample treated at 15 ° C. 10 minutes after the treatment was measured to evaluate the speed of image appearance. Further, the density of the 25 ° C. sample was measured 3 days after the treatment, and compared with the density 2 hours later, to evaluate the density fluctuation after image formation. Tables 10 and 11 show the measurement results.
Put together.

[0139]

[Table 10]

[0140]

[Table 11]

In order to evaluate color turbidity, blue, green, and red filters were individually superposed instead of the continuous gray wedge, and the exposure was performed in the same manner as described above except that the exposure was adjusted and the exposure was performed. Was done. Unnecessary densities of blue, green, and red parts (complementary colors of each color) were measured and evaluated. The smaller the value is, the less the color mixture is. Table 12 summarizes the results.

[0142]

[Table 12]

As described above, by using the emulsified dispersion of the present invention in the color mixture preventing layer, it can be seen that an image appears quickly, the maximum density is high, and the color turbidity is small even at a low temperature. It was also shown that the density change after completion of the image was small.

[0144]

According to the present invention, a color diffusion transfer photosensitive material and a color diffusion transfer film having a high image density and excellent color reproducibility even at a low temperature, capable of rapidly obtaining an image, and having a small density change after completion of the image. It turned out that a unit was obtained.

Claims (4)

[Claims] Claims: 1. A non-diffusible dye image-forming compound which forms or releases a diffusible dye or its precursor in association with silver development on a support or a dye image forming compound which changes its diffusivity itself. A color diffusion transfer photosensitive material having at least two photosensitive silver halide emulsion layers combined with a compound, wherein at least one non-diffusible reducing agent and at least one non-diffusible reducing agent are interposed between the photosensitive silver halide emulsion layers.
Water-insoluble and low-boiling organic solvent-soluble homopolymer or copolymer having a repeating unit having a kind of —C (＝ O) —O— bond in a main chain or a side chain is integrated as individual particles. A dispersion dispersed in a hydrophilic organic colloid, wherein the average size of the particles is 0.1 μm or more and 0.3 μm or less, and the content of the low boiling organic solvent in the dispersion is 0.2 μm or less.
4% by weight or less and 4% by weight or less, and prevention of color mixing formed by applying a dispersion having a weight ratio of the polymer to the hydrophilic organic colloid (solid content) in the dispersion of 0.2 to 1.5. A color diffusion transfer photosensitive material having a layer. 2. The non-diffusible reducing agent for the particles is a hydroquinone derivative, and the particles are formed in combination with a high-boiling organic solvent represented by the following general formula (1). Item 6. A color diffusion transfer photosensitive material according to Item 1. Embedded image In the formula (1), R represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and has a total carbon number of 15 or more and 50 or less. 3. An image receiving layer, a white reflective layer, a light-shielding layer, at least two photosensitive silver halide emulsion layers combined with the dye image-forming compound, and a photosensitive silver halide emulsion layer on a transparent support. A photosensitive sheet (1) having the color mixture preventing layer between them, a transparent cover sheet (2) having at least a neutralization layer and a neutralization timing layer on a transparent support, and the photosensitive sheet (1) and the transparent cover sheet ( 2. The color diffusion transfer photosensitive material according to claim 1, wherein the color diffusion film unit comprises a light-shielding alkali treatment composition (3) arranged so as to be developed between 2). 4. An image receiving sheet (1) comprising at least a neutralization layer, a neutralization timing layer, an image receiving layer and a release layer on a support, and the dye image forming compound on a support provided with a light-shielding property. A light-sensitive sheet (2) having at least two silver halide emulsion layers and the color mixture preventing layer between the light-sensitive silver halide emulsion layers, and between the image receiving sheet (1) and the light-sensitive sheet (2) 2. The color diffusion transfer photosensitive material according to claim 1, which is a color diffusion transfer film unit comprising an alkali treatment composition (3) arranged so as to be developed in a color.