JPH02251954A - Color diffusion transfer photographic film unit - Google Patents

Abstract

PURPOSE:To obtain the color diffusion transfer unit of a release type having high image quality and excellent handling characteristic by incorporating at least one kind of compds. selected from aliphat. sulfinic acid or the salts thereof and arom. sulfinic acid or the salts thereof into a processing compsn. CONSTITUTION:At least one of the compds. which are selected from the aliphat. sulfinic acid or the salts thereof and arom. sulfinic acid or the salts thereof and are expressed by formula I are incorporated into the processing compsn. of the unit having a layer provided with a light shielding function on a base on the side opposite to the silver halide emulsion layers thereof. In the formula I, M denotes a hydrogen atom, sodium, etc.; Y denotes an alkyl group, substd. alkyl group, etc.; n denotes 1 or 2. The images having the particularly excellent handling characteristic together with the high image quality are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color diffusion transfer photographic film unit;
More specifically, the present invention relates to a color diffusion transfer photographic film unit that is a peelable integrated film unit and has less staining after peeling.

(Prior Art) Conventionally, in a peelable type color diffusion transfer photographic film unit, a photosensitive layer and an image receiving layer are coated on separate supports, as shown in Japanese Patent Publication No. 49-26896, for example. After image exposure, the photosensitive element and the image-receiving element are overlapped, a processing composition is spread between them, and the image-receiving element is then peeled off to obtain a dye image transferred to the image-receiving layer (type A), for example. As shown in JP-A-59-220727, a photosensitive layer and an image-receiving layer are coated on the same support, and after image exposure, a processing composition is spread between the cover sheet and the photosensitive layer and image-receiving layer. A type (type B) in which the image-receiving layer is peeled off through a peeling layer between the layers and the image is observed through a transparent support, or as shown in JP-A No. 63-226649, the photosensitive layer and the image-receiving layer are separated. is coated on the same support, and after image exposure, a processing composition is spread between the cover sheet and the image-receiving layer is peeled off through a peeling layer between the photosensitive layer and the image-receiving layer, and the support is removed. There is a type (type C) that allows images to be directly observed without any intervention.

Among these, type C peel-off color diffusion transfer photographic film units are superior to other types in that they are easy to handle and provide high image quality. especially,
On a white support, at least (a) a dye image-receiving layer, (b)
a release layer; (c) a light-sensitive element having in sequence at least one silver halide emulsion layer in combination with a dye image-forming substance; an alkaline processing composition containing a light-blocking agent; and a transparent cover sheet having a neutralizing function; In a system having a layer having a light-shielding function on the side of the white support opposite to the silver halide emulsion layer, images with high image quality and particularly excellent handling properties can be obtained.

(Problems to be Solved by the Invention) However, in such a system, the image after peeling does not have a neutralizing function, so if the image is peeled off before the pH has sufficiently decreased,
The pH of the image remains high. At this time, a pink stain appears on the image.

(Object of the Invention) An object of the present invention is to provide a peelable color diffusion transfer unit that has high image quality and excellent handling properties.

Another object is to provide a color diffusion transfer unit with less staining in the image after peeling.

SUMMARY OF THE INVENTION The object is to provide at least one halogen compound on a white support in combination with at least (a) a dye image-receiving layer, (b) a release layer, and (c) a dye image-forming material. It consists of a light-sensitive element having successively silver halide emulsion layers, an alkali processing composition containing a light shielding agent, and a transparent cover sheet having a neutralizing function, the white support having a light shielding function on the side opposite to the silver halide emulsion layer. A color diffusion transfer photographic film unit, characterized in that the processing composition contains at least one compound selected from aliphatic sulfinic acids or salts thereof, aromatic sulfinic acids or salts thereof. achieved by.

In the preferred embodiment, at least (
a photosensitive element having sequentially a) a dye image-receiving layer, (b) a release layer, (c) at least one silver halide emulsion layer in combination with a dye image-forming substance, and a transparent cover sheet having a neutralizing function; A unit comprising an alkali processing composition containing a light-shielding agent spread between the uppermost layer of the photosensitive element and the cover sheet, and having a layer having a light-shielding function on the side of the white support opposite to the silver halide emulsion layer. This was achieved by including a compound represented by the following general 2N) in the treatment composition.

General formula (1) : %formula%) hydrogen atom, sodium, potassium Alkali metal atoms such as Aluminum such as sium and magnesium Potassium earth metal or triethyl acetate amine, trimethylamine, etc. machine base Y: Alkyl group, substituted alkyl group, Aryl group or substituted group Base.

n: 1 or 2 The total carbon number of the alkyl group or substituted alkyl group represented by Y above is preferably 5 to 30, more preferably 8 to 2.
4, and may be linear or branched, and examples of substituents for the alkyl group include hydroxy group, carboxy group,
1 sulfonic acid group, amino group, nitro group, alkyl residue
an alkoxy group having ~5 carbon atoms, a phenyl group,
Examples include halogen atoms (chlorine atoms, etc.).

The aryl group represented by Y is, for example, a phenyl group or a naphthyl group, and the substituents of the substituted aryl group are, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group (such as a vinyl group), or an alkyl group having 1 to 18 carbon atoms. an alkoxy group, a hydroxy group, a carboxy group having ~5 carbon atoms,
Examples include a sulfonic acid group, an amino group, a nitro group, a phenyl group, and a halogen atom (chlorine atom, etc.).

The sulfinic acids used in the present invention are specifically shown below.

9゜10゜CsH+? 5OtNa C,,13,sO,Na The amount of the compound of the present invention used is 0.02-100 mol%, preferably 10-40 mol%, based on the developing agent in the processing composition.

Conventionally, the incorporation of sulfinic acid or its salts into treatment compositions has been disclosed in JP-A-59-58428, etc., but the system shown in this patent is not mentioned, and the desired effect is not achieved. They are completely different.

That is, in JP-A-59-58428, a preferred embodiment includes an image-receiving layer, a substantially opaque light-reflecting layer (e.g., a titanium white layer and a carbon black layer), and a photosensitive layer on a transparent support. There is also a laminated integrated monosheet type in which an alkali treatment composition containing a light blocking agent is spread between a coated photosensitive sheet and a cover sheet with a neutralizing function, and also a support, a neutralizing layer, An image receiving sheet consisting of a neutralization rate adjusting layer and a mordant layer, and a photosensitive layer on a support.
This is a so-called beer-apart type method in which an alkali processing composition is spread between layers of a photosensitive sheet, and the photosensitive sheet is peeled off after processing. In all of these systems, a layer with a neutralizing function remains in the image obtained after processing and is designed to naturally lower the pH, but in the system of the present invention, the image obtained after processing In order to simplify the structure of the image, no layer having a neutralizing function is left behind. Therefore, for example, if HIM after processing is performed too quickly, the pH of the image may not be completely lowered. The above-mentioned pink stain is likely to occur in such a system with a high pH (9 or higher), but not in a system such as that disclosed in JP-A-59-58428.

Therefore, JP-A-59-58428 does not mention the pink stain of the present invention, and it does not mention the performance deterioration (density decrease) during long-term storage of the processing solution and the long-term
This article describes an improvement in yellow staining after a period of one month or more, which is completely different from the effect of the present invention. (The above-mentioned pink stain occurs immediately after peeling off.) Each of these components will be explained in turn below.

The white support as used in the present invention refers to a support that is white at least on the side on which the dye image-receiving layer is coated, and any support can be used as long as it has sufficient whiteness and smoothness. I can do it. For example, titanium oxide with a particle size of 0.1 to 5μ,
Polymer films made white by adding white pigments such as barium sulfate or zinc oxide or by forming microvoids by stretching, such as films made of polyethylene terephthalate, polystyrene, or polypropylene made by conventional sequential biaxial stretching, synthetic paper, and paper. A material laminated with polyethylene, polyethylene phthalate, polypropylene, etc. containing titanium white on both sides is preferably used. The thickness of the support is 50-350 μm, preferably 70-21
0 μm2, more preferably 80-150 μm. Further, if necessary, a light-shielding layer may be provided in the support.9 For example, a support formed by laminating polyethylene containing a light-shielding agent such as a carbon blank on the back side of a white support is used.

As a raw material for carbon black, for example, Donnei
Voet “Carbon Black” Marce
Any manufacturing method can be used, such as the channel method, thermal method, and furnace method as described in Dekker+Inc. (1976).

The particle size of carbon black is not particularly limited, but 9
Preferably 0 to 1800 people.

The amount of black pigment added as a light-shielding agent may be adjusted depending on the sensitivity of the light-sensitive material to be light-shielded, but the optical density should be 5 to 1.
About 0 is desirable.

The dye image-receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants with different mordant powers are coated overlappingly.
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 s, ooo or more are particularly preferable. is 10,00
It is 0 or more.

For example, U.S. Pat. No. 2,548,564, U.S. Pat.
．． No. 430, No. 3,148,061, No. 3.756,
Vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in US Pat. No. 814, etc.; vinylimidazolium cationic polymers disclosed in US Pat. No. 4,124.386, etc.;
No. 25,694, No. 3,859,096, No. 4.12
No. 8538, a polymer mordant capable of crosslinking with gelatin etc. as disclosed in British Patent No. 1.277.453; US Pat. No. 3,958,995, British Patent No. 2.721,85
No. 2, No. 2,798,063, JP-A-54-115,
No. 228, No. 54-145529, No. 54-126,
No. 027, No. 54-155.835, No. 56-17,
Aqueous sol type mordant disclosed in No. 352 specification etc.;
A water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088, etc.; Reactive mordants that can be used; furthermore, US Pat.
09,690, 3,788.855, 3,6
No. 42,482, No. 3.488,706, No. 3,
No. 557.066, No. 3,271,147, No. 3
．． 271゜148, JP-A No. 53-30328, JP-A No. 52-155528, JP-A No. 53-125, JP-A No. 53-1
No. 024, No. 53-107,835, British Patent 2.0
Examples include mordants disclosed in US Pat. No. 64,802 and the like.

Others: U.S. Patent No. 2,675,316, U.S. Patent No. 2゜882
．． Mention may also be made of the mordants described in No. 156.

In the present invention, a peeling layer is provided between the emulsion layer combined with the dye image-forming substance and the dye image-receiving layer, and the emulsion layer is peeled off after processing. Therefore, this release layer must be able to maintain close contact between the image-receiving layer and the emulsion layer in an untreated state and be easy to peel off after processing.

Materials for this purpose include, for example, JP-A-47-823
7, 59-220727.59-229555, 4
9-4653, U.S. Pat. No. 3,220,835, U.S. Patent No. 43,595
18, Japanese Patent Publication No. 49-43.34, 56-65133,
No. 45-24075, U.S. Pat. No. 3,227,550, No. 27
59825, 4401746, 4366227, etc. can be used. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives, such as hydroxyethyl cellulose, cellulose acetate-phthalate, plasticized methyl cellulose, ethyl cellulose, nitric cellulose,
carboxymethylcellulose, etc. 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. Furthermore, other examples include water-soluble synthetic polymers such as polyvinyl alcohol, polyacrylate, polymethyl methacrylate, butyl methacrylate, or copolymers thereof.

The release layer may be a single layer or may be composed of a plurality of layers.
0-60642, etc.

In the present invention, a photosensitive layer consisting of a silver halide emulsion layer combined with a dye image-forming substance is provided above the release layer. Its components will be described 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 @The T
theory of the Photographic
Process" 4th edition. All of these compounds can be represented by the following general formula (+).

DYE-Y (1) Here, DYE represents a dye or its precursor, and Y
represents a component that provides a compound with diffusivity different from that of the above compound under alkaline conditions. Due to the function of Y, a negative-type compound becomes diffusive in the silver developed area and a positive-type compound becomes diffusible in the undeveloped area. It is broadly divided into

Particularly preferred are dye-releasing redox compounds that are themselves non-diffusible, and particularly preferred are negative-working dye-releasing redox compounds that are themselves non-diffusible.

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

Specific examples of Y are U.S. Pat. Nos. 3,928,312 and 3,9.
No. 93,638, No. 4,076.529, No. 4,15
No. 2,153, 4. 055. No. 428, 4.0
No. 53,312, No. 4.198235, No. 4,179
．． No. 291, No. 4,149.892, No. 3,844,
No. 785, No. 3443.943, No. 3,751,40
No. 6, No. 3,443,939, No. 3,443,940
No. 3,628,952, No. 3,980,479, No. 4,183,753, No. 4,142,891,
4,278,750, 4,139°379, 4,218,368, 3,421.964, 4
, 199.355, 4゜199.354, 4,
No. 135,929, No. 4.336,322, No. 4.1
No. 39,389, JP-A-53-50736, JP-A No. 51-
No. 104343, No. 54-130122, No. 53-1
No. 10827, No. 56-12642, No. 56-161
No. 31, No. 57-4043, No. 57-650, No. 5
No. 7-20735, No. 53-69033, No. 54-1
No. 30927, No. 56-164342, No. 57-11
It is described in No. 9345, etc.

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

H H3O1- H CtHw(t) H For positive-type compounds, Angewante Hemi International Edition
gev, Chew, In5t, Ed, Engl
), 22+191 (1982).

A specific example is one that releases a diffusible dye by self-closing under alkaline conditions, but substantially stops releasing the dye when oxidized during development.

For specific examples of Y having such a function, see U.S. Pat.
-130927, U.S. Patent No. 3,421,964, 4.
199. 355, 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,
The diffusible dye can be released imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. Regarding atomic groups having such functions, for example, U.S. Pat.
18.368, JP 53-110827, U.S. Patent 4
゜278.750, 4,356,249, 4358
．． 525, JP 53-110827, JP 54-130
927, 56-164342, public branch root 87-619
9, European Patent Publication No. 220746A2, etc.

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

O Hff CH2 C+Jts 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, for example, U.S. Pat. No. 4,263,39
No. 3, No. 4,278°750, JP-A-56-1387
It is described in No. 36, etc.

On the other hand, specific examples of the dye represented by the general formula DYE are described in the following literature.

Example of yellow dye: U.S. Pat. No. 3,597,200, U.S. Pat. No. 3,309°199
No. 4,013,633, No. 4,245.028, No. 4,156.609, No. 4゜139.383,
No. 4,195,992, No. 4,148,641, No. 4,148,643, No. 4,336,322; JP-A-51-114930, No. 56-71072: R
e5earchDisclosure 17630
(1978) and No. 16475 (1977).

Example of magenta dye: U.S. Pat. No. 3,453,107, U.S. Pat. No. 3,544°545
No. 3,932,380, No. 3,931.144, No. 3,932,308, No. 3954.476,
4,233.237, 4,255,509, 4,250,246, 4,142,891, 4
, 207,104, 4,287,292; JP-A-52-106.727, 52-106727, 53-23,628, 55-36,804, 5
No. 6-73.057, No. 56-71060, No. 55-
What is described in No. 134.

Examples of cyan dyes: U.S. Pat. No. 3,482,972, 3. 929760
No. 4,013,635, No. 4,268.625, No. 4,171,220, No. 4242.435, No. 4,142,891, No. 4.195,994, No. 4
, No. 147,544, No. 4,148,642; British Patent No. 1.551138: JP-A No. 54-99431, No. 52-8827, No. 53-47823, No. 53-1
No. 43323, No. 54-99431, No. 567106
No. 1; European Patent (RPC) No. 53037-53
*040; Re5search Disclo
sure17.630 (1978) and 16.
475 (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 made by taking advantage of the solubility difference of silver halides, and emulsions that are doped with metal ions, chemically sensitized, 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 shell.
There are emulsions, etc., which are described in U.S. Patent No. 2.592.
250, 3.206,313, British Patent No. 1027.1
46, U.S. Patent No. 3,761.276, U.S. Patent No. 3,935,0
14, 3,447,927, 2,497.875,
2,563,785, 3,551,662, 4,
No. 395,478, West German Patent No. 2,728,108, and US Pat. No. 4,431,730.

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

As a nucleating agent for this purpose, U.S. Patent No. 2,563.78
5, hydrazines described in 2,588,982,
Hydrazides and hydrazones described in U.S. Patent No. 3,227,552, British Patent No. 1.283,835, JP-A-52-69613, U.S. Patent No. 3,615,615, No. 3
．． 719. 494, 3,734,738, 4.
Heterocyclic quaternary salt compounds described in U.S. Pat. No. 094.683, U.S. Pat. , U.S. Patent No. 4,030,925, U.S. Patent No. 4,031
, 127, 4,245,037, 4,255,51
1, thiourea-bonded acylhydrazine compounds described in British Patent No. 4,266.013, No. 4,276.364, British Patent No. 2,012,443, etc., and U.S. Patent No. 4,080
, 270, 4,278,748, British Patent 2,011
For example, acylhydrazine compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorption group, as described in , 391B, etc., can be 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, Research Disclosure (RD) 17029, U.S. Patent No. 1846.300. Same 2
,078,233, 2゜089.129, 2,16
5,338, 2゜231.658, 2,917.5
16, 3°352.857, 3,411,916,
2゜295.276, 2,481,698, 2゜688.545, 2,921,067, 3゜282
．． 933, 3,397,060, 3゜660.10
3, 3,335,010, 3,352.680, 3,384,486, 3,623.881, 3,7
18,470, 4°025.349, etc.

(3) Structure of the photosensitive layer In order to reproduce natural colors by the subtractive color method, the above-mentioned 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 in combination with a photosensitive layer is used. The emulsion and the dye image-forming substance may be coated as separate layers, or
Alternatively, they may be mixed and applied as a single layer. If the dye image-forming material, when coated, has absorption in the spectral sensitivity range of the emulsion with which it is combined, a separate layer is preferred.

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 material layer. For example, JP-A-60-17354
A layer containing the nucleating development accelerator described in 1, Japanese Patent Publication No. 1983-
It is also possible to increase the color image density by providing a barrier layer as described in JP-A No. 15267, and to increase the sensitivity of the photosensitive element by providing a reflective layer as described in JP-A No. 60-91354.

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

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

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 diffusion of the oxidized developer. Specifically, non-diffusible hydroquinone, sulfonamide phenol,
Examples include sulfonamide naphthol, and more specifically, JP 50-21249, JP 50-23813, JP 49-106329, JP 49-129535, US Pat. No. 2,336,327, US Pat. No. 2,360,290 , same 2
,403,721, 2,544,640, 2,73
2,300, 2,782,659, 2,937,0
86. 3,637,393, 3,700,453,
It is described in British Patent No. 557,750, Japanese Patent Application Publication No. 57-24941, Japanese Patent Application Publication No. 5B-21249, etc. Moreover, regarding those dispersion methods, JP-A No. 60-238831, JP-A No. 60-Sho.
-18978.

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

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

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 layer with a neutralization function installed on the cover sheet is a layer containing an acidic substance in an amount sufficient to neutralize the alkali brought in from the processing composition, and if necessary, a neutralization rate adjusting layer (
The material may have a multilayer structure consisting of a timing layer), an adhesion reinforcing layer, etc. Preferred acidic substances are substances containing acidic groups with a pKa of 9 or less (or precursor groups that provide such acidic groups through hydrolysis). , more preferably higher fatty acids such as oleic acid as described in U.S. Pat. No. 2,983,606, U.S. Pat. No. 3,362,81
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in No. 9: Acrylic acid and acrylic acid as disclosed in Buddhist Patent No. 2.290,699 Ester copolymers; U.S. Patent No. 4,139,383 and Research Disclosure
)m 16102 (1977).

In addition, U.S. Patent No. 4,088,493, Japanese Patent Application Laid-open No. 1987-
No. 153,739, No. 53-1,023, No. 53-4
．． No. 540, No. 53-4, 541, No. 53-4, 54
Acidic substances disclosed in No. 2 and the like can also be mentioned.

Specific examples of acidic polymers include ethylene, vinyl acetate,
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,
These include acetate and hydrogen phthalate.

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

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

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 0.9-2.0. If the amount of polymer acid is too small, the hue of the transferred dye may change, staining may occur on the white background, or there may be too many layers. In some cases, inconveniences such as a change in hue or a decrease in light resistance may occur. A more preferred equivalent ratio is 1.0-1.3. If the amount of hydrophilic polymer mixed is too large or too small, the quality of the photograph will deteriorate. The weight ratio of lE aqueous polymer to polymeric acid is 0.1-10, preferably 0.3-3.0.

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. In addition, antioxidants, development inhibitors, precursors thereof, and the like may be added as necessary.

The timing layer used in combination with the neutralization layer may be a polymer that reduces alkali permeability, such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, etc.; Latex polymers that are made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomers and that increase the activation energy for alkali permeation; polymers that have lactone rings are useful.

Among them, Japanese Patent Application Publication No. 54-136328, U.S. Patent No. 4,
No. 267.262, 4. 009. No. 030, 4
Timing layer using cellulose acetate disclosed in JP-A No. 54-128335, No. 56-69,629, No. 57-6.843, U.S. Pat. No. 4,056°394. No. 4,061.496, No. 4,199.362, No. 4,250.243,
A latex polymer made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid, disclosed in U.S. Pat. No. 4,256.827, U.S. Pat. Polymers having a lactone ring; Others
-97346, 57-6842, European Patent (EP) 31°957AI, 37,724A1,
Particularly useful are the polymers disclosed in 48° 412A1 and others.

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

U.S. Patent No. 3,421.893, U.S. Patent No. 3,455°686
No. 3,575,701, No. 3,778.265, No. 3,785,815, No. 3゜847.615,
4,088.493, 4.123.275, 4,148,653, 4,201,587, 4
．． No. 288.523, No. 4,297.431, OLS No. 1,622,936, No. 2,162
゜No. 277, Re5earch Disclosure
15. 162 Sho 151 (1976), JP-A-59-202463.

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

In addition, timing layers made of these materials are covered by, for example, U.S. Patent No. 4,009,029, West German Patent Application (OLS)
, 913,164, 3,014.672, JP 54-155837, JP 55-138745, etc., and the development inhibitors and/or precursors thereof, as well as U.S. Pat. It is also possible to incorporate the hydroquinone precursor disclosed in , No. 578, and other additives useful for photography or their precursors.

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 front side of the support or on the opposite side of the photosensitive layer to the processing solution. In combination with this, 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 and a development inhibitor to control development, and an antioxidant to prevent deterioration of the developer. A light shielding agent is always included in the composition containing the following.

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.

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

As a 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 titanium A combination of white and dye is 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 can be any that cross-oxidize the dye image-forming material. Such developers may be used alone or in combinations of two or more, and may be used in the form of precursors.These developers may be included in an appropriate layer of the light-sensitive element, or may be used in alkaline processing. Specific compounds that may be included in the liquid include amine phenols and pyrazolidinones, and among these, pyrazolidinones are particularly preferred.

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

Dan-Hikoto 1 In the present invention, the light-shielding layer in the photosensitive element and the light-shielding processing liquid developed on the photosensitive element during processing completely shield the photosensitive layer from external light during the development process. Allows processing under daylight.

Specifically, a layer containing a light shielding agent may be coated on the front surface of the support or between the emulsion layer and the support, or a layer containing a light shielding agent may be provided in the support. Although any material having a light shielding function can be used, carbon black is preferably used.

As the binder for applying the light shielding agent, any binder that can disperse carbon black may be used, and gelatin is preferable.

The film unit of the present invention can be used for mask materials, rail materials, etc. as described in Japanese Patent Publication Nos. 48-33697, 48-43317, 50-153628, 52-11027, and 5648629. , surplus liquid trapping material, etc. are used to form a monosheet.

In particular, in order to make it easier to peel off after treatment, research and
Disclo + (Research Disclo
It is effective to insert a slit as described in (1983). the shape of the slit,
The depth etc. are selected depending on the physical properties of the white support used.

The present invention will be explained in more detail with reference to Examples below.

Example 1 A carbon black layer (as a light shielding layer) was sequentially applied to the back side of a polyethylene terephthalate support containing a titanium dioxide white pigment.
Carbon black 3.0g/g, gelatin 4.5g/r
rr) and titanium oxide layer (titanium oxide 3.0g/
rd, gelatin 1. og7M) was applied.

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.

fi+ 3g/rrl of the following polymer latex mordant
and an image-receiving layer containing 3g1rd of gelatin.

(cI-CHzh (cIl-CHzhl, 5 (cH-CHlht, 5 (cH-CHzh* Hydroquinone 0.008 g/rrr, carbon bra.

Tsuku 0.05g/rr+ and gelatin 0.8g/n (
A layer containing.

The following compounds 0゜ The first peel consisting of 1g/rd Delamination.

L (cHz-CO)r (cHz-CHX/7=85/
15COOHC00CJ* (3) Acetylation degree 51% cellulose acetate 0.7g/n
(A second release layer consisting of

(4) 1 g/d of ethyl acrylate latex
, a layer containing 2.5 g/nf of gelatin.

(5) The following cyan dye-releasing redox compound 0°44
g/rd, tricyclohexyl phosphate 0.09
g/rd, 2.5-di-t-pentadecyl (6), titanium oxide 2 g/rd, and gelatin 0°5 g/n.

(7) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.0 μm (silver amount: 0.15 g/n), red-sensitive sensitizing dye, gelatin 0.4 g/rd, the following structure: Nucleating agent (NA
) 1.1 μg/d, and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.02 g/n?
A low sensitivity red-sensitive emulsion layer containing.

NA (8) Octahedral internal latent image type direct positive silver bromide emulsion with grain size of 1.6 μm (silver amount O: 5 g/rd), red-sensitive sensitizing dye, gelatin 0. 8g/rrr, same nucleating agent (NA) as layer 0υ, 3.0μg/n (and 2-sulfo-5-n-pentadecylhydroquinone strium salt 0.04g/n?, high sensitivity red sensitivity) Emulsion N.

+912.5-di-t-pentadecylhydroquinone 1
．． 2g/rd, polymethyl methacrylate 1.2g/rd
n (and a color mixing prevention layer containing gelatin 0.1 g/rd.

OI Layer containing 0.3 g/rd of gelatin.

aυ The following magenta dye-releasing redox compound 0.1
5g/n (,) lycyclohexyl phosphate 0.1g
/n(, 2,5-di-t-pentadecylhydroquinone 0.009 g/rI? and gelatin 0.9 g/rd layer.

(b) Titanium oxide Ig/rrr and gelatin 0. 2
5g/n? Contains a light reflective layer.

α turbidity Particle size 1. O/Jm octahedral internal latent image type direct positive silver bromide emulsion (silver content 0.12 g/rrr), red-sensitive sensitizing dye, gelatin 0.25 g/r/, same nucleating agent as layer aυ (NA) 1.1 μg/rd and 2 sulfo-5
-n-pentadecylhydroquinone sodium salt 0.
A low-speed green-sensitive emulsion layer containing 0.02g/rrr.

0 荀 Octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.6 μm (silver content 0.35 g/rrr), red-sensitive sensitizing dye, gelatin 0.7 g/rrr, layer (IL+ and High-sensitivity green-sensitive emulsion layer containing the same nucleating agent (NA) 1.7 μg/rtr and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.04 g/rrr.

α92,5-di-t-pentadecylhydroquinone 0.
8g/rIr, polymethyl methacrylate 0, 8
g/n (and gelatin 0.45 g/n).

QQ Gelatin 0.3g/rd4: Contains i.

α force A yellow dye-releasing Donks compound with the following structure (
0.53g/rrr), tricyclohexyl phosphate
) (0.13 g/rrr), 2.5-di-t-pentadecylhydroquinone 0.014 g/r+? ) and gelatin (0,7 g/rr+).

C (cHiha barrel) Light reflective layer containing 0.7 g/nf of titanium oxide and 0.18 g/nf of gelatin.

Alpha octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.1 μm (silver content 0.25 g/rrr), blue-sensitive sensitizing dye, gelatin 0.4 g/+yr, same as layer αυ Nucleating agent (NA) 2μglrd, and 2-sulfo-5-
n-pentadecylhydroquinone sodium salt 0.0
45g/n? A low-speed blue-sensitive emulsion layer containing

4. Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.7 μm (silver content: 0.42 g/rd), blue-sensitive sensitizing dye, gelatin 0. 45 g/rd, same nucleating agent (NA) as layer OD, 3.3 ttg/rtr, and 2 sulfo-
5-n-pentadecylhydroquinone sodium salt 0
．． High-speed blue-sensitive emulsion layer containing 0.025 g/rrf.

■ Add the following ultraviolet absorbers to 4 x 10-' mol/l and gelatin 0. UV absorbing layer containing 5g/rrf.

The coatings were applied in the following order to prepare a cover sheet.

fal Contains 10.4 g/M of acrylic acid-butyl acrylate (molar ratio 8:2) copolymer with an average molecular weight of 50,000 and 0.1 g/nf of 1.4-bis(2,3-epoxypropoxy)-butane. Neutralization layer.

(bl Neutralized timing layer containing 4 g/rd of the following copolymer.

(2) A protective layer containing a matting agent and 0.5 g/rrf of gelatin.

C00CHi on a gelatin-subbed polyethylene terephthalate support containing anti-piping dye on the left.
C00CtHaOHC00H (c) Adhesion reinforcing layer consisting of gelatin 1.0g/rd.

The above image-receiving photosensitive sheet and cover sheet are stacked face-to-face, and a bag filled with an alkaline processing solution containing a light-shielding agent having the composition shown below that can be ruptured under pressure is fixed together. A photographic film unit (2) of the present invention was prepared.

Treatment liquid 1-phenyl-4-hydroxymethyl-4-methyl-3 pyrazolidinone 16g benzotriazole 6g potassium sulfite
1g hydroxyethylcellulose 25g potassium hydroxide
73g benzyl alcohol 3.4
g Carbon blank 68 g Titanium white 136 g Total weight after adding water 31 1 kg Film unit B-E which is the same as film unit A except that the above-mentioned sulfinic acid exemplified compounds as shown in Table 1 were further added to the processing liquid. It was created. Also, film unit F
was the same as film unit A except that the amount of potassium sulfite was increased for comparison.

After each of the above film units was exposed to light from the cover sheet side using a gray wedge, development processing was performed by spreading the processing solution to a thickness of 70 μm using a pressing member at 25° C. and 70% RH. Table 1 shows the results of measuring the image density immediately after and 2 hours after each film unit was peeled off 2 minutes after the treatment solution was developed.

From Table 1, it can be seen that compared to the control unit A, the units B-E of the present invention are G? It can be seen that the sting at f4 degrees is low, and that the comparison unit F also has a slight effect of lowering the sting.

Claims (1)

[Claims] On a white support, at least (a) a dye image-receiving layer, (b)
a release layer; (c) a light-sensitive element having in sequence at least one silver halide emulsion layer in combination with a dye image-forming substance; an alkaline processing composition containing a light-blocking agent; and a transparent cover sheet having a neutralizing function; In a unit having a layer having a light-shielding function on the side opposite to the processing solution with respect to the silver halide emulsion layer, the processing composition contains a compound selected from aliphatic sulfinic acids or salts thereof, aromatic sulfinic acids or salts thereof. A color diffusion transfer photographic film unit characterized in that it contains at least one compound.