JP2001174961A - Color diffusion transfer photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color diffusion transfer photosensitive material having high photographing sensitivity and ensuring a short image appearance time and a small density change after image completion. SOLUTION: In the color diffusion transfer photosensitive material having at least two photosensitive silver halide emulsion layers each combined with a dye image forming compound on the substrate, the coating weight of a diffusible anionic surfactant having a molecular weight of <=2,000 in the photosensitive material satisfies expression I, wherein Ai is the number of anionic groups in an i-th surfactant, Oi is the organic numerical value of the i-th surfactant, Ii is the inorganic numerical value of the i-th surfactant, Ni is the content (mol) of the i-th surfactant per 1m2 of the photosensitive material and M is the content (mol) of a mordanting part in a mordant per 1m2 of the photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer photographic light-sensitive material, and more particularly to a color diffusion transfer photographic light-sensitive material in which the content of a diffusible anionic surfactant is suppressed to a certain level or less.

[0002]

2. Description of the Related Art A color diffusion transfer photographic material generally has two functions of a photographing material and a viewing material. Therefore, the sensitivity at the time of photographing, the image appearance time and image completion time after photographing, and the image completion time are required. It is a particularly important performance that no subsequent concentration change occurs. A method of providing a reflective layer below an emulsion layer as viewed from the exposure side in order to improve photographic sensitivity is widely known. For example, JP-A-60-91354 discloses an example of a reflective layer. However, the provision of the reflective layer has the disadvantage that the appearance of an image is delayed and the density change after completion of the image is increased. That is, in the diffusion transfer photosensitive material, the dye released from the dye image forming compound in the photosensitive element diffuses into the mordant layer in the image receiving element to form a dye image, but the coating of the reflective layer hinders the diffusion of the dye. This causes not only a delay in dye transfer, but also a change in density after completion of the image.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color diffusion transfer photosensitive material having a high photographic sensitivity, a short image appearance time, and a small change in density after completion of the image.

[0004]

As a result of intensive studies, the present inventors have found that the objects of the present invention can be effectively achieved by the following photographic materials. 1) A dye image-forming compound (for example, a non-diffusible dye image-forming compound that forms or releases a diffusible dye or its precursor in connection with silver development, or a compound that changes its diffusivity itself on a support) A) a color diffusion transfer photosensitive material having at least two photosensitive silver halide emulsion layers in combination with a diffusible anionic surfactant having a molecular weight of 2000 or less (hereinafter referred to as a diffusible anion); A color diffusion transfer photographic light-sensitive material, characterized in that the coating amount of a (system surfactant) is a compound having a molecular weight of 2,000 or less satisfies the following formula (I).

[0005]

(Equation 2)

In the formula, Ai is the number of anionic groups in the ith surfactant. Oi is the organic value of the ith surfactant. Ii is the inorganic value of the ith surfactant. Ni is the ith interface. The content (mol) of the activator per 1 m ² of the photographic material M represents the content (mol) of the mordant in the mordant per 1 m ² of the photographic material. It is difficult to make the value of the formula (I) zero, but the smaller the better, the better. 2) A photosensitive sheet (1) containing an image receiving layer, a white reflective layer, a light-shielding layer, and at least two photosensitive silver halide emulsion layers combined with a dye image forming compound on a transparent support; A transparent cover sheet (2) having at least a neutralization layer and a neutralization timing layer, and the photosensitive sheet (1)
A color diffusion film unit comprising a light-shielding alkali treatment composition (3) disposed so as to be developed between the photosensitive sheet (1) and the transparent cover sheet (2). (1) The color diffusion transfer photosensitive material as described in (1) above, wherein the coating amount of the anionic surfactant satisfies the range of the formula (I). 3) At least a neutralization layer, a neutralization timing layer,
An image receiving sheet (1) comprising an image receiving layer and a release layer, comprising at least two silver halide emulsion layers combined with a dye image forming compound on a light-shielding support, and When the amount of the surfactant applied is the above formula (I)
And a color diffusion transfer film unit comprising an alkali treatment composition (3) arranged so as to be developed between the image receiving sheet (1) and the photosensitive sheet (2). The color diffusion transfer photosensitive material according to item 1), wherein (4) The color diffusion transfer photographic light-sensitive material as described in (1) above, further comprising a white reflective layer between at least one photosensitive silver halide emulsion layer and at least one dye image forming compound-containing layer. 5) A color diffusion transfer photographic light-sensitive material according to 2), comprising a light-sensitive sheet having a white reflective layer between at least one light-sensitive silver halide emulsion layer and at least one dye image forming compound-containing layer. material. (6) The color diffusion transfer photographic light-sensitive material according to (3), comprising a photosensitive sheet having a white reflective layer between at least one photosensitive silver halide emulsion layer and at least one dye image forming compound-containing layer. material.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The anionic surfactant specified in the present invention will be described in detail below. Examples of the anionic surfactant which can be used in the present invention include, for example, JP-A-3-2
No. 39252, No. 3-249775, No. 4-7654
No. 3, No. 3-226748, No. 4-190341,
It can be selected from the anionic surfactants described in JP-A-4-190342 and JP-A-4-278946. In diffusion transfer photography, the mordant often has both a cationic part and a hydrophobic part. On the other hand, a dye generally has an anion portion and a hydrophobic portion. The image is formed by dyeing the dye firmly by the electrostatic force of the mordant and the cation / anion and the affinity between the hydrophobic parts. On the other hand, the photosensitive material contains anionic surfactants used as emulsifying aids or coating aids, but since these compounds have an anionic part and a hydrophobic part, they strongly dye to the mordant. Have the property of Therefore, when a certain amount or more of an anionic surfactant is present in the light-sensitive material, they compete with the dye for dyeing on the mordant site, and thus dyeing is inhibited. Among the anionic surfactants, those having a large number of anionic moieties in one molecule and those having a large number of hydrophobic moieties have higher dyeing power, and have a greater inhibitory effect. On the other hand, it was found that those having many non-dissociated hydrophilic groups tended to have low dyeing power. From the above examination, the present inventor can obtain a color diffusion transfer photographic film unit having a short image appearance time and an image completion time by specifying the application amount of the diffusible anionic surfactant as in the above formula (I). I found something. The organic parameter and the inorganic parameter in the above formula (I) are scales indicating the hydrophilicity and hydrophobicity of the compound, and can be calculated by, for example, the calculation method in Yoshio Koda, “Organic Conceptual Diagram” (Sankyo Shuppan). It is. Further, when a white reflective layer is provided between the emulsion layer and the dye image-providing compound-containing layer, the density change after completion of the image can be reduced by defining the amount of the anionic surfactant as in the above formula (I). It was found to be significantly smaller. The white 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 is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.2 g / m ^{2 to} 4 g / m ²
It is. With respect to the types and proportions of the white pigment and the hydrophilic binder that can be used for the white reflective layer, those used for the white reflective layer forming a white background shadow of a color image described later can be applied.

Next, the color diffusion transfer photosensitive material of the present invention will be described. The color diffusion transfer photosensitive material is preferably used in the form of a film unit. 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 (here, the term “infrared-sensitive emulsion layer” means an emulsion layer having a spectral sensitivity maximum with respect to light of 700 nm or more, particularly 740 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.

In another embodiment of the present invention, which is a laminated type and is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, on 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 mode 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 of a peelable type and the other is of a peelable 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 peeling-free film unit, 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. The layer application surface and the mordant layer application surface face each other and are overlaid.

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 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, polyvinylpyrrolidone 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 a 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 kind 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 commercial products are
Surface treatment is performed with alumina, silica, zinc oxide, or the like, and a surface treatment amount of 5% or more is desirable in order to obtain high reflectance. 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 (mass ratio), preferably 5/1 to 10/1 (mass 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, No. 10-239793
No. 10-186564 and No. 10-293388. 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 Unexamined Patent Publication No. Hei.
No. 42, No. 4-155332, No. 4-172344
Nos. 4-172450, 4-318844, 4-356046, 5-45824, 5-45
No. 825, No. 5-53279, No. 5-107710
No. 5,241,302, No. 5,107,708, No. 5,232,659 and 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.

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

(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 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 fogging 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, a spectral sensitizing dye can be used in combination with the negative emulsion and the internal latent image type direct positive emulsion. 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 dye which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the 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.

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

As a material for this purpose, 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-53-153739.
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 as a mixture 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 mass ratio of the hydrophilic polymer to the polymer acid is 0.1 to 10, preferably 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,
To harden this layer, hardeners well known to those skilled in the art can be added, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin and the like can be added to improve the brittleness of the film. In addition, if necessary, an antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof may be added.

The timing layer used in combination with the neutralizing layer has low alkali permeability such as, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like. 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.

Among them, 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 3,014,6
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 the layer having a neutralizing function, a layer having an auxiliary function may have a back layer, a protective layer, a filter dye layer and the like. 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. The alkali metal hydroxide (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 preferred 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, pp. 72-91, a hardener described on pages 146-155, a hardener described in page 201-210. 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 alkaline 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, [0128] of JP-A-7-219180. From [01
59].

[0057]

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 3,6-dithia-1,8-octanediol, 0.034 mg 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 was added to Emulsion-A
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 an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were changed, and the amounts of added chemicals were 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.

[0064]

[Table 1]

Preparation of Emulsion-T (hexagonal plate-like internal latent image type direct positive emulsion): In 1.2 liter of an aqueous gelatin solution containing 0.05 M of potassium bromide and 0.7% by mass 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 mass 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, a 25% by mass aqueous ammonia solution was added, and aging was performed 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) are washed with water by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate are added thereto, and 750 g of a hexagonal plate is 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.

200 g of the above hexagonal tabular core emulsion was mixed with 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 (major plane (111) plane tabular grains).

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 formed 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 that of the emulsion-T was performed to prepare a hexagonal tabular internal latent image type direct positive emulsion (main plane (111) plane tabular grains).

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.

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

Preparation of a cover sheet A cover sheet was prepared by coating a transparent support having a thickness of 75 μm with a layer constitution as shown in Table 7.

[0092]

[Table 7]

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

[0094]

Embedded image

[0095]

Embedded image

The formulation 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

[0097]

Embedded image

The light-sensitive material 1 was prepared in the same manner except that the amount of the anionic surfactant added to the light-sensitive material 101 and the amount of titanium dioxide in the sixth and eighteenth layers were changed to those shown in Table 8.
Nos. 02 to 112 were produced. Next, the photosensitive elements 101 to 101
After exposing 112 from the emulsion layer side through a gray continuous wedge, it was superimposed on the cover sheet, and the alkali treatment composition was spread between both materials using a pressure roller to a thickness of 62 μm. After one day and two weeks at 25 ° C., the transfer density was measured with a color densitometer, and the change in density after completion of the yellow, magenta, and cyan images was evaluated. Further, the time until the image appeared (the time from the start of the development of the processing solution to the time when the image began to be seen) was measured by the same processing.

[0099]

[Table 8]

[0100]

[Table 9]

As is clear from the comparison of Samples 101 to 112 in Table 9, by setting the coating amount of the low molecular weight anionic surfactant within the range of the present invention, a color diffusion transfer photographic light-sensitive material having a short image appearance time can be obtained. You can see that. In addition, when a reflective layer is present between the emulsion layer and the dye image-providing compound-containing layer, a color diffusion transfer photographic material having a shorter image appearance time and a small change in density after completion of the image may be obtained. Understand.

Example 2 In the above Example 1, the alkaline treatment composition was used in an amount of 49 μm.
The same experiment as in Example 1 was performed except that the development was performed using a pressure roller so as to have a thickness of m. Even with the use of such a small amount of the processing composition, it is necessary that the reflective layer is contained between the emulsion layer and the dye image-providing compound-containing layer, and the coating amount of the low molecular anionic surfactant is set within the range of the present invention. As a result, it was found that a color diffusion transfer photographic light-sensitive material having a short image appearance time and a small change in density after completion of the image was obtained.

[0103]

According to the present invention, the image appearance time is short,
It was also found that a color diffusion transfer photographic light-sensitive material and a color diffusion transfer film unit having a small density change after completion of an image were obtained.

Claims (6)

[Claims] 1. A color diffusion transfer light-sensitive material having at least two photosensitive silver halide emulsion layers combined with a dye image-forming compound on a support, wherein the color diffusion transfer light-sensitive material has a molecular weight of 2,000 or less. A color diffusion transfer photographic light-sensitive material, characterized in that the coating amount of the diffusible anionic surfactant is satisfies the following formula (I). (Equation 1) In the formula, Ai is the number of anionic groups in the ith surfactant. Oi is the organic value of the ith surfactant. Ii is the inorganic value of the ith surfactant. Ni is the number of the ith surfactant. the content of the photosensitive material 1 m ² per (mol) M represents the content of the mordant portion in mordant per photosensitive material 1 m ² a (mol), respectively. 2. An image receiving layer, a white reflective layer, a light shielding layer and at least two dyes combined with a dye image forming compound on a transparent support.
Photosensitive sheet (1) containing a photosensitive silver halide emulsion layer, a transparent cover sheet (2) having at least a neutralizing layer and a neutralizing timing layer on a transparent support, and the photosensitive sheet (1) and the transparent sheet A color diffusion film unit comprising a light-shielding alkali treatment composition (3) disposed so as to be spread between transparent cover sheets (2), wherein said diffusible anion in said photosensitive sheet (1) is provided. 2. The color diffusion transfer photosensitive material according to claim 1, wherein the coating amount of the system surfactant satisfies the range of the formula (I). 3. An image receiving sheet (1) comprising at least a neutralizing layer, a neutralizing timing layer, an image receiving layer and a release layer on a support, and a dye image forming compound combined on a light-shielding support. A photosensitive sheet (2) containing at least two silver halide emulsion layers and having a coating amount of the diffusible anionic surfactant satisfying the range of the above formula (I); Alkali processing composition (3) arranged to be spread between photosensitive sheets (2)
The color diffusion transfer photosensitive material according to claim 1, wherein the color diffusion transfer film unit comprises: 4. A color diffusion transfer photographic material according to claim 1, further comprising a white reflective layer between at least one photosensitive silver halide emulsion layer and at least one dye image forming compound-containing layer. . 5. The color diffusion according to claim 2, comprising a photosensitive sheet having a white reflective layer between at least one photosensitive silver halide emulsion layer and at least one dye image forming compound-containing layer. Transfer photographic light-sensitive material. 6. The color diffusion according to claim 3, comprising a photosensitive sheet having a white reflective layer between at least one photosensitive silver halide emulsion layer and at least one dye image forming compound-containing layer. Transfer photographic light-sensitive material.