JPH01255858A - Color diffusion transfer photographic film unit - Google Patents

Abstract

PURPOSE:To form a color diffusion photograph which has stable peelability, excellent sharpness and high quality of color reproducibility by forming a release layer of a layer contg. hydroxyalkyl cellulose and providing a layer contg. cellulose ester between the release layer and a photosensitive layer. CONSTITUTION:The release layer is the layer contg. the hydroxyalkyl cellulose and the layer contg. the cellulose ester is provided between the release layer and the photosensitive layer. The hydroxyalkyl cellulose is exemplified by hydroxyethyl cellulose, etc. The layer consisting of the cellulose ester is saponified by the alkali in a processing liquid in development processing and is thereby made into a water permeable layer; therefore, the dye diffusion is retarded if said layer is too thick. The effect of shielding color materials is lost and a long-term stable release effect is lost if the layer is too thin. The thickness of said layer is, therefore, adequately 0.02-0.9g/m<2>, more preferably 0.05-0.6g/m<2>. The color diffusion transfer photographic film unit of the release type having the excellent release property, the low min. image density and the excellent sharpness is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to color diffusion transfer photographic film units. More specifically, the present invention relates to a peelable color diffusion transfer film unit.

(Prior Art) A conventional color diffusion transfer photographic film unit
A peel-off mold that requires an 81M process to see, and its?
, ff1l+separation-free type, which does not require an lIM process.

In the peel-off type, the light-sensitive layer and the dye-receiving layer are coated on separate supports, and after image exposure, the light-sensitive element and the dye-receiving element are superimposed, a processing composition is spread between them, and then the dye is applied. By peeling off the image-receiving element, the dye image transferred to the dye image-receiving layer is obtained on the peeling surface side (hereinafter referred to as the beer-apart type), and the other is the high-quality image obtained by the Eri release type color diffusion transfer film unit. As a diffusion transfer photographic film unit that combines the excellent handling properties of a peel-free type color diffusion transfer photographic film unit, it has at least an image-receiving layer, a release layer, and a photosensitive element on the same support in this order, and is processed by alkali treatment. After developing the composition, remove the image-receiving layer from the release layer. An example is a peelable type color diffusion transfer film unit (hereinafter referred to as a peelable monosheet type).

However, these methods are inconvenient when handling the processed film, in that the alkaline processing liquid tends to stick to the image surface and adhere to the surrounding area after peeling, and when peeling, ff, l
The I delamination is destroyed, and the delamination layer irregularly adheres to the 2II delaminated surface.

In the 7-sho non-use type, a dye image-receiving layer and a silver halide emulsion layer are coated between a transparent support and another support. There are two types: one in which it is coated on the other support, and one in which it is coated on another support.

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

However, if the used emulsion, pot, cover sheet, etc. are not peeled off, there is an inconvenience that the resulting print will be too thick, so it has been proposed to peel off these.

However, after peeling off, the alkaline processing solution tends to stick to the back of the image and stick to the surrounding area, which is inconvenient when handling the processed film, and when peeling off, the peeling layer is destroyed and the peeled surface is damaged. Jl Defects of '7.11 mold release such as irregular adhesion of delamination appear.

Whether it is the Beer-apart type (ff, lI El type), the peelable monosheet type, or the 'fll Uf-free type where unnecessary parts can be peeled off, this is because it causes the film to fall between the image-receiving layer and the photosensitive element. be. However, when the distance between the photosensitive layer and the image-receiving layer is less than 10 μm, the cyan coloring material in the photosensitive layer is dissolved and diffused by an alkaline developer during development, resulting in a drawback that fog occurs on the image-receiving layer.

Techniques using acrylic acid-based delamination in JP-A No. 1-214357, alkaline processing solutions in photographic layers described in JP-A 60-257446 and JP-A 60-257447, etc. There is a technique for providing a layer that temporarily provides a barrier against the diffusion of The transfer film unit is
The release layer is characterized by comprising a layer made of a copolymer containing a reversible unit derived from an ethylenically unsaturated carboxylic acid or a salt thereof, and a layer containing a cellulose ester, without affecting the release time. TI can be released stably,
A diffusion transfer film unit is also disclosed that can reduce stickiness on the image surface after peeling. However, even with these layers, it was not possible to sufficiently prevent the coloring material in the photosensitive layer from being dissolved in an alkaline developer and being diffused into the image-receiving layer.

In addition, the technology of using hydroxyethyl cellulose as a release layer and the technology of using a layer of hydroxyethyl cellulose and a layer of gelatin as a release layer were published in Japanese Patent Publication No. 63-3300.
No. 61-48834, etc.

Furthermore, Japanese Patent Publication No. 63-3300 discloses a technique for improving the selective releasability of the release layer by incorporating particulate matter into one of the hydrophilic layers adjacent to the release layer; Although the property has been improved, it is not sufficient to prevent the coloring material from spreading, and an improvement has been strongly desired.

(Problems to be Solved by the Invention) When trying to improve sharpness without increasing the film thickness between the photosensitive layer and the image-receiving layer while maintaining stable releasability, an alkaline developer may cause damage to the photosensitive layer during development. The coloring material dissolves and diffuses, causing fog on the image-receiving layer and reducing the minimum image density (Dmin).
) has the disadvantage of resulting in a highly fogged image.

(Objective of the Invention) The object of the present invention is to provide a peelable film unit that can be processed in a bright room, and which has stable peelability, low minimum image density, and high quality color diffusion transfer photographs with excellent sharpness and color reproducibility. The goal is to provide the following.

(Means for Solving the Problems) The above problems are such that at least a dye image-receiving layer is formed on the support.
In a peelable ff1ll release type color diffusion transfer photographic film unit having a release layer and a photosensitive layer, 31
PHI delamination was achieved by a color diffusion transfer photographic film unit characterized by a layer containing hydroxyalkylcellulose and having a layer containing cellulose ester between the release layer and the photosensitive layer.

In the preferred embodiment, at least (
a) A layer having a neutralizing function, (b) a dye image-receiving layer, (C)!
lI delamination, (d) layer containing cellulose ester, (e)
an alkali light-sensitive element having a light-sensitive element having sequentially at least one silver halide emulsion layer in combination with a dye image-forming material and a transparent cover sheet, the light-shielding agent being spread between the top layer of the light-sensitive element and the cover sheet; A color diffusion transfer photographic film unit comprising a processing composition and a layer having a light shielding function on the side of the emulsion layer opposite to the side on which the processing composition is applied.

In a color diffusion transfer photographic film unit, the peelability is improved by providing a release layer between the image-receiving layer and the photosensitive layer, but by providing this release layer or other layers, the distance between the image-receiving layer and the photosensitive layer If the image is expanded, it takes time to diffuse during development and the sharpness decreases. If the distance is narrowed, the releasability will be lowered and the surface strength of the obtained image will be lowered. In either case, during development, the minimum image density (D+++in) increased due to unnecessary diffusion of the coloring material dissolved in the alkaline developer into the image-receiving layer, making it impossible to obtain a high-quality color image. .

It is an unexpected effect that the above-mentioned problems can be solved at the same time by the present invention, which has a layer containing hydroxyalkylcellulose in the release layer and a layer containing cellulose ester between the release layer and the photosensitive layer. there were.

This effect is particularly noticeable with the peelable monosheet type, which allows you to obtain high-quality diffusion transfer photographs with stable peelability, excellent color reproducibility with low minimum image density, and excellent sharpness. Alternatively, a mold that does not require peeling may be used, but the unnecessary portion can be peeled off.

After exposure, the film unit of the present invention is processed by a pressing member, and the alkali processing composition is uniformly spread within the film unit to start development.

After processing, the area containing the white support and dye image-receiving layer is peeled off from the rest of the film unit at the position of the release layer to remove used emulsion layers, pots, cover sheets, etc. You can get something similar to Hensional's print.

Examples of the hydroxyalkyl cellulose that can be used in the hydroxyalkyl cellulose layer of the release layer in the invention include hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose. Mixtures of these are also effective. This delamination is 0.02g/- to 0.9g/
- is suitable, preferably 0.05g/- to 0.6
g/monkey 4. A layer using acetylated gelatin may be provided on the opposite side of the cellulose ester-containing layer adjacent to the release layer.

The layer made of cellulose ester of the present invention is saponified by the alkali in the processing solution during development processing and becomes a water-permeable layer, so if it is too thick, dye diffusion will be delayed.

Also, if it is too thin, the blocking effect of the coloring material and the long-term stability ff1
0.02g/rd~0.9 because l+ separation effect disappears
g/n (is suitable, preferably 0.05 g/n)
n(~0.6 g/rt).

Any cellulose ester can be used as long as it can be hydrolyzed with alkali, such as cellulose triacetate,
Cellulose diacetate, cellulose propionate,
Cellulose esters such as cellulose acetate butyrate are used.

Below, the release layer used in the present invention and each element other than the laminate containing cellulose ester will be sequentially explained.

A) Support Any support can be used as the support in the present invention, as long as it does not adversely affect the photographic properties of the film unit and has dimensional stability. For example, cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, poly(vinyl acetal) film,
Examples include polystyrene film, polyethylene terephthalate film, polycarbonate film, paper, metal, and glass. Preferred are cellulose acetate film, polyethylene terephthalate film, polyethylene-coated paper, and the like.

B) Layer having a light-shielding function In the present invention, a layer having a light-shielding function exists on the side opposite to the emulsion layer, and a processing solution for the light-shielding layer is developed on the photosensitive layer element during the development process. By completely shielding it from outside light, it is possible to process it in a bright room or under daylight.

Specifically, a layer containing a light-shielding layer may be coated on the back surface of the support or between the image-receiving layer and the support, or a layer containing a light-shielding agent may be provided in the support. As the layer containing the light-shielding agent, any material having a light-shielding function can be used, but preferably black pigment dispersion, such as gelatin,
Carbon black dispersed in an alkaline solution permeable polymer matrix such as hydroxyethyl cellulose or polyvinyl alcohol is used.

The light-shielding function in the present invention is to shield the photosensitive layer from light in a bright room or daylight, and includes one side (surface of the photosensitive layer) of the photosensitive layer.
Light-shielding is achieved by applying a processing composition having a light-shielding function on the opposite side of the photosensitive layer (1) between the reflective layer and the support, (2) on the support itself, and/or (2) on the support. This is done by providing a layer containing a light-blocking agent on the back side of the body (the side opposite to the photosensitive layer) to block light. At this time,■
It is sufficient that both (1) and (2) can block light as a whole, and each may not have sufficient light-shielding ability.

C) Dye 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. Regarding this, JP-A No. 61-25255
It is stated in No. 1. As the mordant, a polymer mordant is preferred.

The polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., and those having a molecular weight of 5,000 or more are particularly preferable. is 10,00
It is 0 or more.

For example, US Patent Nos. 2,548,564 and 248,443.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat. No. 0, US Pat. No. 3,148,061, US Pat.
Vinylimidazolium dione polymers disclosed in U.S. Patent Nos. 36.25694 and 38590
No. 96, No. 4128538, British Patent No. 127745
Polymer mordant crosslinkable with gelatin etc. disclosed in US Pat. No. 3,958,995 and US Pat. No. 27,218
No. 52, No. 2798063, JP 54-11522
No. 8, No. 54-145529, No. 54-126027
No. 54-155835, No. 56-17352, etc.; U.S. Patent No. 389
Water-insoluble mordants disclosed in U.S. Pat. No. 3642482, No. 3488706, No. 35570
No. 66, No. 3271147, No. 3271148, No. 53-30328, No. 52-155528, No. 53-125, No. 53-1024, No. 53-107
Examples include mordants disclosed in No. 835, British Patent No. 2,064,802, and the like.

Others: U.S. Patent No. 2675316, U.S. Patent No. 2882156
The mordants described in No. 1, etc. can also be mentioned. Any hydrophilic polymer can be used as the hydrophilic colloid in the image-receiving layer. When the image-receiving layer is adjacent to the release layer, gelatin or acetylated gelatin is preferred.

D) Layer having a neutralizing function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali brought in from the treatment composition, and if necessary, a layer having a neutralizing function. It may also have a multilayer structure including a sum rate adjusting layer (timing layer), an adhesion reinforcing layer, and the like. Preferred acidic substances include substances containing acidic groups (or precursor groups that provide such acidic groups upon hydrolysis) with a pKa of 9 or less, and more preferably oleic acid as described in U.S. Pat. No. 2,983,606. Higher fatty acids, polymers of acrylic acid, methacrylic acid or maleic acid as disclosed in U.S. Pat. No. 3,362,819 and their partial esters or acid anhydrides; acrylic acid as disclosed in French Patent No. 2,290,699 and acrylic acid ester copolymer; US Pat. No. 4,139,383 and Re5earch Disc
Mention may be made of latex-type acidic polymers as disclosed in Losure Na 16102 (1977).

Others: U.S. Patent No. 4088493, Japanese Unexamined Patent Publication No. 1987-1
No. 53739, No. 53-1023, No. 53-4540
No. 53-4541, No. 53-4542, etc. can also be mentioned.

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

The polymeric acid can be used in combination with a hydrophilic polymer. Examples of such polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, polymethylvinyl ether, and the like. Among these, polyvinyl alcohol is preferred.

The amount of polymeric acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of polymer acid to alkali per unit area is preferably 0.9 to 2.0. If the amount of polymeric acid is too small, the hue of the transferred dye may change or staining occurs in the colored area, and if it is too large, problems such as a change in hue or a decrease in light resistance occur. A more preferable equivalent ratio is 1.0 to 1.3. If the amount of hydrophilic polymer mixed is too large or too small, the quality of the photograph will deteriorate. The weight ratio of hydrophilic polymer to polymeric acid is between 0.1 and 10, preferably between O93 and 3.0.

Additives can be incorporated into the neutralizing layer of the present invention for various purposes. For example, hardening agents 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 antioxidants, as necessary.
Optical brighteners, dyes for blue tint, etc. can also be added.

The timing layer used in combination with the neutralizing layer may be made of a polymer with low alkali permeability, such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, etc. ; A latex polymer that increases the activation energy for alkaline permeation, which is made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer; A polymer having a lactone ring is useful.

Among them, JP-A-54-136328, U.S. Patent No. 4
No. 267262, No. 4009030, No. 402984
Timing layer using cellulose acetate disclosed in JP-A-54-128335 and JP-A-56-69.
No. 629, No. 57-6843, U.S. Patent No. 40563
No. 94, No. 4061496, No. 4199362, No. 4250243, No. 4256827, No. 42686
A latex polymer made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid, as disclosed in No. 04, etc.; A polymer having a lactone ring as disclosed in U.S. Pat.
No. 56-97346, European Patent Publication No. 57-6842, European Patent Publication No. 31957A1, European Patent Publication No. 37724A1, European Patent Publication No. 4
Particularly useful are the polymers disclosed in US Pat. No. 8,412A1 and others.

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

U.S. Patent Nos. 3,421,893, 3,455,686, 3,575,701, 3,778,265, and 37,858
No. 15, No. 3847615, No. 4088493, No. 4123275, No. 4148653, No. 42015
No. 87, No. 4288523, No. 4297431, West German Patent Application (OLS) No. 1622936, No. 21622
No. 77, Re5earch Disclosure
15162thl 51 (1976).

A timing layer using these materials can be used alone or as a combination of two or more layers.

Furthermore, timing layers made of these materials are disclosed in, for example, U.S. Pat.
No. 13164, No. 3014672, Japanese Unexamined Patent Application Publication No. 1983-15
Development inhibitors and/or their precursors disclosed in U.S. Pat. It is also possible to incorporate

E) Photosensitive Element In the present invention, a photosensitive element is provided which comprises a silver halide emulsion layer combined with a dye image-forming material above the release layer. I will talk about its components below.

(1) Dye-image-forming substance The dye-image-forming substance used in the present invention is either a non-diffusible compound that releases a diffusible dye (which may also be a dye precursor) in conjunction with silver development, or it has its own diffusive properties. "The theory of photographic process"
Theory of the Photography
cProcess'' 4th edition. All of these compounds can be represented by the following general formula (1).

(DYE>-Y (1) Here, (
DYE) represents a dye or its precursor, and Y represents a component that provides a compound having a diffusive group different from that of the compound under alkaline conditions.

Specific examples of negative-type Y include those that oxidize and cleave as a result of development to release a diffusible dye.

Specific examples of Y include US Pat. No. 3,928,312 and US Pat. No. 3,993.
No. 638, No. 4076529, No. 4152153,
No. 4055428, No. 4053312, No. 4198
No. 235, No. 4179291, No. 4149892,
No. 3844785, No. 3443943, No. 3751
No. 406, No. 3443939, No. 3443940,
No. 3628952, No. 3980479, No. 4183
No. 753, No. 4142891, No. 4278750,
No. 4139379, No. 4218368, No. 3421
No. 964, No. 4199355, No. 4199354,
No. 4135929, No. 4336322, No. 4139
No. 389, JP-A No. 53-50736, JP-A No. 511043
No. 43, No. 54-130122, No. 53-11082
No. 7, No. 56-12642, No. 56-16131,
No. 57-4043, No. 57-650, No. 57-20
No. 735, No. 53-69033, No. 54-13092
No. 7, No. 56-164342, No. 57-119345
It is stated in the number etc.

Among Y of the negative dye-releasing redox compound, particularly preferred groups include N-substituted sulfamoyl and 1 (the N-substituent is a group derived from an aromatic hydrocarbon ring or a petero ring). Typical groups for Y are illustrated below, but are not limited to these.

For positive compounds, Angewante Hemi International Edition English (Ang
ev, Chem, In5t, Ed, Engl, ),
22. 191 (1982).

A specific example is a compound (dye developer) that is initially diffusible under alkaline conditions but becomes non-diffusible after being oxidized during development. Typical examples of Y that are effective for this type of compound include those listed in US Pat. No. 2,983,606.

Another type is one that releases a diffusible dye by self-closing under alkaline conditions, but substantially ceases to release the dye when oxidized during development. For specific examples of Y having such a function, see U.S. Patent No. 3980479, U.S. Pat.
No. 199355, JP-A-53-69033, JP-A No. 54-
130927, etc.

Another type is one that does not itself release any pigment, but
Some release dyes when reduced.

This type of compound is used in combination with an electron donor,
Diffusible dye can be released into the image by reaction with the remaining electron donor oxidized into the image by silver development. Regarding atomic groups having such functions, for example, U.S. Pat.
No. 8368, No. 4356249, No. 4358525, JP-A-53-110827, No. 54-130927
No. 56-164342, Technical Report 87-6199
No., European Patent Publication No. 220746A2, etc.

Specific examples are shown below, but the invention is not limited to these.

CH.

I H3 C+tHts CH3 When this type of compound is used, it is preferably used in combination with a diffusion-resistant electron donor compound (known as an ED compound) or its precursor. E
Examples of compounds D include US Pat. No. 4,263,393.
No. 4278750, JP-A-56-138736, etc.

As specific examples of other types of dye image-forming materials, the following can also be used.

CI&H33 (In the formula, (DYE) represents a dye having the same meaning as mentioned above or its precursor.) Details of this can be found in U.S. Pat. Nos. 3,719,489 and 40,987.
It is described in No. 83.

On the other hand, specific examples of the dye represented by the general formula (D Y E) are described in the following literature.

Examples of yellow dyes: US Pat. No. 3,597,200, US Pat. No. 3,309,199, US Pat. No. 4,013,633, US Pat.
No. 09, No. 4139383, No. 4i95992, No. 4148641, No. 4148643, No. 43363
No. 22, JP-A-51-114930, JP-A No. 56-710
No. 72, Re5earch Disclosure
1 7 6 30 (1978), 1647
5 (1977).

Examples of Mazenk dyes: US Pat. No. 3,453,107, US Pat. No. 3,544,545, US Pat. No. 3,932,380, US Pat.
No. 08, No. 3954476, No. 4233237, No. 4255509, No. 4250246, No. 41428
No. 91, No. 4207104, No. 4287292, JP-A No. 52-1゜6727, No. 52-106727,
No. 53-23628, No. 55-36804, No. 56
-73057, 56-71060, 55-13
What is listed in No. 4.

Examples of cyan dyes: U.S. Pat. No. 3,482,972, U.S. Pat. No. 3,929,760, U.S. Pat.
No. 20, No. 4242435, No. 4142891, No. 4195994, No. 4147544, No. 41486
No. 42, British Patent No. 1551138, Japanese Unexamined Patent Publication No. 1987-9
No. 9431, No. 52-8827, No. 53-47823
No. 53-143323, No. 54-99431,
European Patent Publication No. 56-71061, European Patent Publication No. 53037, European Patent Publication No. 53040, Re5earch Disclosure
re 17630 (1978) and re 16475
(1977).

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

Internal latent image type direct positive emulsions include, for example, so-called "conversion type" emulsions that are created by taking advantage of the solubility difference of silver halides, and emulsions that are doped with metal ions, chemically enriched, or both. "Core/shell type" in which at least the photosensitive sites of the coated silver halide inner core grains are covered with a silver halide outer layer (shell).
There are emulsions, etc., which are described in U.S. Patent No. 25922.
No. 50, No. 3206313, No. 3761276, No. 3935014, No. 3447927, No. 24978
No. 75, No. 2563785, No. 3551662, No. 4395478, No. 4431730, West German Patent No. 2
728108, British Patent No. 1027146, etc.

Further, when using an internal latent image type direct positive emulsion, it is necessary to apply fog nuclei to the surface using light or a nucleating agent after imagewise exposure.

As a nucleating agent for this purpose, US Pat. No. 2,563,785
No. 2,588,982, hydrazides described in U.S. Patent No. 3,227,552,
Hydrazines, British Patent No. 1283835, JP-A-5
No. 2-69613, U.S. Pat. No. 3,615,615, No. 3
No. 719494, No. 3734738, No. 409468
Heterocyclic quaternary salt compounds described in No. 3, No. 4115122, etc., sensitizing dyes having substituents with nucleating effect in the dye molecule described in U.S. Pat. No. 3,718,470, U.S. Pat. No. 4,030,925, No. 4031127, No. 42
No. 45037, No. 4255511, No. 4266013
Thiourea-bonded acylhydrazine compounds described in U.S. Pat.
Acylhydrazine compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorption group as described in No. 8, British Patent No. 2011391B, etc. are used.

In the present invention, a spectral sensitizing dye is used in combination with these negative emulsions and internal latent image type direct positive emulsions.

For specific examples, see JP-A-59-180550,
No. 60-140335, Re5earch Discl.
osure 17029, US Patent No. 1846300
No. 2078233, No. 2089129, No. 21
No. 65338, No. 2231658, No. 2917516
No. 33528.57, No. 3411916, No. 2
No. 295276, No. 2481698, No. 268854
No. 5, No. 2921067, No. 3282933, No. 3
No. 397060, No. 3660103, No. 333501
No. 0, No. 3352680, No. 3384486, No. 3
No. 623881, No. 3718470, No. 402534
It is described in No. 9 etc.

(3) Structure of the light-sensitive element In order to reproduce natural colors by the subtractive color method, the dye image-forming substance provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized with the above-mentioned spectral sensitizing dye. A photosensitive layer consisting of at least two of the following combinations is used. The emulsion and the dye image-forming substance may be coated as separate layers, or may be mixed and coated as a single layer. A separate layer is preferable when the dye image-forming material coated has absorption in the spectral sensitivity range of the emulsion with which it is combined.

Further, the emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming substance layer.
Layer containing a nucleating development accelerator described in No. 1, JP-A-60
It is also possible to increase the color image density by providing a barrier layer as described in Japanese Patent Laid-Open No. 15267, and to increase the sensitivity of the photosensitive element by providing a reflective layer as described in Japanese Patent Application Laid-Open No. 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 arranged in this order from the exposure side.

Any layer may be provided between each emulsion layer unit, if necessary. In particular, it is preferable to provide an intermediate layer in order to prevent the effects of development of one emulsion layer from having an unfavorable effect on other emulsion layer units.

When a developer is used in combination with a non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent the oxidized form of the developer from diffusing. Specific examples include non-diffusible hydroquinone, sulfonamidophenol, sulfonamide naphthol, and more specifically, Japanese Patent Publications Nos. 50-21249 and 50-2381.
No. 3, JP-A-49-106329, JP-A No. 49-1295
No. 35, U.S. Patent No. 2,336,327, U.S. Patent No. 2,36029
No. 0, No. 2403721, No. 2544640, No. 2
No. 732300, No. 2782659, No. 293708
No. 6, No. 3637393, No. 3700453, British Patent No. 557750, Japanese Patent Application Laid-open No. 57-24941, Japanese Patent Application Publication No. 58-21249, and the like. Dispersion methods thereof are described in JP-A No. 60-238831 and JP-B No. 6-18978.

When using a compound that releases a diffusible dye with silver ions as described in Japanese Patent Publication No. 7576/1982, it is preferable to include a compound that captures silver ions in the intermediate layer.

In the present invention, an irradiation prevention layer, an isolation layer, a protective layer, etc. are applied as necessary.

Processing The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is applied to a light-shielding layer provided on the back side of the support or on the opposite side of the photosensitive layer to the processing solution. Paired with the photosensitive layer, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed using the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light shielding agent, a developer, a development accelerator to control development, a development inhibitor, an antioxidant to prevent deterioration of the developer, etc. A light shielding agent is always included in the 0Mi composition.

The alkali is sufficient to adjust the pH of the liquid to 12 to 14, and includes alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (e.g., potassium phosphate). , guanidines,
Examples include hydroxides of quaternary amines (eg, tetramethylammonium hydroxide), and among them, potassium hydroxide and sodium hydroxide are preferred.

The thickener is necessary to spread the processing solution uniformly and to maintain close contact between the photosensitive layer and the cover sheet when the used photosensitive layer is peeled off together with the cover sheet. For example, alkali metal salts of polyvinyl alcohol, hydroxyethylcellulose, and carboxymethylcellulose are used, preferably hydroxyethylcellulose,
Sodium carboxymethyl cellulose is used.

Also, oxime-containing polymers described in US Pat. No. 4,397,996 may be used.

As the light shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse into the dye image-receiving layer and cause staining. Carbon black is a typical example, but combinations of titanium white and dyes are also used. This dye may be a temporary light blocking dye that becomes colorless after a certain period of time of treatment.

Preferred developing agents are any that cross-oxidize the dye image-forming material and do not substantially stain when oxidized.

Such developers may be used alone or in combination of two or more, or may be used in the form of a precursor. These developing agents may be contained in a suitable layer of the photosensitive element or in an alkaline processing solution. Specific compounds include aminophenols and pyrazolidinones, among which pyrazolidinones are This is particularly preferable because staining is less likely to occur.

For example, l-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1-(3'-methyl-phenyl)-4-methyl-4
Examples thereof include -hydroxymethyl-3-pyrazolidinone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and 1-p-)lylu-4-methyl-4-hydroxymethyl-3-pyrazolidinone.

G) Cover Sheet In the present invention, a transparent cover sheet is used to uniformly spread the processing liquid on the photosensitive element.

After processing, the cover sheet is peeled off along with the processing solution and the used photosensitive layer. Therefore, it is preferable to perform a surface treatment or apply a suitable adhesive layer to ensure sufficient adhesion with the treatment liquid.

As an example of such an adhesive layer, Japanese Patent Publication No. 61-49658
The hydrophilic layer described in the above is particularly preferred. It is also possible to adjust the sensitivity of the photosensitive layer by incorporating a filter dye into the cover sheet. The filter dye may be added directly into the support of the cover sheet or may be applied as a separate layer.

The support for the cover sheet used in the present invention may be any smooth transparent support commonly used for photographic materials, such as cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate, etc.
An undercoat layer may also be provided. For the undercoat layer, an undercoat liquid commonly used for photographic light-sensitive materials is used.

The cover sheet may include a layer having the above-mentioned neutralizing function.

The film unit of the present invention includes a mask material, It is processed into a monosheet using rail material, surplus liquid trap material, etc.

In particular, in order to facilitate peeling after treatment, Re5ea
rch Disclosure Na23026
(1983), it is effective to make a slit as described in (1983). The shape, depth, etc. of the slit are selected depending on the physical properties of the white support used. - The size of the film unit is arbitrary, but in addition to the size of the instant film currently available on the market, a more compact film size or a larger film size can be used.

In order to photograph using the film unit of the present invention, it is necessary to form a mirror image of the subject on the film. For this purpose it is necessary to use mirrors.

For this type of camera, U.S. Patent No. 344
It is known as No. 7437.

(Example) Example 1 A carbon black layer (
Carbon black 3.0g/r+? .

(contains 4.5 g/% gelatin) and titanium oxide layer (3.0 g/n titanium oxide (contains 1.0 g/m' gelatin)
was painted.

Next, the following layers were sequentially coated on the opposite side of the light-shielding layer of this support to prepare an image-receiving photosensitive sheet.

(1) Cellulose acetate (oxidation degree 55%) 6g/resistant,
Methyl vinyl ether-maleic anhydride copolymer 4 g
/rd, titanium dioxide 0.05 g/n (and a neutralization layer containing 0.82 g/% of the following compound.

H (2) Styrene-n-butyl acrylate-acrylic acid-methylolacrylamide 49.7 vs. 42.3
4:4 copolymer latex solids content 1.3g/m
, and a 93:3:4 copolymer latex solids content of 1.3 g/rtr of methyl methacrylate-acrylic acid-methylolacrylamide.

(3) Styrene-n-butyl acrylate-acrylic acid-methylolacrylamide 49.7 vs. 42.3
4:4 copolymer latex solid content 0.5g/, 1
A layer containing 0.5 g/n of gelatin and 0.5 g/n of gelatin.

(4) Titanium oxide 5g/m and gelatin 0.5g/m'
reflective layer.

(5) Add the following polymer latex mordant at 3 g/rtr and acetylated gelatin (jelly strength 182 g, viscosity 43
Image receiving layer containing mp, conductivity 6.2, pH 6.2, isoelectric point 4°3, acetylation 7%) 3 g/rd.

(6) Hydroxyethyl cellulose (5P-900 manufactured by Daicel Chemical Industries) 0.7 g/m ff:
II delamination.

(7) Layer consisting of diacetyl cellulose 0.1 g/m.

(8) A layer containing 2.5 g/m of gelatin.

(9) The following cyan dye-releasing redox compound 0°44
g/rd,) cyclohexyl phosphate 0゜09g
/rrr, 2.5-di-t-pentadecylhydroquinone 0.008g/i-carbon black 0.05g/i
and a layer containing 0.8 glrd of gelatin.

Et O [titanium oxide 2g/rd, and gelatin 0.5g/rd
A light-reflecting layer containing a.

0υ Octahedral internal latent image type direct positive silver bromide emulsion with grain size of 1.0 μm (silver amount 0.15 g/m), red-sensitive sensitizing dye, gelatin 0.4 g/n? , the following nucleating agent (NA
) 1.1 μg/rrr, and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.02 g/rrr
A low-speed red-sensitive emulsion layer containing n(.

NA (2) Octahedral internal latent image type direct positive silver bromide emulsion with grain size of 1.6 μm (0.5 g/% silver amount), red-sensitive sensitizing dye, gelatin 0.8 g/n (layer) Same nucleating agent (NA) as at+ 3.0 μg/rrr and 2~sulfo-5-n
-Pentadecylhydroquinone sodium salt 0.04
Highly sensitive red-sensitive emulsion layer containing g/d.

α12.5-di-t-pentadecylhydroquinone 1.
2 g/rd, polymethyl methacrylate 1°2 g/
rd and gelatin 0.7 g/m.

Q41 Layer containing 0.3g/rrr of gelatin.

051 The following magenta dye-releasing redox compound 0
゜15g/n? ,) 0.1 g/cd of cyclohexyl phosphate, 0.009 g/rrr of 2.5-di-t-pentadecylhydroquinone and 0.0 g/rrr of gelatin. 9g
/A containing layer.

αe Titanium oxide 1 g/rd and gelatin 0.25
A light reflecting layer containing g/rrr.

01 Octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.0 μm (silver content 0.12 g/m), green-sensitizing enhancing dye, gelatin 0.25 g/rr+, same structure as layer OD. Nucleating agent (NA)1. A low-speed green-sensitive emulsion layer containing Iμg/rrr and 0.02g/rrr of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

Ql octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.6 μm (silver content 0.35 g/m), green-sensitizing enhancing dye, gelatin 0.7 g/rr+, same nucleation as layer αυ agent (NA) 1.1 υg/rd and 2-sulfo-5-
n-pentadecylhydroquinone sodium salt 0.0
4 g/n (high sensitivity green-sensitive emulsion layer).

α'J2.5-di-t-pentadecylhydroquinone 0
．． 8g/m, polymethyl methacrylate 0°8g/
Color mixing prevention layer containing RD and gelatin 0.45g/%.

(a) Layer containing 0.3 g/rd of gelatin.

(21) Yellow dye-releasing redox compound with the following structure (0.53 g/rd), tricyclohexyl phosphate (0.13 g/m), 2.5-di-t-pentadecylhydroquinone 0. Layer containing O1Ag/n () and gelatin (0,7 g/rrr).

(22) Titanium oxide 7g/m and gelatin 0
A light reflecting layer containing 18 g/rrr.

(23) Octahedral internal latent image direct positive silver bromide emulsion with grain size 1.1 μm (silver content 0.25 g/m), blue-sensitive sensitizing dye, gelatin 0.4 g/m, layer 0 υ. The same nucleating agent (NA) 2 μg/m, and 2-sulfo-5-
n-pentadecylhydroquinone sodium salt 0.0
A slow blue-sensitive emulsion layer containing 45 g/m.

(24) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.7 μm (silver content: 0.42 g/n(),
Blue-sensitive sensitizing dye, gelatin 0.45g/rrr, layer αυ
The same nucleating agent (NA) 3.3 μg/rrr, and 2-
A high-temperature blue-sensitive emulsion layer containing 0.025 g/m of sulfo-5-n-pentadecylhydroquinone sodium salt.

(25) The following ultraviolet absorbers were each used in 4×10
-'mol/, (and an ultraviolet absorbing layer containing 0.5 g/n of gelatin).

(26) Preservative containing matting agent and gelatin 0.5 g/n.

Next, coating was carried out in the following order on a polyethylene terephthalate support containing a light piping prevention dye and undercoated with gelatin to prepare a cover sheet.

(1) Cellulose acetate (oxidation degree 55.5%) 6g/ff
l, methyl vinyl ether-maleic anhydride copolymer 4
A neutralization layer containing g/rd.

(2) Styrene-n-butyl acrylate-acrylic acid-N-methylol acrylamide at a weight ratio of 49.7
A polymer latex emulsion-polymerized with a weight ratio of 93/3/4 and a polymer latex with a solid content ratio of 5 A layer blended in a ratio of 5 to 5 and containing a total solids content of 3.9 g/+d.

(3) Styrene-n-butyl acrylate-acrylic acid-N-methylol acrylamide at a weight ratio of 49.1
/42. A layer containing 0.5 g/ffl of emulsion-polymerized polymer latex and 0.5 g/ffl of gelatin in a ratio of 3/4/4.

Layer the above image-receiving photosensitive sheet and cover sheet in a face-to-face relationship.1. Furthermore, a photographic film unit of the present invention was prepared by fixing an alkaline processing liquid containing a light-shielding agent having the composition shown below in a bag that can be ruptured under pressure.

The film unit of the present invention is the same as the film unit except that the following Ji (7') is provided in place of the layer (7).
, Ig/rrr. And, a film unit ◎ of the present invention was prepared which was the same as the film unit except that the following layer (6') was provided in place of layer (6).

(6') Release layer consisting of 0.7 g/d of hydroxypropyl cellulose.

Next, layer (7) and layer (6) are used as comparison samples.
A film that is the same as film unit ■, except that the following layer (6#) is provided in place of film unit ■, film unit ■, which is the same as film unit ■, and layer (6). Unit [F] was created.

(6#) Butyl methacrylate-acrylic acid copolymer (copolymerization ratio 50/50) 0. 06 g/n? The support on the side where the processing liquid pot is attached is
Discontinuous perforations were made as described in No. 6-67840.

After a color test chart was exposed through the cover sheet through this film unit, the film unit was passed between a pair of rollers to uniformly spread the processing liquid in the processing pot between the photosensitive element and the cover sheet. After a certain period of time had elapsed after the treatment solution was applied, the perforation was cut by strongly bending and the cover sheet was peeled off.

Wet peelability was evaluated based on the area ratio between the peeling layers that was cleanly peeled off and the desired image was obtained, with the time taken to peel off being 5 minutes. When complete peeling is performed, 100
Shown in %. To measure the minimum image density Dmin, the peeling time was set to 10 minutes, and the transferred image after peeling was passed through a red filter to measure the minimum white image density Dmin. The smaller the value, the better. Table 1 shows the above measured values for each film unit.

Table 1 As is clear from Table 1, Samples ■■ and ◎ of the present invention have lower DIIlin and are superior in wet releasability than Comparative Example ■■.

Example 2 A carbon black layer (3.0 g of carbon black/
rrr, gelatin 4. 5g/n (including.

and Titanium White N (Titanium White 3.0g/d,
Gelatin 1. Qg, , 'n (including) were painted.

Next, the following layers were sequentially coated on the opposite side of the light-shielding layer of this support to prepare an image-receiving photosensitive sheet.

+11 Maleic anhydride and vinyl methyl ether 1
:1 copolymer butyl half ester (average molecular weight approximately 1
00,000) 30g/rrf, titanium dioxide 0.05g/m,
and a neutralization layer containing 0.8 g/m of the following compound.

S -CHzCHzSOzCHz-CH-CHzS(h
cLcII□-8H (2) Copolymer of butyl acrylate, diacetone-acrylamide, styrene, and methacrylic acid (copolymerization ratio 60/30/4/6) 0, 49
g/m, polyacrylamide 0.01g/+y?
A timing layer containing.

) (3, 2, g/i, zeutia 1 g
Reflective layer containing / m.

(4) An image-receiving layer containing poly-4-vinylpyridine (average molecular weight: 80,000), 3.2 g/rtr, and polyvinyl alcohol (saponification degree: 98%: average molecular weight: approximately 80,000), 3.2 g/n.

(5) Hydroxyethylcellulose (5P-900, manufactured by Taisel Kagaku Kogyo ■) 0.7 g/R group.

(6) Cellulose acetate with a degree of acetylation of 51% 0.1g/
A layer consisting of M.

(7) Ethyl acrylate latex at 1 g/m
, a layer containing 2.5 g/m of gelatin.

(8) Negative silver iodobromide emulsion (iodine: 2 mol%, silver amount 2.3 g/n(), gelatin 1.1 g/rd, red-sensitive sensitizing dye 3.3', 9-) riethyl-5 .A red-sensitive emulsion layer containing 5'-dichlorothiacarbocyanine iodine salt.

(9) The following temporary shortwave cyan dye developer 0.8 g/d
, N,N-diethyl-laurylamide 0.8g/n(,
Layer containing 1.1 g/m of gelatin.

QO) Layer containing 3.5 g/m of gelatin.

aυ negative silver iodobromide emulsion (iodine: 2 mol%, iI amount 1
．． 7g/n? ), 1.3 g/rd of gelatin, and a green-sensitive emulsion layer containing 3.3', 9-)liethyl-5,5'-diphenyloxacarbocyanine bromide, a green-sensitive sensitizing dye.

03 Temporary short wave magenta dye developer with the following structure 0°6g
/m, N, N-diethyl laurylamide 0゜6g/rd
, a layer containing 1.2 g/I of gelatin.

Q3 Layer containing 3.0 g/m' of gelatin.

041 Blue-sensitive emulsion layer containing negative silver iodobromide emulsion (iodine = 2 mol %, silver amount 1.8 g/rrr) and gelatin 1.6 g/m.

QSI Temporary shortwave yellow dye developer 1 with the following structure
゜og/=1N, N-diethyl laurylamide 1゜0
g/', layer containing 1.8 g/m of gelatin.

11614'-methylphenylhydroquinone 0.45
g/n(, tri-cresyl phosphate 0945g
/n (, a layer containing 1.3 g/rd of gelatin (0.02 g/m of mucochloric acid was included as a hardening agent).

The above image-receiving photosensitive sheet and the cover sheet of Example 1 were stacked face-to-face, and then an alkaline processing solution containing a light-shielding agent having the composition shown below was filled in a bag that could be ruptured under pressure. The film unit (2) of the present invention was prepared by fixing it in the body.

Processing Solution The photographic film unit (2) was exposed to light from the cover sheet side using a gray wedge, and then developed at 25° C. by spreading the processing solution to a thickness of 100 μm using a pressing member. After developing the processing solution, if Ml+ is released after 3 minutes, the image-receiving photosensitive sheet becomes wet due to ff and lI delamination? JI release property 100%
Peeling occurred, and an excellent image with a low minimum image density Dmin O,] of 7 was obtained.

(Effects of the Invention) According to the present invention, a peelable color diffusion transfer photographic film unit having excellent peelability, low minimum image density, and excellent sharpness can be obtained.

Claims (1)

[Claims] A peelable color diffusion transfer photographic film unit having at least a dye image-receiving layer, a release layer, and a photosensitive layer on a support, wherein the release layer is a layer containing hydroxyalkylcellulose, and the release layer and the photosensitive layer are A color diffusion transfer photographic film unit having a layer containing cellulose ester between the layers.