JPH02244138A - Color diffusion transfer photographic film unit - Google Patents

Abstract

PURPOSE:To lower min. density (Dmin) without lowering max. density (Dmax) or deteriorating photographic performance during storage by forming a layer contg. a precursor of a development inhibitor by coating between a white support layer and a dye image receiving layer. CONSTITUTION:A layer contg. a precursor of a development inhibitor is formed by coating between a white support layer and a dye image receiving layer. The precursor is a compd. which releases a compd. inhibiting the (development) of silver halide by the action of alkali. The precursor is previously dissolved in an org. solvent having a high b.p. and the resulting soln. is emulsified or dispersed in a water soluble polymer such as gelatin to prepare a coating liq. used, or the precursor is dissolved in a soln. of a polymer insoluble in water but soluble in an org. solvent and the resulting soln. is dispersed in a water soluble polymer such as gelatin. Dmin can be lowered without lowering Dmax.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to color diffusion transfer photographic film units. For more details, please refer to the peel-off type integrated film unit.
This invention relates to a color diffusion transfer photographic film unit in which both units are highly safe after peeling.

(Prior Art) Conventional color diffusion transfer photographic film units are broadly classified into peelable type and peelable type. In the peel-off type, the photosensitive layer and the dye image-receiving layer are coated on separate supports, and after image exposure, the photosensitive element and the dye image-receiving element are overlapped, a processing composition is spread between them, and then the dye image-receiving layer is formed. Stripping off the element yields a dye image transferred to the dye-receiving layer.

The feature of this form is that the dye image formed on the image-receiving layer coated on the support can be directly observed, so there is no deterioration in image quality as seen in the non-peelable type, which will be described later, and the color is excellent. It is to show reproduction. On the other hand, there is the operational inconvenience of overlapping the photosensitive element and the image receiving element in the camera;
There are inconveniences in handling the processed film, as the alkaline processing solution becomes sticky after being removed and tends to adhere to the surrounding area.

On the other hand, in the peel-free type, a dye image-receiving layer and a silver halide emulsion are coated between a transparent support and another support, but the image-receiving layer and silver halide emulsion layer are the same transparent layer. There are two types: one in which it is coated on a support, and the other 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 layer, and in the latter case, a white reflective layer is applied to the processing composition developed between the image-receiving layer and the silver halide emulsion layer. By containing the white pigment, the dye image transferred to the image-receiving layer can be observed using reflected light.

These peel-free types are characterized by being very easy to handle, unlike the above-mentioned peel-off type, without the stickiness of the processing liquid and the inconvenience of handling due to overlapping of film sheets. However, since the color image is observed through a transparent support, the image quality is lower than that of the peel-off type described above due to a decrease in color saturation due to surface reflection, a lack of whiteness in the white background due to insufficient reflectance of the white reflective layer, etc. decline is inevitable.

Another disadvantage is that the resulting print is too thick because the used emulsion layer, pot, cover sheet, etc. are not peeled off. In order to solve such problems, JP-A No. 63-226649 discloses at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, (c) a release layer, and (d) a layer having a neutralizing function on a white support. A color diffusion transfer photographic film unit is described, comprising a light-sensitive element having sequentially at least one silver halide emulsion layer in combination with a dye image-forming material, an alkaline processing composition containing a light-blocking agent, and a transparent cover sheet. has been done. In peel-off type color diffusion transfer photography, it is required to keep the pH of the system high until just before peeling in order to speed up the image completion time, but if the pH remains high even after peeling, the image sheet In some cases, the image storage stability may be deteriorated due to staining, and the rejected sheet containing the photosensitive layer, processing liquid layer, etc. may come in contact with hands or eyes and cause damage.

Furthermore, conventional neutralization systems use a neutralization process that gradually lowers the pH, and lowering the pH requires a corresponding amount of neutralization layer and time. However, there is a limit to how quickly this can be done, and it has not been possible to use an alkaline treatment solution with a high pH while ensuring safety. Conversely, traditional neutralization systems speed up neutralization;
If an attempt is made to lower the pH during peeling, development, dye separation reaction, and dye diffusion will not proceed sufficiently, resulting in a significant decrease in image density.

In order to solve these problems, in Japanese Patent Application No. 63-21808 filed by the applicant of the present invention, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, (
c) a release layer; (d) a light-sensitive element having sequentially 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 layer having a neutralizing function. A color diffusion transfer photographic film unit is described which is characterized in that it consists of a transparent cover sheet having one layer of both.

Japanese Patent Application No. 63-120201 describes the use of a cover sheet having an inverted S-shaped layer having the function of lowering the pH.

Regarding the peelable 1li1 layer and/or its adjacent layer for easy peeling, Japanese Patent Application No. 63-23493, No. 63-33763, No. 63-84665, No. 6
No. 3-84666, No. 63-155934, No. 63-
185201 etc.

The purpose of these peelable integral films, which include a cover sheet, a release layer and its adjacent layers, is that the user does not have to worry about the amount of time required for peeling, as opposed to simple conventional peeling. In other words, in the conventional peel-off type, if the film is peeled off 5 minutes later than the manufacturer's recommended time, the resulting image density will be too high or the color balance will be significantly disrupted, so it is often not possible to obtain a desirable image. However, when a peelable integrated film is developed at a relatively high temperature such as 35°C, the minimum density value (hereinafter abbreviated as Dmin) of the image tends to increase, and furthermore, it takes a long time to fade after development. and Dmi
Dmin tends to be high for photosensitive elements where n tends to be high and the photosensitive element is located far from the place where the processing liquid is developed.

In order to prevent Dmin from becoming high, for example, US Patent No. 4,009,029, West German Patent Application (OLS) 2,
No. 913,164, No. 3,014゜672, Japanese Unexamined Patent Publication No. 1973
4-155,837, 55-138,745, etc., and the hydroquinone precursor disclosed in U.S. Pat. No. 4.201.5T8 can be incorporated into the cover sheet. Are known.

However, with this method, if you try to lower the Dmin of the photosensitive element located farthest from the cover sheet, the development of the photosensitive element located closest to the cover sheet will be excessively suppressed, and the maximum density value (hereinafter abbreviated as D wax) will also decrease. There is a drawback that it tends to be low. Furthermore, a method of directly adding a dispersed development inhibitor precursor to a photosensitive element whose Dsin is desired to be lowered is described, for example, in JP-A-63-168647. The development inhibitor precursor may partially decompose and release the development inhibitor which acts on the photosensitive element, making it impossible to obtain the desired photographic performance.

In particular, such undesirable results are likely to occur when the photosensitive material is exposed to a high temperature of 45° C. or higher and/or a high temperature of 80% RH or higher.

(Intelligence IJ to be solved by the invention) The main purpose of the present invention is to lower Dmin without lowering Dmax or deteriorating photographic performance during storage.

(Means for Solving the Problem) It has been found that this object can be achieved by coating a layer containing a precursor of a development inhibitor between the support and the dye image-receiving layer.

That is, the present invention provides a light-shielding light-sensitive element having, on a white support, sequentially at least (a) a dye image-receiving layer, (b) a release layer, and (c) at least one silver halide emulsion layer combined with a dye image-forming material. In a color diffusion transfer photographic film unit consisting of an alkali processing composition containing an alkali processing agent and a transparent cover sheet having at least a layer having a neutralizing function on the side on which the processing composition is applied, the white support layer and the dye image receiving layer are combined. This is a peel-off type integral film unit characterized in that a layer containing a precursor of a development inhibitor is coated between the two layers.

The development inhibitor precursor used in the present invention is a compound that releases a compound that inhibits the development of silver halide by the action of an alkali, and many known development inhibitor precursors can be used.

As the development inhibitor precursor, for example, Japanese Patent Publication No. 59-339
No. 01, JP-A-55-138745, JP-A No. 55-533
No. 30, No. 56-77842, No. 57-135949
Examples include compounds described in German Patent Application (OLS) No. 3.612.258A1, and the compounds shown below are preferred.

Representative useful compounds in the present invention include the following.

Compound 2 Compound 7 Compound 8 Compound 9 Compound 10 Compound 15 Compound 16 Compound 17 Hs Hs Compound 11 Compound 12 Compound 13 Compound 14 H H Compounds (1) to (8) can release 1 equivalent of the development inhibitor from 1 mole. , compounds (9) to 07) are 1 mol to 2 mol
equivalent amount can be released.

These development inhibitor precursors can be dissolved in a high boiling point organic solvent and emulsified and dispersed in a water-soluble polymer such as gelatin by a method well known in the photographic industry, or can be made into a water-insoluble and organic solvent as described in JP-A-63-168647. It is used by dissolving it in a solvent-soluble polymer and dispersing it in a water-soluble polymer such as gelatin.

The amount of the development inhibitor precursor to be used is preferably 0.05 to 0.2 milliequivalents/unit, more preferably 0.07 to 0.15 milliequivalents/unit in terms of released development inhibitor. The amount of water-soluble polymer binder applied such as gelatin is preferably 0.5 to 1.5 g/I.

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 be provided, and an undercoat liquid commonly used for photographic light-sensitive materials is used for the undercoat layer.

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 an appropriate adhesive layer to ensure sufficient adhesion with the treatment liquid. Examples of such an adhesive layer include the hydrophilic coating described in Japanese Patent Publication No. 61-49658. A photosensitive layer is particularly preferred, and the cover sheet may contain a filter dye to adjust the sensitivity of the photosensitive layer. The filter dye may be added directly into the support of the cover sheet or may be applied as a separate layer.

The cover sheet of the present invention has a neutralization system for lowering the pH of the alkaline processing solution, that is, it has a neutralization function by sequentially having a neutralization layer and a neutralization timing layer on the transparent cover sheet. A neutralizing system can be achieved by providing a layer with. This timing layer is
The alkaline treatment liquid is placed between the treatment liquid and the neutralization layer in a positional relationship such that it reaches the neutralization layer via the timing layer, and after maintaining a high pH for a certain period of time,
A process in which the pH rapidly decreases (a process called ``inverted S-shaped J'')
(H lowering process), preferably at pH 10 during peeling.
, 5 or less. The period of maintaining this high pH is controlled by the components, composition, coating amount, etc. of the neutralization timing layer.

Such polymers include ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylic acid,
methacrylic acid, itaconic acid) and one or more copolymerizable ethylenically unsaturated monomers, polymers such as those described in JP-A-59202463, and U.S. Patent No. 4,297. , No. 431, 4
, 288.523, 4,201,587, 4゜229.516, JP-A-55-121438, 5
No. 6-166212, No. 55-41490, No. 55-
No. 54341, No. 56-102852, No. 5'? -1
No. 41644, No. 57-173834, No. 57-17
No. 9841, West German Patent Application Publication (OLS) 2,910,
No. 271, European Patent Application Publication EP 31957A1.
Re5earch Disclosure811184
Examples include those described in No. 52 and the like. Examples of ethylenically unsaturated monomers include ethylene, propylene, 1-butene, isobutyne, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N
, N,N-trimethyl-N-vinylbenzylammonium chloride, N,N-dimethyl-N-benzyl-N-
Vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, 1
- vinyl-2-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate) , n-hexyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate,
N, N-diethylamine ethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N.

N-diethylaminoethyl methacrylate, NN, N-
Triethyl-N-methacryloyloxyethylammonium p-)luenesulfonate, N,N-diethyl-N
-methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconate, maleic acid monobenzyl ester), amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylamide, N,N-dimethylacrylamide, N
-Methylolacrylamide, N-(N.

N-dimethylaminopropyl)acrylamide, N,N
, N-)limethyl-N-(N-acryloylpropyl)
Ammonium-P-toluenesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, acryloylmorpholine, methacrylamide, N,N-dimethyl-N"-acryloylpropanediamine propionate betaine, N,N-dimethyl-N '-methacryloylpropanediamine acetate betaine).

Preferred specific examples of the polymer for the neutralization timing layer are given below, but are not limited to these (the copolymerization ratio is a molar ratio) HI Hs 1ls CH coH3 Preferably, the above (1) to (8) Particularly preferred are (1), (2), (3), and (8).

The neutralization timing layer may be a single layer or multiple 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, or other photographically useful additives or their precursors, in an amount that does not reduce the Dmax of the photosensitive element located close to the cover sheet.

As the acidic substance for the neutralization layer, conventionally known ones can be used, and there are no particular restrictions. Preferred acidic substances include pKa
9 or fewer acidic groups (or precursor groups that provide such acidic groups upon hydrolysis), more preferably higher oleic acids such as oleic acid as described in U.S. Pat. No. 2,983,606. Fatty acids, U.S. Patent No. 3,3
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in FR 2.290.699;
Copolymers of acrylic acid and acrylic esters as disclosed in U.S. Pat. No. 4,139,383 and R.
e5earch Disclosure Sou 16102
(1977), acidic polymers of the latex type may be mentioned.

Others: U.S. Patent No. 4゜08B, 493, JP-A-52
-153739, 53-1023, 53-45
Acidic substances disclosed in No. 40, 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 polymer acid is too small, the hue of the transferred dye may change or staining may occur on the white background, and if it is too large, In some cases, inconveniences such as a change in hue or a decrease in light resistance may occur. A more preferable equivalent ratio is 1. 0-1. It is 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 aqueous polymer to polymeric acid is between 0.1 and 10, preferably between 0.3 and 3.
It is 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.
It is also possible to add dyes and the like.

In the present invention, by adopting a neutralization process in which the pH decreases in an inverted S-shape,! Since the pH of the system can be kept high until just before IJ separation, the time required to complete the image can be shortened. In addition, since the pH is sufficiently low at the time of peeling, it is possible to ensure safety when touching the film and to prevent staining of the image.

Furthermore, since the pH at the time of peeling can be lowered by using a high pH developer, it is possible to further speed up the image completion time.

Furthermore, by rapidly lowering the pH, development, dye separation reaction, and dye diffusion can be reliably stopped, so even if it takes a long time to peel off, the image quality hardly changes.

Each component other than the cover sheet used in the present invention will be sequentially explained 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. For example, titanium oxide with a particle size of 0.1 to 5μ,
Polymer films whitened 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 two-wheel stretching, synthetic paper, or 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 to 350 μm, preferably 70 to 21 μm
0 μm1, more preferably 80 to 150 μm. Further, if necessary, a light-shielding layer may be provided in the support. For example, a support formed by laminating polyethylene containing a light-shielding layer such as carbon black on the back side of a white support is used. As a raw material for carbon black, for example,
ck” Marcel Dekker, Inc.
(1976), the channel method,
Any manufacturing method such as the Samual method or the furnace method can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 1,800 particles.

The amount of black pigment added as a light-shielding layer 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.
A value of about O 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 5,000 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.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Pat. No. 814 and others; vinylimidazolium cationic polymers disclosed in U.S. Pat.
No. 25,694, No. 3,859,096, No. 4,12
8°, No. 538, polymer mordants capable of crosslinking with gelatin etc. as disclosed in British Patent No. 1,277.453; US Pat.
No. 852, No. 2,798,063, Japanese Unexamined Patent Publication No. 1986-11
No. 5228, No. 54-145529, No. 54-126
No. 027, No. 54-155835, No. 56-1735
Aqueous sol-type mordant disclosed in U.S. Pat. No. 2, etc.; Water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088, etc.; U.S. Pat. No. 4,168,976, U.S. Pat. Reactive mordant dyeing capable of forming a covalent bond with the dye disclosed in the specification, etc.; and US Pat. No. 3,709
, No. 690, No. 3,788,855, No. 3,642,
No. 482, No. 3,488,796, No. 3,557,0
No. 66, No. 3,271゜No. 147, No. 3,271, 14
No. 8, JP-A-53-30328, JP-A No. 52-15552
No. 8, No. 53-125, No. 53-1024, No. 53
Examples include mordants disclosed in British Patent No. 107835 and British Patent No. 2,064.802.

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.

Presentation JυU In the present invention, a release layer is provided between the emulsion layer combined with the dye image-forming material and the dye image-receiving layer, and the emulsion layer is peeled off after processing. Therefore, this release layer must maintain close contact between the image-receiving layer and the emulsion layer in an untreated state, and must be easily peelable after processing. No. 56-65133,
No. 59-220727, No. 59-229555, Special Publication No. 49-4334, No. 49-4653, No. 45-
No. 24075, U.S. Patent No. 3,220,835, U.S. Patent No. 435
Those described in No. 9518, No. 3227550, No. 2759825, No. 4401746, No. 4366227, etc. can be used. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives such as hydroxyethylcellulose, cellulose acetate-phthalate, plasticized methylcellulose, ethylcellulose, cellulose nitrate, and carboxymethylcellulose. 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 examples include water-soluble synthetic polymers.

For example, 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.
-60642 etc.

E) Photosensitive Element In the present invention, a photosensitive element comprising a silver halide emulsion layer combined with a dye image-forming material is provided 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 property. The theory of photographic process The T
theory of the photography
Process" 4th edition. All of these compounds can be represented by the following formula (1).

(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 previous compound under alkaline conditions.The function of Y allows for a negative-tone compound that becomes diffusive in the silver development area and an unformed compound. It is broadly classified into positive-type compounds that become diffusible in the developing section.

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 U.S. Patent Nos. 3,928,312 and 3,
No. 993.638, No. 4,076.529, No. 4,1
No. 52,153, No. 4,055,428, No. 4,05
No. 3,312, No. 4,198゜235, No. 4.179
, No. 291, No. 4,149.892, No. 3,844,
No. 785, No. 3゜443.943, No. 3,751,4
No. 06, No. 3.443,939, No. 3,443,94
No. 0, No. 3,628.952, No. 3,980,479
No. 4,183.753, No. 4,142,891, No. 4,278,750, No. 4.139379, No. 4.218.368, No. 3,421.964, No. 4
, No. 199,355, No. 4゜199.354, No. 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 preferable group is N-substituted sulfamoyl 1& (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 C4H (wo-) 0 ■ For positive-type compounds, Angewante Hemi International Edition English (Ang
ev, Chew, In5t, Bd, Engl,
)+22.

191 (19B2).

A specific example is a compound (dye developer) that is initially diffusible under alkaline conditions but becomes non-diffusible after being oxidized by development.U.S. Pat. , 983°606 is representative.

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 US Pat. No. 3,980°479, US Pat. No. 3,421,
No. 964, No. 4゜199.355, JP-A-53-69
No. 033, 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,
A diffusible dye can be released into the image pattern by reaction with the remaining electron donor oxidized as in image 81 by silver development. Regarding atomic groups with such functions,
For example, U.S. Patent No. 4. No. 183.753, 4,14
No. 2.891, No. 4゜278.750, No. 4,139
, No. 379, No. 4.218.368, No. 4,356.
No. 249, No. 4,358,525, Japanese Unexamined Patent Publication No. 53-11
No. 0827, No. 54-130927, No. 56-164
No. 342, Technical Report No. 87-6199, European Patent Publication 2
20746A2 etc.

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

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. 4,263.3.
No. 93, No. 4,278.750, JP-A-56-138
It is described in No. 736, etc.

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

C,,H,.

(In the formula, (DYE) represents a dye having the same meaning as mentioned above or a precursor thereof.) Details of this can be found in U.S. Pat.
No. 98,783.

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

Examples of yellow dyes: U.S. Pat. No. 3,597.200, U.S. Pat. No. 3.309.19
No. 9, No. 4,013,633, No. 4゜245.028
No. 4,156.609, No. 4.139,383, No. 4,195.992, No. 4.148,641,
4,148.643, 4,336,322, JP-A-51-114930, JP-A-56-71072, R
e5earchDisclosure 7630 (
197B), No. 16475 (1977).

Examples of magenta dyes: U.S. Patent Nos. 3,453,107 and 3,544.54
No. 5, No. 3,932,380, No. 3゜931.144
No. 3,932.308, No. 3.954,476, No. 4,233,237, No. 4,255,509,
4,250,246, 4,142,891, 4,207,104, 4,287,292, JP 52-106727, 53-23628, 5
No. 5-36804, No. 56-73057, No. 56-7
No. 1060 and No. 55-134.

Examples of cyan dyes: U.S. Pat. No. 3.482.972, U.S. Pat. No. 3.929.76
No. 0, No. 4,013.635, No. 4゜268.625
No. 4,171,220, No. 4.242.435, No. 4,142,891, No. 4,195.994,
No. 4,147.544, No. 4,148,642, British Patent No. 1.551.138, Japanese Unexamined Patent Publication No. 54-9943
No. 1, No. 52-8827, No. 53-47823, No. 53-143323, No. 54-99431, No. 56
-71061, European Patent (Publication) No. 53037, European Patent (Publication) No. 5
No. 3040, Re5earch Disclosure
e17630 (197B) and e16475 (1
977).

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

Internal latent image type direct positive emulsions include, for example, so-called "converzidine type" emulsions that are made by taking advantage of the difference in solubility of silver halides, and those that are doped with metal ions, chemically sensitized, or both. "Core/shell type" in which at least the photosensitive site of a silver halide inner core particle coated with a silver halide outer shell
There are emulsions, etc., which are described in U.S. Patent No. 2.592.
．． No. 250, No. 3,206.313, No. 3, 761.
No. 276, No. 3,935.014, No. 3.447,9
No. 27, No. 2,497,875, No. 2,563.78
No. 5, No. 3,551.662, No. 4,395,478
No. 4,431,730, West German patent tube 2,728,
No. 108, British Patent No. 1,027,146, 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, U.S. Patent No. 2,563.7
85, hydrazines described in 2,588,982, hydrazides and hydrazones described in U.S. Patent No. 3,227,552, British Patent No. 1.283,8
No. 35, JP-A No. 52-69613, U.S. Patent No. 3.6
No. 15,615, No. 3,719,494, No. 3,73
No. 4,738, No. 4,094,683, No. 4,115
．． Heterocyclic quaternary salt compounds described in U.S. Pat.
No. 030,925, No. 4.031127, No. 4.24
No. 5.037, No. 4,255.511, No. 4,266
．． No. 013, No. 4°276.364, British Patent Section 2,
Thiourea-bonded acylhydrazine compounds described in No. 012,443, etc., and U.S. Patent No. 4,080,27
No. 0, No. 4,278,748, British Patent Section 2゜011
．． For example, acylhydrazine compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorption group, which are described in No. 391B, 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, U.S. Pat. No. 1,846.
No. 300, No. 2,078,233, No. 2゜089.1
No. 29, No. 2,165,338, No. 2.231,65
No. 8, No. 2,917,516, No. 3,352,857
No. 3,411,916, No. 2,295,276, No. 2,481,698, No. 2,688,545,
2,921°067, 3,282,933, 3,397.060, 3,660,103, 3
゜335 010, 3,352,680, 3.
No. 384,486, No. 3,623,881, No. 3,7
No. 18,470, No. 4,025,349, 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. The emulsion and the dye image-forming substance may be coated as separate layers, or they 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 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, 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. 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, 2°36
No. 0.290, No. 2,403,721, No. 2.544
, No. 640, No. 2,732,300, No. 2,782.
No. 659, No. 2,937.086, No. 3,637,3
No. 93, same 3. 700. No. 453, British Patent Section 55
No. 7,750, JP-A-57-24941, JP-A No. 5B-2
It is described in No. 1249, etc. Regarding those dispersion methods, Japanese Patent Application Laid-Open No. 60-238831, Japanese Patent Publication No. 60-1
No. 8978.

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 eradication prevention layer, a separation layer, a protective layer, etc. are applied as necessary.

F) 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 applied to the light-shielding layer provided on the back side of the support or on the opposite side of the photosensitive layer from the processing solution. The photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light shielding agent, a developer, and a developer. A light-shielding agent is always included in a composition containing a development accelerator for binding, a development inhibitor, an antioxidant for preventing deterioration of the developer, and the like.

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 peeling off the used photosensitive layer together with the cover sheet9.For example, polyvinyl alcohol, Hydroxyethylcellulose, alkali metal salts of 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 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 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 included in appropriate layers of the photosensitive element or may be included in the alkaline processing solution. Specific compounds include aminophenols and pyrazolidinones, and among these, pyrazolidinones are particularly preferred because they cause less staining.

For example, l-phenyl-3-pyrazolidinone, IP-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone,
1-(3'-Methyl-phenyl)-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-
Examples thereof include 4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-P-toIJ7Lz-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and the like.

The film unit of the present invention is disclosed in Japanese Patent Publication No. 4 B-33697.
No., JP-A-48-43317, JP-A No. 50-153628
No. 52-11027 and No. 56-48629, it is processed into a monosheet using a mask material, a rail material, a surplus liquid trap material, etc.

In particular, in order to facilitate peeling after treatment, Re5ea
rch Disclosure Na23026 (1
It is effective to make a slit as described in 983). 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 instant films currently available on the market, more compact film sizes and larger film sizes can be used.

In order to take a 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.

Regarding this type of camera, U.S. Patent Nos. 3 and 4
It is known from No. 47,437.

Example 1 Samples (A), (B), and (c) were created with the same configuration except for the presence or absence of a layer containing a development inhibitor precursor between the white support and the image-receiving layer. did.

A carbon black layer (as a light shielding layer) is sequentially applied to the back side of a polyethylene terephthalate support containing a titanium pentoxide white pigment.
Carbon black 3.0g/rrf, gelatin 4.5g
/+d) and titanium oxide layer (titanium oxide 3.0g
/Po, containing 1.0g/Po of gelatin) was coated.

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) An image-receiving layer containing 3 g/rd of the following polymer latex mordant and 3 g/rd of gelatin.

(2) Sample (^): 694 g of polymethyl methacrylate and 66 g of the development inhibitor precursor of compound (1) were mixed with 1 1 of ethyl acetate.
．． 61 and disperse it in 2 kg of 10% gelatin aqueous solution fi with sodium dodecylbenzenesulfonate as a dispersion aid, and the compound (+) is released onto the white support, which is 0 in terms of development inhibitor. The coating was applied so that the gelatin was 1 meq/nf and the gelatin was Ig/p.

Sample (B): A solution was prepared by dissolving 8 g of the development inhibitor precursor of compound (9) and 56 g of tricyclohexyl phosphate in 1.61 g of methyl ethyl ketone, and this was added to 3.7 kg of a 10% aqueous gelatin solution with dodecylbenzenesulfone. The emulsion is dispersed using sodium chloride as a dispersion aid, and the compound (9) is released onto a white support with a development inhibitor conversion rate of 0. 1 milliequivalent of gelatin was coated at Ig/rrf.

Sample (c): A comparative example in which the first release layer shown below was directly coated on a white support.

(3) The first compound consisting of 0.1g/rrf of the following compound
Peeling layer.

11= (4) 0.7 g of cellulose acetate with 51% acetylation degree
A second release layer consisting of /rrr.

(5) Ig/rrf of ethyl acrylate latex,
A layer containing 2.5 g/pot of gelatin.

(6) The following cyan dye-releasing redox compound 0°44
g/rrr, tricyclohexyl phosphate 0.0
9g/nf, 2,5-di-t-pentadecylhydroquinone 0.008g/ITr, carbon black 0.05
A layer containing g/I and 0.8 g/Po of gelatin.

(7) Titanium oxide 2g/po, and Zera f-y0.
11 reflective layers containing 5 g/rd.

(8) Internal latent image type direct bed di-silver emulsion with grain size
/po), nose/l! ! Increase the sacrifice! Momo, gelatin...
4g/rd, below am&, 911'(1'J A
) 1, 1 u g frdl, and 2-sulfo-'5-n'' pentadecylhydroquinone natricam salt 0.02 g/po.

'NA Sensitive emulsion layer.

Oω 2.5-di-t-pentadecylhydroquinone 1
2g/rrr, polymethyl methacrylate 1.2g
/rd and gelatin 0.7g/rrf.

Tsukuda Gelatin 0. Layer containing Lg/ITr.

Q21 The following magenta dye-releasing redox compound'
O, 15g/rd,) Lithic hexyl phosphate 0
．． 1 g/nf, 2.5-di-t-pentadecylhydroquinone 0.009 g/nf and gelatin 0.9 g/nf.

^1 (9) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (silver amount: 0.5 g/n?), red-sensitive sensitizing dye, gelatin 0.8 g/rd, Same nucleating agent as layer θ, (NA) 3°Oug/rd and 2-sulfo-5-n
-Pentadecylhydroquinone sodium salt 0.04
Highly sensitive red titanium oxide containing g/nf 1
g/rrr and 0.25 g/po of gelatin.

(b) Particle size 1.0! m octahedral internal latent image type direct positive silver bromide emulsion (silver amount 0.12 g/n?), green-sensitive sensitizing dye, gelatin 0.25 g/n, same nucleating agent as layer Q ( NA)1. 1! g/i and 2-sulfo-5-:
n-pentadecylhydroquinone sodium salt 0.0
Low anger green sensitive emulsion layer containing 2g/rrf.

09 Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (0.35 g/n in an amount of 1!)
, green-sensitive sensitizing dye, gelatin 0.1g/rrf, nucleating agent (NA) 1.7, same as layer 0! A high-temperature green-sensitive emulsion layer containing g/a and 0.04 g/rrf of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

Gω 2.5-di-t-pentadecylhydroquinone 0
．． 8g/rrf, polymethyl methacrylate 0°8g
/rrt and gelatin 0.45g/rd.

(17) A layer containing 0.3 g/lrf of gelatin.

cm Yellow dye-releasing redox compound with the following structure (0.53 g/ryf), ) Lithic hexyl phosphate (0.13 g/ryf), 2.5-di-t-pentadecylhydroquinone 0. 014 g/rrf) and gelatin (0,7 g/nf).

09 M titanium 0.7g/nf and gelatin 0°1
Light reflective layer containing 8g/po.

(To) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.1 μm (silver amount: 0.25 g/bo), blue-sensitive sensitizing dye, gelatin O, 4 g/rrf, layer Q21. Same nucleating agent (NA) 2! g/po, and 2-sulfo-5-n-
Pentadecylhydroquinone sodium salt 0.045
Low speed blue sensitive emulsion layer containing g/rd.

(21) 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 sensitizing dye, gelatin 0. 45g/rr? , layer 0
A high-temperature blue-sensitive emulsion layer containing 3.3 μg/po of the same nucleating agent (NA) and 0.025 g/rrf of 2-sulfo-5-n-pentadecylnohydroquinone sodium salt.

(22) Add the following ultraviolet absorbers to 4X10-'
UV absorbing layer containing mol/nf and gelatin 0.5g/rrf.

(23) Matting agent and gelatin 0.5'g/rr
A protective layer containing f.

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

(al) Acrylic acid-butyl acrylate (molar ratio 8:2) copolymer with an average molecular weight of 50,000 was mixed with IO, 4 g/I and 1.4-bis(2,3-epoxypropoxy)-butane 0.1 g/rrf. Contains a neutralizing layer.

(b) A neutralization timing layer containing 4 g/rrf of the exemplary copolymer (1).

(c) Adhesion reinforcing layer consisting of gelatin 1.0g/rrr.

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 of the present invention was prepared.

The film was peeled off after 1 minute and 40 seconds of treatment, and after drying, the optical density was measured using a color densitometer. The results are shown in Table 1.

Each of the above film units was exposed to light through a gray wedge with a sheet side force of 1, and then developed at 35° C. by spreading a processing solution to a thickness of approximately 70 μm using a pressing member. Table 1 shows that by developing each film unit and coating a layer containing a development inhibitor precursor between the white support and the image-receiving layer, Dmin can be reduced without reducing Dmax.

Example 2 Samples (c), (D), and (E) shown below.

(F) was created.

Sample (c): All (same) as sample (c) of Example 1.

Sample (D): The emulsion of compound (9) was placed between the white base and the image-receiving layer at an amount of 0.07 milliequivalent/I in terms of the development inhibitor released from this, and gelatin was applied as Ig/I. Same as sample (B) of Example 1.

Sample (E): Sample (c) except that an emulsified dispersion of compound (9) was added to the white reflective layer (7) in an amount of 0.07 milliequivalent/po in terms of development inhibitor released from compound (9). Same as .

Sample (F): Sample (c) except that an emulsion dispersion of compound (9) was added to the red-sensitive emulsion layer (8) in an amount of 0407 milliequivalents/bo as a development inhibitor released from compound (9). Same as .

Each of the above film units was exposed to light from the cover sheet side through a gray wedge, and then developed and developed at 30°C. After developing each film unit and peeling it off after 60 minutes and drying, the optical density was measured using a color densitometer.
shown in the table.

From Table 2, sample CD) in which a development inhibitor precursor was coated between the support and the image-receiving layer had Dmax compared to comparative example (c).
However, sample (F) in which the development inhibitor precursor emulsified dispersion was added directly to the emulsion layer and sample (E) in which it was added to the layer adjacent to the emulsion layer lower Dmin. It can be seen that there is a negative effect that Dmax also decreases.

In addition, samples (c), (D), (E), and (F) were heated at 60°C.
After being stored in an ink evaporator for 3 days at 20% RH,
Samples (c), (D) stored at 25°Cl2O%RH,
Develop and develop at 25°C at the same time as (E) and (F).
The sample was peeled off after a few minutes and dried, and the cyan area was measured using a color densitometer. The results are shown in Table 3.

Table 3 Optical Density of Cyan Area From Table 3, when a development inhibitor precursor is added to the emulsion layer or a layer adjacent to the emulsion layer, the Dma when stored at 60°C and 320% RH.
x is significantly reduced, but when a layer containing a development inhibitor precursor is coated between the support and the image-receiving layer, the temperature is 60°C, 920% RH.
It can be seen that the degree of Dmax decrease during storage is considerably small.

Procedural amendment

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 sequentially at least one silver halide emulsion layer in combination with a dye image-forming material;
In a color diffusion transfer photographic film unit comprising an alkaline processing composition containing a light-shielding agent and a transparent cover sheet having at least a layer having a neutralizing function on the side on which the processing composition is applied, the white support layer and the dye image-receiving layer are provided. A peelable type integrated color diffusion transfer photographic film unit, characterized in that a layer containing a precursor of a development inhibitor is coated between the film unit and the film unit.