JPH02302756A - Color diffusion transfer photographic film unit - Google Patents

Abstract

PURPOSE:To obtain a strippable type color diffusion transfer photographic film capable of indicating a correct stripping time by imparting a neutralizing function to a photosensitive element and/or a cover sheet and incorporating a pH indicator coloring substantially not in a high pH side but clearly in a lower pH side. CONSTITUTION:The color diffusion transfer photographic film unit comprises the photosensitive element consisting of a dye image receiving layer, a strippable layer, at least one silver halide emulsion layer successively laminated on a substrate, an alkaline processing composition containing a light shielding agent, and the cover sheet on the transparent substrate alone or that on some layer formed on the substrate. The photosensitive element and/or the cover sheet has a neutralizing function and the pH indicator coloring substantially not in a higher pH side but clearly in a lower pH side, thus permitting the obtained color diffusion transfer photographic film unit to have a function of indicating the time of completion of an image, that is, the correct stripping time.

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 can be processed in a bright room, in which an integrated film unit is peeled off after processing and a dye image is observed without passing through a support.

[Conventional technology]

Conventional color diffusion transfer photographic film units are broadly classified into non-peelable types and peelable types.

Types that do not require peeling are described, for example, in Japanese Patent Publication No. 16356/1982 and Japanese Patent Publication No. 33697/1982. In these configuration examples, development can be performed and the dye can be transferred to the image-receiving layer and then stored as an integrated image, and the dye present in the image-receiving layer can be observed through the transparent support. It is something.

With the no-peel type, the processing solution is spread between the two supports, so there is no wet feeling due to moisture in the processing solution, and since it is integrated before and after exposure, there is no inconvenience in terms of handling. However, there are limits to image quality improvement due to the following reasons.

The reason why there is a limit to the image quality improvement of the peel-free type is that firstly, observation is performed through the support, surface reflection on the surface of the support, light absorption and scattering inside the support, and so-called so-called light transmission in which the support acts as a light transmitter. The light absorption and light scattering of the T:ot fine particles contained in order to prevent the piping effect causes an increase in the minimum density and a decrease in the maximum density of the image.

The second reason is that the white reflective layer that serves as the background for observing images is a layer to which dyes are transferred by enlarging this layer. Therefore, in order to increase the reflectance, it is necessary to increase the density of the reflective material or Increasing the layer thickness slows down the diffusion of the dye, making it impossible to obtain sufficient reflectance.
This increases the minimum density of the image.

The third reason is that the photosensitive layer and processing solution coexist with the dye image-receiving layer even after image formation, resulting in an increase in the minimum density of the image due to transfer and staining after image formation, and deterioration and sharpness due to changes in color balance. This causes deterioration in image quality due to deterioration.

There are two types of peelable types. One is, as shown in U.S. Pat. No. 3,362,819, in which the light-sensitive layer and the dye-image-receiving layer are coated on separate supports, and after imagewise exposure, the light-sensitive element and the dye-receiving element are separated. A dye image transferred to the dye image-receiving layer is obtained by superimposing the dye image-receiving layer, spreading a processing composition therebetween, and then peeling off the dye-receiving element.

In this case, the dye image formed on the dye image-receiving layer coated on the support can be directly observed, so there is no limit to image quality improvement as described above for the peel-free type.
Shows very good color reproduction. However, there is the operational inconvenience of overlapping the photosensitive element and the dye image-receiving element in the camera, and the alkaline processing solution becomes sticky after peeling.
There is an inconvenience in handling the processed film that it tends to stick to the surroundings.

Another type includes a +III dye-receiving layer on the support, as shown in U.S. Pat. No. 4,328,301.
A release layer and a photosensitive layer are coated, and the photosensitive layer is peeled off after processing to obtain a print.In this case, the dye image formed on the dye image receiving layer coated on the support is directly observed. It exhibits very good color reproduction.

A film unit belonging to the latter type, as shown in U.S. Pat. No. 4,606,992 (JP 62-95530), comprises the following layers; a transparent support; a reflective layer; a dye image-receiving layer; a release layer which allows said support, reflective layer and dye image-receiving layer to be separated from the rest of the element after processing; an opaque layer through which an alkaline solution is permeable; and at least one silver halide dye image-forming material. Film units containing successive emulsion layers are known. However, with these photosensitive materials that do not have a neutralizing function, stable color images cannot be obtained unless they are stabilized using a processing bath.

Additionally, as shown in Japanese Patent Application No. 63-120201, the following elements are provided on a white support: (a) a dye-receiving layer; (b) said support and dye-receiving layer are separable from the rest of the element after processing; (c) a light-sensitive element having 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 at least a neutralizing side on which the processing composition is developed. Film units made of transparent cover sheets having a functional layer are known.

Although this film unit is a peelable film, the processing liquid does not stick to it, there is no handling inconvenience associated with overlapping film sheets other than the peeling operation, and since the image is not observed through the support, This is a photo-developable film unit that can provide superior image quality compared to non-peel-required types that require observation through the lens.

The film unit shown in Japanese Patent Application No. 120200/1983 has a different layer structure from the above-mentioned film unit, but similarly provides excellent images.

(Problems to be Solved by the Invention) Generally, in these diffusion transfer photographic film units, the progress of development differs depending on the ambient temperature during processing. On the other hand, with the above-mentioned peel-off type, the progress of image formation is not known until peeling occurs, and the appropriate peeling time can be determined by looking at a clock, but since the appropriate time varies depending on the temperature, it is not possible to truly perform proper peeling. To keep track of time, it is necessary to always have a temperature monitor and a watch with you.

In order to eliminate such inconveniences, for the two-sheet type release type sensitive material as shown in the above-mentioned US Pat. No. 3,362,819, the " Although a "peel indicator" has been invented, the indicator is not incorporated into the film development system and does not provide proper summer time, especially when the ambient temperature changes.

In addition, it is difficult to incorporate the above-mentioned peel indicator into the peel-off type photosensitive material of the type disclosed in Japanese Patent Application No. 120201/1986 due to space constraints, and the present invention provides a peel-off type color diffusion transfer photographic film unit that can indicate the appropriate peeling time. was strongly desired.

(Object of the Invention) The object of the present invention is to provide a novel film unit that has both the high image quality obtained by a peel-off type color diffusion transfer unit and the excellent handling properties of a peel-free color diffusion transfer unit. It is in.

Another object is to provide a color diffusion transfer photographic film unit that has the ability to indicate when the image is complete and the proper time for peeling.

Another object is to provide a color diffusion transfer photographic film unit that has the ability to indicate when the image is complete and the proper time for peeling.

(Means for Solving the Problems) The object is to provide on a support at least one halogen compound in combination with (a) a dye image-receiving layer, (2) a release layer, and (c) a dye image-forming material. It consists of a light-sensitive element having sequential silveride emulsion layers, an alkali processing composition containing a light-shielding agent, and a cover sheet having a transparent support alone or some layer on the transparent support. This was achieved by a color diffusion transfer photographic film unit having a neutralizing function and containing in the processing composition a pH indicator that is substantially colorless on the high pH side and colored on the low pH side. .

The processing composition is a viscous liquid that is spread uniformly between the photosensitive element and the cover sheet after the photosensitive element is exposed (photographed). The color of the light shielding agent in the composition can be seen, but when the pH of the treatment composition decreases due to the neutralization function built into the system, the pH indicator develops color after a certain period of time. Adjust the color range (pka) of the pH indicator appropriately! If you use the j1 section, you can make it possible to develop color in the target peeling time. That is, the peeling time can be notified by color development.

By the way, in Japanese Patent Publication No. 56-13936, an integrated film unit that does not require peeling and contains dyes that change color depending on pH in the processing solution or in the top layer of the photosensitive layer unit is described, but these dyes are temporary. It is intended to provide a light-shielding function, and is pre-colored in an alkaline treatment solution.
Alternatively, it is colored simultaneously with the development of the processing liquid and becomes colorless after a while, and is completely different from the present invention in many respects, such as the dye incorporation position, purpose, function, and film form.

Any pH indicator used in the present invention may be used as long as it is substantially colorless in the alkaline treatment composition and develops color as the system neutralizes and the pH decreases.

That is, it is sufficient if it is substantially colorless on the high pH side and colored on the low pH side, and the pH at which coloring occurs is preferably pH 5 to 11.
More preferably, the pH is 7 to 1°, but it may vary depending on the components in the processing composition, the salt concentration, and the constituent components of the photosensitive layer and cover sheet.

Specific examples of pH indicators are shown below, but are not limited thereto.

N (1; tHsJ x Q6) Ct)Is
CtHsl ol N
CJsl ol O[D CJs
CJsl1 09 CtHs
CtHslI HscI″”□C5HhSOJa (20) CzHs
CJsl1 (21) CJs
C! Hs(22) C2H4
CtLI H, C6″″C+l1iSO3Na (23) CtHs
CJsl1 usc! /ゝC3H4SOJa N (cHs) z 5U3Na Additionally, the amount of the PH indicator added may be such that the reflected optical density is 1 or more when color is developed in a state where it is uniformly developed between the photosensitive element and the cover sheet. , preferably 2 or more. Further, two or more types of indicators may be mixed.Details of the processing composition will be described below.

The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is paired with a light-shielding layer provided on the back side of the support or on the opposite side of the photosensitive layer to the processing solution. It completely shields the layer from external light and at the same time develops the photosensitive layer using the components it contains. For this purpose, the composition contains an alkali, a thickening agent, a light shielding agent, a developer, a development accelerator and a development inhibitor to control development, an antioxidant to prevent deterioration of the developer, etc. A light shielding agent is always included in the composition.

Further, in the present invention, it is preferable to add a white pigment to make it easier to see the color of the pH indicator in the processing solution.

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.1 For example, polyvinyl alcohol, Hydroxyethylcellulose, alkali metal salts of carboxymethylcellulose are used, preferably hydroxyethylcellulose,
Sodium carboxymethylcellulose is used.

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

As the light-shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse into the dye image-receiving layer and cause staining.A typical example is carbon blank.

The amount of light blocking agent added is sufficient to shield the photosensitive element during processing even under strong external light, and is 30 g per 1 processing solution.
~200 g, preferably 40-120 g.

Any white pigment can be used as long as it does not have a photographic sensitizing effect. For example, inorganic titanium white pigments as well as hollow polymer beads (e.g. Rose
0P-84 (trade name) manufactured by J.D. and Hass Co., Ltd.) can also be used.

The content of white pigment is 50g to 400 per kg of processing liquid.
g, preferably 100 g to 300 g.

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 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 aminophenols and pyrazolidinones, and among these, pyrazolidinones are particularly preferred because they cause less staining.

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

In the present invention, the layer having a neutralizing function may be provided on either the photosensitive layer side or the cover sheet side, or may be provided on both sides. As a representative, we applied for a special request in 1988.
A system containing a neutralizing function on the cover sheet side, as disclosed in No. 120201, will be explained.

A-1) Support Any support may be used as the support for the photosensitive element, as long as it does not adversely affect the photographic properties of the film unit and as long as it has dimensional stability. For example, cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, poly(vinyl acecool) film, polystyrene film, polyethylene terephthalate film, polycarbonate film, paper, metal, and glass. Preferred are cellulose acetate film, polyethylene terephthalate film, polyethylene-coated paper, and the like.

Further, preferably it is a white support.

The white support here 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. , a polymer film whitened by the addition of a white pigment such as titanium oxide, barium sulfate, or zinc oxide with a particle size of 0°1 to 5 μm or by forming microvoids by stretching, such as polyethylene terephthalate film formed by sequential biaxial stretching in a conventional manner; Films or synthetic paper made of polystyrene or polypropylene, or paper laminated with titanium white-containing polyethylene, polyethylene phthalate, polypropylene, etc. on both sides are preferably used. The thickness of the support is 50 to 350 μm, preferably 70 to 210 μm.
μm, more preferably 80 to 150 μm. Also,
If necessary, a light-shielding layer can be provided in the support.

For example, a support formed by laminating polyethylene containing a light shielding agent such as carbon black on the back side of a white support is used.

As a carbon black raw material, for example, DonneiV
oet 'Carbon Black' Marc
El Dekker, Inc.

Any manufacturing method can be used, such as the channel method, thermal method, and furnace method as described in (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.

Furthermore, instead of incorporating a light-shielding agent into the support, a light-shielding layer may be coated on the side of the support opposite to the dye image-receiving layer.

Further, the light-shielding layer may be provided between the dye image-receiving layer and the photosensitive element, which will be described later.

A-2: 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
Polymer mordants capable of crosslinking with gelatin etc. as disclosed in U.S. Pat. No. 8.538 and British Patent No. 1,277.453;
No. 52, No. 2,798,063, I Japanese Unexamined Patent Publication No. 1983-
No. 115,228, No. 54-145゜529, No. 54
-126,027, 54-155.835, 5
Aqueous sol-type mordant disclosed in U.S. Pat. No. 6-17,352, etc.; Water-insoluble mordant disclosed in U.S. Pat. No. 3,898.088, etc.; U.S. Pat. No. 4,168,9
No. 76, US Pat. No. 4,201,840, etc., and reactive mordants capable of forming a covalent bond with the dyes; and US Pat. No. 3,709,690, US Pat.
3.642,482, 3.488.706, 3,557,066, 3,271,147
No. 3.271゜148, JP-A-53-3032
8, No. 52-155528, No. 53-125, No. 53-1024, No. 53-107,835, British Patent No. 2.064,802, etc. can.

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.

Any hydrophilic polymer may be used as long as it has good compatibility with the mordant, and gelatin used in the timing layer is preferred.

In the present invention, a release 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 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.

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. 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
Theory of The Photography
cProcess" 4th edition. All of these compounds can be represented by the following general formula (1).

(DYE)-Y (1) Here, (DYE)
E) 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. Depending on the function of Y, silver is roughly divided into negative compounds that become diffusible in the silver developed area and positive compounds that become diffusible in the undeveloped area.

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, 3°443; No. 943, 3,751
．． No. 406, No. 3.443,939, No. 3,443,
No. 940, No. 3,628,952, No. 3,980,4
No. 79, No. 4,183,753, No. 4,142,89
No. 1, No. 4,278,750, No. 4,139°379
No. 4,218,368, No. 3,421.964, No. 4,199,355, No. 4゜199.354,
4,135.929, 4,336,322, 4,139,389, 53-50736, 51-104343, 54-130122, 5
No. 3-110827, No. 56-12642, No. 56-
No. 16131, No. 57-4043, No. 57-650, No. 57-20735, No. 53-69033, No. 5
No. 4-130927, No. 56-164342, No. 57
-119345 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 CaHq(t-) 0 ■ For positive compounds, Angewante Hemi International Edition English (Ang
ew, Che+w, Int, Ed, Engl,
), 22°191 (1982).

A specific example is a compound (dye developer) that is initially diffusible under alkaline conditions but becomes non-diffusible by oxidation during development.U.S. Pat. No. 2,983,606 is an effective Y for this type of compound. The ones listed in No. 1 are representative.

Another type is one that releases a diffusible dye by self-ring closure under alkaline conditions, but substantially no longer releases 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,
Diffusible dye can be released into the image by reaction with the remaining electron donor oxidized into the image by silver development. Regarding atomic groups having such functions, for example, US Pat. No. 4,183.753, US Pat.
No. 891, No. 4゜278.750, No. 4,139,3
No. 79, No. 4.218,368, No. 4,356.24
No. 9, No. 4,358.525, JP-A-53-1108
No. 27, No. 54-130927, No. 56-16434
No. 2, Published Technical Report No. 87-6199, European Patent Publication No. 220
746A2 etc.

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

Hs When compounds of this type are used, they are preferably used in combination with diffusion-resistant electron donor compounds (known as ED compounds) or their precursors, 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 Hs s (In the formula, (DYE) represents a dye having the same meaning as mentioned above or its precursor.) Details of this can be found in U.S. Pat. No. 3,719,489 and 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. Patent Nos. 3,597,200 and 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, l
researchDisclosure 7630
(197B) and 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. No. 551.138, JP-A-54-994
No. 31, No. 52-8827, No. 53-47823,
No. 53-143323, No. 54-99431, No. 5
No. 6-71061, European Patent (Publication) No. 53037, European Patent No. 53040, Research Disclosure
re17630 (197B) and re16475 (
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.
．． 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 No. 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 US Pat. No. 3,718,470, aggravating dyes having a nucleating substituent in the dye molecule, US Pat. No. 4,
No. 030,925, No. 4,031゜127, No. 4,2
45.037, 4.255.511, 4.26
No. 6.013, No. 4゜216.364, British Patent No. 2
, 012,443, etc., and U.S. Patent No. 4.080,2.
No. 70, No. 4,278,748, British Patent No. 2゜01
An acylhydrazine compound having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorption group, as described in No. 1.391B, 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, Re5earch Discl.
osure 1.7029, U.S. Patent No. 1.846
．． No. 300, No. 2,078,233, No. 2゜089.
No. 129, No. 2,165,338, No. 2,231,6
No. 58, No. 2,917.516, No. 3,352,85
No. 7, No. 3,411,918, No. 2,295.276
No. 2. 481. No. 698, 2,688,54
No. 5, No. 2,921゜067, No. 3.282,933
No. 3,397.060, No. 3,660,103, No. 3335.010, No. 3,352,680,
It is described in No. 3,384,486, No. 3,623,881, No. 3,718,470, No. 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 two is used.The emulsion and the dye image-forming substance may be coated as separate layers, or may be mixed and coated as a single layer.) A separate layer is preferable when the dye image-forming material is coated and has absorption in the spectral intensity range of the combined emulsion.

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 layer 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, No. 3,700.453, British Patent No. 557,
No. 750, JP-A No. 57-24941, JP-A No. 58-212
It is described in No. 49 etc. Regarding those dispersion methods, JP-A No. 60-238831, Japanese Patent Publication No. 60-189
It is described in No. 78.

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 anti-irradiation layer, an isolation layer, a protective layer, etc. are applied as necessary.

By the way, the image-receiving photosensitive element used in the present invention is disclosed in Japanese Patent Application Laid-open No. 6
3-226649, 63-21808, etc., a layer structure having a neutralizing function may be added.

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

In particular, in order to facilitate peeling after treatment, Re5ea
rch DrscIosure Nα23026 (
It is effective to insert a slit as described in 1983). The shape, depth, etc. of the slit are selected depending on the physical properties of the white support used.

The size of the film unit is arbitrary, but in addition to the size of 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 7 of the present invention, it is necessary to form a mirror image of the subject on the film. For this purpose it is necessary to use mirrors.

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

B) Cover sheet Here, a cover sheet having a neutralizing function for lowering the pH of the alkaline treatment liquid will be explained.
200, the cover sheet may be placed closest to the support of the photosensitive element, and in this case, the cover sheet may be placed on the support alone or with a dye as described in Japanese Patent Application No. 63-23492 and Kenpoku No. 8198. It is coated with a capture layer and does not need to have a neutralizing function.
Both the photosensitive element and the cover sheet may have a neutralizing function as described in .

By the way, the neutralization function is generally obtained by sequentially applying and combining a neutralization layer and a neutralization timing layer, and the positional relationship is such that the alkali treatment composition reaches the neutralization layer via the neutralization timing layer. The cover sheet used in the present invention is preferably one such as those described in Japanese Patent Application No. 63-120201 and Japanese Patent Application Laid-Open No. 59-202463.

After processing, the cover sheet is peeled off together with the processing solution and the used irradiation 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 coloring layer or a dye trapping layer as described in Japanese Patent Application No. 63-23492 may be provided as the uppermost layer, that is, in contact with the processing composition.

It is also possible to adjust the sensitivity of the angry light layer by incorporating a filter dye into the cover sheet. The filter dye may be added directly into the support of the cover sheet or may be applied as a separate layer.

Each component of the cover sheet will be explained below.

B-1) Support The support for the cover sheet used in the present invention can 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.

B-2) Neutralizing Layer The neutralizing layer is a layer containing an acidic substance in an amount sufficient to neutralize the alkali brought in from the processing composition.

Favorable acidity! The substance containing an acidic group with a pKa of 9 or less (or a precursor group that provides such an acidic group through hydrolysis) is more preferably a substance containing oleic acid as described in U.S. Pat. No. 2,983,606. higher fatty acids such as polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in U.S. Pat. No. 3,362,819; Copolymers of acrylic acid and acrylic esters as disclosed;
U.S. Patent No. 4,139.383 and Research Disclosure
) Nα16102 (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,
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, polyvinylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl 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 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 hydrophilic polymer to polymeric acid is from 0.1 to 10, preferably from 0.3 to 3.0.

Additives can be incorporated into the neutralizing layer of the present invention for various purposes. For example, hardening agents known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. Other antioxidants, development inhibitors,
and its precursor can also be added.

B-3) Timing layer The timing layer used in combination with the neutralization layer may be an alkali-permeable material such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, etc. Useful polymers include polymers that lower the properties of the alkali; latex polymers that increase the activation energy for alkali permeation, which are made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomers; and polymers that have lactone rings.

Among them, Japanese Patent Application Publication No. 54-136328, U.S. Patent No. 4,
No. 267.262, No. 4,009,030, No. 4.0
Timing layer using cellulose acetate disclosed in JP-A-54-128335, JP-A No. 56-69,629, JP-A No. 57-6.843, U.S. Pat. No. 4,056°394 , No. 4,061,496, No. 4.199.362, No. 4,250.243, No. 4
A latex polymer made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid, which is disclosed in U.S. Pat. Polymers having a lactone ring; Others JP-A-56-25735
No. 97346, No. 57-6842, European patent (
Particularly useful are the polymers disclosed in EP) 31°957A1, EP 37.724A1, EP 48°412A1, and the like.

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, West German patent 1! I(OLS) No. 1,622,936, 2,1
No. 62,277, Re5earch Disclo
sure 15, 162Nl1151 (197
6), 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 include, for example, U.S. Patent No. 4,009,029 and West German Patent No. 11 (OLS).
2,913,164, 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. 201,578, other additives useful for photography, or their precursors.

(Example) Example 1 A carbon black layer (
Carbon blank 3.0g/rrf, gelatin 4.5g
/rrf) and titanium oxide layer (titanium oxide 3.0
g/po, containing 1.0 g/po of gelatin).

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) A dye-receiving layer containing the following polymer latex mordant at 3 g/rrf and gelatin at 3 g/rrf.

(2) A first release layer consisting of 0.1 g/nf of the following compound.

Hs (3) Cellulose acetate with 51% acetylation degree 0.15g/
A second release layer consisting of po.

(4) Ethyl acrylate latex Ig/rr? ,
A layer containing 2.5 g/pot of gelatin.

(6) The following cyan dye-releasing redox compound 0°44
g/n (,) lycyclohexyl phosphate 0.09g
/I, 2.5-Gmo-1 Pentadecyl Hydroquinone 0
．． 008 g/rrf, carbon black o, o5 g/i and gelatin 0.8 g/rrf.

(6) Titanium oxide 2g/rrf and gelatin 0.
A light reflecting layer containing 5 g/rrf.

(7) Particle size 1. 0 μm octahedral internal latent image type direct positive silver bromide emulsion (0.15 g/rrf in silver amount)
, red-sensitive sensitizing dye, gelatin 0.4 g/p, the following nucleating agent (NA) 1.1 μg/p, and 2-sulfo-5-n
-Pentadecylhydroquinone sodium salt 0.02
Low speed red sensitive emulsion layer containing 8/rrf.

(8) Octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.6 μm (0.5 g/nf in amount of II), red-sensitive sensitizing dye, gelatin 0.8 g/rrf, layer (7 ) Same nucleating agent (NA) 3.0 μg/I and 2-sulfo-
5-n-pentadecylhydroquinone sodium salt 0
．． A highly sensitive red-sensitive emulsion layer containing 04'g/rff.

(9) 2.5-G-Mo-1 Pentadecyl Hydroquinone 1
．． 2g/rrf, polymethyl methacrylate 1.2
g/n (and color mixing prevention layer containing gelatin 0.7 g/rd).

00) Layer containing 0.3g/r+f of gelatin.

00 The following magenta dye releasing redox compound 0.
15g/nf, tricyclohexyl phosphate 0.1
g/nf, 2.5-di-t-pentadecylhydroquinone o, oo9g/rr? and a layer containing 0.9 g/po of gelatin.

u (121 titanium oxide Ig/nf and gelatin 0.25
A light reflecting layer containing g/a.

Surface: Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.0 μm (silver amount: 0.12 g/bo), green-sensitive sensitizing dye, gelatin 0.258/ITf, layer (7) and Same nucleating agent (NA) 1.1 μg/rrf and 2-sulfo-5
-n-pentadecylhydroquinone sodium salt 0.
A low-speed green-sensitive emulsion layer containing 0.02 g/rd.

Round octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (ilO content: 0.35 g/po), green-sensitive sensitizing dye, gelatin 0.7 g/rrf, same as N(7) Nucleating agent (NA) 1.7 μg/po and 2-sulfo-5-n
-Pentadecylhydroquinone sodium salt 0.04
High-sensitivity green-sensitive emulsion layer containing g/rrf.

05) 2,5-di-t-pentadecylhydroquinone 0
．． 8g/rrf, polymethyl methacrylate 0°8g
/rrf and 0.45 g/po of gelatin.

00 Layer containing 0.3 g/nf of gelatin.

07) Yellow dye-releasing redox compound 'J with the following structure
h (0,53 g/nf), l-licyclohexyl phosphate (0,13 g/nf), 2,5-di[-pentadecylhydroquinone 0. 014 g/nf) and gelatin (O17 g/rd).

Side Titanium oxide 0.7g/rTf and gelatin 0°1
Light reflective layer containing 8g/po.

0g1 Particle size i, tI! m octahedral internal latent image type direct positive silver bromide emulsion (silver amount 0.25 g/n (
), blue-sensitive sensitizing dye, gelatin 0.4 g/rrf, layer (
Low-sensitivity blue-sensitive pores containing the same nucleating agent (NA) 2 μs/nf as in 7) and 0.045 g/nf of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.
agent layer.

(20) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.7 μm (0.42 g/nf at an amount of 11!
), blue-sensitive sensitizing dye, gelatin 0.45g 10f, layer (
The same nucleating agent (NA) 3.3 μg/bo as in 7), and 2-
High-speed blue-sensitive emulsion layer containing 0.025 g/I'rf of sulfo-5-n-pentadecylhydroquinone sodium salt.

(21) 4x10 each of the following ultraviolet absorbers
- UV absorbing layer containing 'mol/ryf and 0.5 g/rd gelatin.

(22) Protective layer containing a matting agent and 0.5 g/nf of gelatin.

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.

(a) 10.4 g/r of acrylic acid-butyl acrylate (mole ratio 8:2) copolymer with an average molecular weight of 150,000 and 0.1 g/r+f of l,4-bis(2,3-epoxypropoxy)-butane. layer containing.

佽) Neutralized timing layer containing 4g/rrr of a polymer having the following structure.

CH, CI.

+CIIt-C-+vTfcHt-C-hT+CHt-
CHsuboCOOCH3C00Czl140HCool(
c) Gelatin 1.0g/n? and a layer consisting of 1.0 g/polymer of the following structure.

A comparative treatment solution was prepared with the following composition.

In addition, 11.2 g of exemplified compound (]) was added to the above composition.
A treatment solution of the present invention was prepared.

The photosensitive sheet was exposed to light through a color test chart, overlapped with the cover sheet, and the comparative and inventive processing solutions were spread out uniformly between both sheets to a thickness of 70 μm (the development was done without adding any additives). This was done with the help of a pressure roller).

When a comparative processing solution was used, images were obtained on the dye image-receiving layer by peeling from the release layer while changing the exposure time as shown in Table 1.

On the other hand, when using the cover sheet of the present invention, 2°
At 30", it was observed from the transparent cover sheet side that the developed processing solution was colored blue over the entire surface, so at this point it also peeled off from the release layer and an image was obtained on the dye image-receiving layer.
From the maximum density (Dmax) and fog density (Dmin) of each image shown in Table 1, it can be seen that the image was completed in 2'30 l' when using the comparative processing solution, and that the processing solution of the present invention It can be seen that the images obtained are equivalent when using the processing solution and when using the comparative processing solution. This means that when the processing liquid of the present invention is used, the pH indicator in the processing liquid develops color at the time of image completion and can be used as a guide for peeling, and that the processing liquid of the present invention has photographic performance (
This indicates that there is no adverse effect on image formation.

Table 1 Furthermore, when the comparative processing liquid was used, an image was visible from the cover sheet side with the gray processing liquid in the background. The unit containing this cover sheet is discarded after being peeled off, but when a comparison treatment liquid is used, the image remains on the disposal unit, making it difficult to maintain confidentiality.

On the other hand, when the processing liquid of the present invention is used, the image is hidden by the indicator dye in the processing liquid at the time of peeling, and the confidentiality is excellent.

Claims (1)

[Claims] A light-sensitive element having, on a support, sequentially at least (a) a dye-receiving layer, (b) a release layer, and (c) at least one silver halide emulsion layer in combination with a dye-image-forming material, comprising a light-shielding agent. It consists of an alkali processing composition and a transparent support alone or a cover sheet having some layer on the transparent support, and the photosensitive element or/and the cover sheet have a neutralizing function, and the processing composition has a neutralizing function. A color diffusion transfer photographic film unit comprising a pH indicator that is substantially colorless on the high pH side and colored on the low pH side.