JP2607958B2 - Color diffusion transfer photo film unit - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer photographic film unit, and more particularly, to a laminated integrated color diffusion transfer photographic film unit capable of bright room processing.

2. Description of the Related Art As a laminated integrated color diffusion transfer photographic film unit, an image receiving layer, a white reflective layer, a light shielding layer, and at least one layer of silver halide combined with at least one dye image-forming substance on a transparent support. A unit for developing a light-shielding alkali treatment composition between an image receiving photosensitive sheet having an emulsion layer and a transparent cover sheet is generally well known.

(Problems to be Solved by the Invention) Originally, in the color diffusion transfer method, development is performed according to exposure, and the dye is diffused from the dye image forming substance-containing layer according to the result of the development and fixed to the image receiving layer. This is a method that enables observation as a color image. Accordingly, the finally obtained color image pattern is compared with the color image pattern formed (diffused) in response to exposure in the dye image forming substance-containing layer,
Since blurring occurs before the light is diffused into the image receiving layer, the image quality, particularly sharpness, is significantly reduced. In addition to the development of the alkali treatment composition and the development, not only until the dye starts to diffuse from the dye image-forming substance-containing layer in accordance with the development, but also after the dye begins to diffuse, until the dye is completely fixed to the image receiving layer. Since it takes time, the completion time of an image is delayed as compared with a so-called peeling type color diffusion transfer film unit, and improvement has been desired.

The development of highly diffusible dyes has been promoted in order to compensate for these disadvantages. However, highly diffusible dyes generally have low immobilization ability in the image receiving layer, and conversely cause a decrease in sharpness. It was difficult to get out of the dilemma. In addition, we have developed mordants with excellent dye immobilization ability and improved the image receiving layer.However, mordants with excellent immobilization ability generally have a strong tendency to reduce the stability of color images to light, There were restrictions. Further, it has been recognized that the image quality of the laminated integrated photographic unit is deteriorated because the color image is observed through the transparent support, and the deterioration of the image quality is particularly large in the case of a transparent support in which light piping is prevented.

Further, in recent years, if the grain size of the silver halide emulsion is increased to improve the photographic sensitivity, or if measures are taken to increase the sensitivity by means of a light reflecting layer, the image completion time tends to be further delayed. With the advent of electronic still photography and the rapid processing of conventional type photography, competition, including in different fields, has become intense. In the color diffusion transfer photographic film unit, the breakthrough image quality (especially sharpness) has been improved, and the image completion time has been improved. Shortening has been desired.

(Object of the Invention) An object of the present invention is to provide a laminated integrated color diffusion transfer photographic film unit having high image quality and a reduced image quality completion time.

It is another object of the present invention to provide a novel laminated integrated color diffusion transfer photographic film unit that can be processed in a bright room with high sensitivity.

Means for Solving the Problems The inventors of the present invention have provided on a transparent support an image-receiving layer, a white reflective layer, a light-shielding layer, and at least one dye combined with at least one dye image-forming substance.
A photosensitive sheet having a silver halide emulsion layer, a transparent cover sheet having at least a neutralization layer and a neutralization timing layer on a transparent support, and a developing sheet between the photosensitive sheet and the transparent cover sheet. In a color diffusion transfer photographic film unit containing a light-shielding alkali treatment composition,
In order to achieve the above object, the above object has been solved by a color diffusion transfer photographic film unit having a dye capture layer as an outermost layer of the cover sheet in contact with the alkali treatment composition.

Diffusion of the dye upon development begins to occur isotropically at first. That is, it diffuses in the direction of the image receiving layer and also in the direction of the alkali treatment composition layer which is directly opposite. The dye that has diffused in the direction of the alkali treatment composition layer, as the dye diffused toward the image receiving layer is fixed by the mordant, will diffuse toward the image receiving layer due to the difference in concentration. For such a dye, the diffusion path becomes remarkably long, resulting in a delay in image completion time and a decrease in sharpness. By disposing a dye capturing layer on the outermost layer of the cover sheet, the dye diffused to the alkali treatment composition layer side is captured, and the color image is formed again by returning to the image receiving layer, thereby delaying image completion time and reducing sharpness. Can be prevented. In addition, the provision of the dye-capturing layer accelerates the development of the image by capturing the development-inhibiting components (eg, bromine ions) generated during development, thereby accelerating the development itself. Probably.

The dye-capturing layer in the present invention is extremely poor when a color image in the image receiving layer is satisfied, that is, when a sufficient color density, a preferable cover balance, a sufficiently low minimum density, and a preferable gradation are obtained. It does not have any function as an image receiving layer. It is expected to accelerate development, shorten image completion time, improve sharpness, and reduce color balance change. It is a layer for realizing the outside effect.

The dye-capturing layer contains a polymer mordant in a hydrophilic colloid in the same manner as the dye image-receiving layer described later. As the polymer mordant, a mordant that can be used in the dye-image receiving layer can be used. The polymer mordant used in the dye-capturing layer may be the same as or different from the mordant used in the dye-receiving layer, and the quality of a color image on the image-receiving layer can be changed by adjusting the amount of dye captured by the mordant power. it can.

As the hydrophilic colloid, those known to those skilled in the art, such as gelatin, polyvinyl alcohol, and denatured products thereof, polyvinylpyrrolidone, and polyacrylamide are used, and gelatin is particularly preferable.

The coating amount of the dye trapping layer can be freely set by a system generally mordant 0.1g / m ² ~10g / m ² preferably ^{0.2g / m 2 ~3g / m 2} , the hydrophilic colloid 0.1g / m ² ~10g / m
² is preferably ^{0.2g / m 2 ~3g / m 2} .

The polymer mordant used in the present invention is a polymer having a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, and a polymer having a molecular weight of 5,000 or more, particularly preferably 10,000. That's all.

For example, U.S. Pat.Nos. 2,548,564, 2,484,430, 3,
Nos. 148,061 and 3,756,814, vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in U.S. Pat. U.S. Pat. No. 3,958,995; U.S. Pat. No. 3,958,995;
No. 2,721,852, No. 2,798,063, JP-A-54-115,228
Nos. 54-145,529, 54-126,027, 54-155,83
5, sol-type mordants disclosed in JP-A-5-17,352 and the like; water-insoluble mordants disclosed in U.S. Patent 3,898,088 and the like; U.S. Patent Nos. 4,168,976 and 4,20
Reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification of U.S. Patent No. 3,709,690;
88,855, 3,642,482, 3,488,706, 3,557,06
No. 6, No. 3,271,147, No. 3,271,148, JP-A-53-30328
Nos. 52-155528, 53-125, 53-1024, 5
Examples thereof include mordants disclosed in 3-107,835 and British Patent 2,064,802.

Other examples include mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156.

Among these mordants, those that are difficult to migrate to other layers are preferable, and for example, mordants that cross-react with a matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants are preferable. Particularly preferred is a latex dispersion mordant, having a particle size of 0.01 to 2 μm.
Preferably, the thickness is 0.05 to 0.2 μm.

Regarding the dye-capturing layer, JP-A-50-142233 discloses a scavenger mordant layer which is located on one side of the alkali treatment composition and the emulsion layer, and the dye image receiving layer is located on the other side of the two layers. It is disclosed as a similar concept that the scavenger mordant layer is disposed in the timing layer or behind the timing layer with respect to the alkali treatment composition layer. JP-A-50-14
The scavenger mordant layer described in No. 2233 is basically in the timing layer to scavenge the undesired processing reaction product and excess dye after a predetermined time, preferably after 20 to 30 seconds, or in the alkali treatment composition layer. It is characterized in that it is located behind the timing layer, and the change in Dmax is reduced depending on the processing temperature, or the change in Dmax is reduced from the time of completion of the treatment to 4 weeks later. When a diffusible dye image-imparting substance is used from the beginning as described above, it is claimed that the effect of reducing excessive dye formation in the image receiving layer without delaying access time is claimed.

In the example of Japanese Patent Application Laid-Open No. 50-142233, it is necessary to take a timing of 20 to 30 seconds before the scavenger function is developed, and it is described that if there is no timing, the dye diffusion to the image receiving layer is hindered. I have. However, as in a preferred embodiment of the present invention, in the case of a photosensitive sheet in which a light reflecting layer is provided adjacent to the silver halide emulsion layer to improve the sensitivity, as a result, the dye image-forming substance containing substance closest to the image receiving layer is contained. Since the distance of the dye image forming substance-containing layer farthest from the image receiving layer as compared with the layer is longer, the comparison of the diffusion distance of the dye and therefore the time required for the transfer of the dye is shifted. In such a case, the change in color balance becomes very large until the color image is completed. For this reason, in such a case, even if the dye diffusion to the image receiving layer is hindered without timing-that is, even if the color image density in the image receiving layer is reduced as it is-the dye capture layer is provided. Has been found to be much more advantageous.

In the present invention, if the timing is set as shown in the embodiment, the desired effect cannot be obtained. The dye-capturing layer of the present invention is characterized in that it is in direct contact with an alkali treatment composition containing a light-shielding agent, whereby the development accelerates sharpness (Sharpness), shortens image completion time, and changes color balance. Reduction was realized.

On the other hand, a color diffusion transfer photographic film unit having two dye image-receiving layers or two dyeable layers is described in JP-B-57-58650 in addition to JP-A-50-142233.
No. 3,620,731. Tokiko Sho 57-586
No. 50 discloses a color diffusion transfer photographic film unit having a dyeable layer on each of two transparent supports.

However, as shown in that example, a preferred embodiment comprises a first dyeable layer and a photosensitive silver halide layer combined with a dye image-forming substance coated on a first support. A light-reflecting white layer and a light-shielding layer are provided between the layers, and a white pigment is added to the alkali developing composition so that any dyeable layer can be observed as a reflection print through a support.

The alkaline treatment composition in the present invention is a substantially black liquid containing carbon black, and although the pattern of the image looks thin, it is not completely a reflection print and is completely different.

Further, U.S. Pat. No. 3,620,731 discloses a dye image-forming substance which releases a dye by intramolecular ring closure.
Having two dye image receiving layers to obtain one color image,
A color diffusion transfer photographic film unit is disclosed. However, the above patent does not disclose a means for stabilizing an image after peeling, for example, a method of installing a neutralizing layer and a method of shading, and the dye image forming substance is different from the present invention.

 Hereinafter, other components will be sequentially described.

I. Sightseeing sheet A) Support The support of the sightseeing sheet used in the present invention may be any smooth and transparent support usually used for photographic tourism materials, such as cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. And
It is preferable to provide an undercoat layer. The support preferably contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping.

The thickness of the support is 50 to 350 μm, preferably 70 to 210 μm
m, more preferably 80-150 μm.

If necessary, a layer for curl balance or an oxygen barrier layer described in JP-A-56-78833 may be provided on the back side of the support.

B) Image receiving layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This is a single layer,
Further, it may have a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-252551. As the dyeing agent, a polymer mordant is preferable.

The polymer mordant is selected from the polymer mordants used in the above-described dye capturing layer.

The coated amount of the mordant, the type of mordant, the content of quaternary cationic groups, dye type and amount to be mordanted, preferably different but 0.5 to 10 g / m ^2, such as by a binder species used 1.0 to 5.
Particularly preferably 0 g / m ² is 2 to 4 g / m ^2.

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferable.

C) White reflective layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder.

As the white pigment for the white reflective layer, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium sodium sulfate, carion, mica, titanium dioxide and the like are used. These may be used alone or as a mixture in a range where a desired reflectance can be obtained.

 A particularly useful white pigment is titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of the pigment, the mixing ratio of the pigment and the binder, and the amount of the pigment applied, but the light reflectance is desirably 70% or more. In general, as the amount of the pigment applied increases, the whiteness improves.However, when the image forming dye diffuses through this layer, the pigment becomes resistant to the diffusion of the dye. Is desirable.

5 to 40 g / m ^{2 of} titanium dioxide, preferably 10 to 25 g / m ²
A white reflective layer which is applied and has a light reflectance of 78 to 85% for light having a wavelength of 540 mm is preferred.

Titanium dioxide can be selected from various commercially available brands.

Among them, it is particularly preferable to use rutile type titanium dioxide.

Many commercially available products are surface-treated with alumina, silica, zinc oxide, or the like, and a surface treatment amount of 5% or more is desirable to obtain high reflectance. Commercially available titanium dioxide, for example, DuPont Ti-pure
In addition to R931, there are those described in Research Disclosure No. 15162.

As the binder for the white reflective layer, an alkali-permeable polymer matrix, for example, gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethylcellulose and carboxymethylcellulose can be used.

A particularly desirable binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1 / 1-20 / 1 (weight ratio),
Desirably, it is 5/1 to 10/1 (weight ratio).

In the white reflective layer, JP-B-62-30620 and JP-B-62-30621
It is preferable to incorporate an anti-fading agent such as No.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer.

As the light-shielding agent, any material having a light-shielding function is used, and carbon black is preferably used.

As the binder for coating the light-blocking agent, any binder capable of dispersing carbon black may be used, and gelatin is preferred.

As a carbon black raw material, for example, Donnel Voet
Any method such as a channel method, a thermal method and a furnace method as described in "Carbon Black" Marcel Dekker, Inc. (1976) can be used. The particle size of the carbon black is not particularly limited, but is preferably 90 to 1800 °. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shaded,
An optical density of about 5 to 10 is desirable.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image-forming substance is provided above the light-shielding layer. The components will be described below.

(1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with silver development, or has a diffusivity of itself. Is changing, and the logic of the photo process “The Theo”
ry of the Photographic Process ", 4th edition. All of these compounds can be represented by the following general formula (I).

DYEY (I) Here, DYE represents a dye or a precursor, and Y
Represents a component which gives a compound having a different diffusibility from the compound under calcaric conditions. According to the function of Y, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion.

Specific examples of the negative type Y include those which oxidize as a result of development and are cleaved to release a diffusible dye.

Specific examples of Y are U.S. Patents 3,928,312, 3,993,638,
No. 4,076,529, No. 4,152,153, No. 4,055,428, No. 4,0
No.53,312, No.4,198,235, No.4,179,291, No.4,149,89
No. 2, 3,844,785, 3,443,943, 3,751,406,
3,443,939, 3,443,940, 3,628,952, 3,9
80,479, 4,183,753, 4,142,891, 4,278,75
No. 0, 4,139,379, 4,218,368, 3,421,964,
4,199,355, 4,199,354, 4,135,929, 4,3
No. 36,322, 4,139,389, JP-A-53-50736, 51-
No. 104343, No. 54-130122, No. 53-110827, No. 56-12
No. 642, No. 56-16131, No. 57-4043, No. 57-650,
Nos. 57-20735, 53-69033, 54-130927, 56
Nos. 164342 and 57-119345.

Among the Y's in the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). The representative groups of Y are illustrated below, but are not limited thereto.

For positive-type compounds, see Angevante Hemi International Edition English
v. Chem. Inst. Ed. Engl.), 22, 191 (1982).

Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions, but are oxidized by development to become non-diffusible. Representative examples of Y effective for this type of compound include those described in U.S. Pat. No. 2,983,606.

Another type is a type in which a diffusible dye is released by, for example, self-cyclization under alkaline conditions, but the dye is substantially not released when oxidized during development. For a specific example of Y having such a function,
U.S. Patent 3,980,479, JP-A-53-69033, JP-A-54-130927,
It is described in U.S. Patents 3,421,964 and 4,199,355.

Another type does not release the dye itself, but releases the dye when reduced. Compounds of this type can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. Regarding atomic groups having such a function, for example, U.S. Pat.
3,753, 4,142,891, 4,278,750, 4,139,379, 4,
218,368, JP-A-53-110827, U.S. Pat.
356,249, 4,358,525, JP-A-53-110827, 54-1309
27, 56-164342, Published Technical Report 87-6199, European Patent Publication 22
0746A2 and the like.

Specific examples will be described below, but the present invention is not limited thereto.

When this type of compound is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or a precursor thereof. ED
Examples of compounds include, for example, U.S. Pat.
78,750 and JP-A-56-138736.

Specific examples of other types of dye image-forming substances include the following.

(Where DYE represents a dye or a precursor thereof as defined above.) The details are described in U.S. Pat. Nos. 3,719,489 and 4,098,783.

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

Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, and 4,013,633
Nos. 4,245,028, 4,156,609, 4,139,383,
4,195,992, 4,148,641, 4,148,643, 4,3
No. 36,322: JP-A-51-114930, JP-A-56-71072: Resear
ch Disclosure 17630 (1978) and 16475 (1977).

Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380
Nos. 3,931,144, 3,932,308, 3,954,476
No. 4,233,237, 4,255,509, 4,250,246,
4,142,891, 4,207,104, 4,287,292: JP-A-52-106,727, JP-A-52-106727, JP-A-53-23,628,
No. 55-36,804, No. 56-73,057, No. 56-71060, No. 5
What is described in 5-134.

Examples of cyan dyes: U.S. Pat. Nos. 3,482,972, 3,929,760, 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. 4,1
48,642; British Patent 1,551,138; JP-A-54-99431;
No. 52-8827, No. 53-47823, No. 53-143323, No. 54
-99431, 56-71061; European Patent (EPC) 53,
No. 037, 53,040; Research Disclosure 17,630 (1978)
And those described in No. 16,475 (1977).

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

The internal latent image type direct positive emulsion includes, for example, a so-called "conversion type" emulsion which is prepared by utilizing the difference in solubility of silver halide, and a metal ion-doped or chemically sensitized or both. There is a "core / shell type" emulsion in which at least the light-sensitive sites of the applied silver halide inner core (core) grains are coated with an outer shell of silver halide, and the like, as described in U.S. Pat. twenty five
0, 3,206,313, UK Patent 1,027,146: U.S. Patent 3,761,27
6, 3,935,014, 3,447,927, 2,497,875, 2,56
3, 785, 3,551,662, 4,395,478, West German Patent 2,728,10
8, US Patent 4,431,730 and the like.

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

U.S. Patent Nos. 2,563,785 and
Hydrazines described in 2,588,982, U.S. Pat.
Hydrazides, hydrazones described in 52, U.S. Patent
1,283,835, JP-A-52-69613, U.S. Pat.
Heterocyclic quaternary salt compounds described in 3,719,494, 3,734,738, 4,094,683, 4,115,122, etc., U.S. Pat.
Described in, a sensitizing dye having a substituent having a nucleating effect in the dye molecule, U.S. Patent Nos. 4,030,925, 4,031,127, and 4,
245,037, 4,255,511, 4,266,013, 4,276,364, thiourea-bonded acylhydrazine-based compounds described in British Patent 2,012,443 and the like, and U.S. Pat.Nos. 4,080,270 and 4,27
For example, an acylhydrazide compound bonded as an adsorptive group of a thioamide ring or a heterocyclic group such as triazole or tetrazole described in U.S. Pat.

In the present invention, a spectral sensitizing dye is used in combination with the negative emulsion and the internal latent image type direct positive emulsion. Specific examples thereof are described in JP-A-59-180550 and JP-A-60-140335, Research Disclosure (RD) 17029, U.S. Pat.
6, 300, 2,078,233, 2,089,129, 2,165,338, 2,
231,658, 2,917,516, 3,352,857, 3,411,916,
2,295,276, 2,481,698, 2,688,545, 2,921,067,
3,282,933, 3,397,060, 3,660,103, 3,335,01
0, 3,352,680, 3,384,486, 3,623,881, 3,718,
470, and 4,025,349.

(3) Composition of photosensitive layer To reproduce a natural color by the subtractive color method, the dye image-forming substance which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye. And a photosensitive layer composed of at least two of the following combinations. The emulsion and the dye image forming substance may be coated as separate layers, or may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred.
The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming substance layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, a partition layer described in JP-A-60-15267 is provided to increase the color image density, or a reflective element is provided with a reflective layer. Can also increase the sensitivity.

The reflective layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The application amount of titanium oxide
^{0.1g / m 2 ~8g / m 2} , and preferably from ^{0.2g / m 2 ~4g / m 2} . This is a preferred embodiment of the present invention. An example of a reflective layer is disclosed in
No. 60-91354.

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

Arbitrary layers can be provided between the emulsion layer units as needed. In particular, it is preferable to provide an intermediate layer in order to prevent an unfavorable effect of the development effect of one emulsion layer on other emulsion layer units.

When a developing agent is used in combination with the non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent in order to prevent diffusion of the oxidized nuclear development product. Specifically, non-diffusible hydroquinone, sulfonamide phenol,
Sulfonamido naphthol; and more specifically, Japanese Patent Publication Nos. 50-21249 and 50-23813, and JP-A-49-10632.
9, ibid. 49-129535, U.S. Patents 2,336,327, 2,360,290,
2,403,271, 2,544,640, 2,732,300, 2,782,65
9, 2,937,086, 3,637,393, 3,700,453, UK patent 5
57,750, JP-A-57-24941 and JP-A-58-21249. The dispersion method is described in JP-A-60-23883.
1, described in JP-B-60-18978.

When a compound capable of releasing a diffusible dye by silver ions as described in JP-B-55-7576 is used, it is preferable to include a compound that captures silver ions in the intermediate layer.

It is also effective to provide a release layer as described in JP-B-63-3300 and remove the used emulsion layer and cover sheet after processing.

The present invention may be applied to an anti-irradiation layer,
An absorbent layer, a protective layer and the like are provided.

II. Cover Sheet In the present invention, a layer having a neutralizing function (neutralizing layer and middle layer) is used to uniformly spread the processing solution on the photosensitive element and neutralize the alkali after processing to stabilize the image. The cover sheet has a dye capture layer of the present invention as the outermost layer of the cover sheet on the side where the processing liquid is developed.

F) Support The support for the cover sheet used in the present invention may be any smooth transparent support usually used for photographic light-sensitive materials, and cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate and the like may be used. Is preferably provided.

The support preferably contains a trace amount of a dye to prevent light piping.

G) Layer having a neutralizing function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried in from the treatment composition. It may have a multilayer structure composed of layers such as a neutralization rate adjusting layer (timing layer) and an adhesion reinforcing layer. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that gives such an acidic group by hydrolysis), and more preferably a higher acidic substance such as oleic acid described in US Pat. No. 2,983,606. Fatty acids, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 3,362,819; acrylic acid and acrylic as disclosed in French Patent 2,290,699 Acid ester copolymers; U.S. Pat. No. 4,139,383 and Research Disclosure No.
Examples include latex-type acidic polymers as disclosed in 16102 (1977).

Others, U.S. Pat.No. 4,088,493, JP-A-52-153,739
No. 53-1,023, No. 53-4,540, No. 53-4,541,
The acidic substances disclosed in JP-A-53-4,542 and the like can also be mentioned.

Specific examples of the acidic polymer include a copolymer of ethylene, vinyl acetate, a vinyl monomer such as vinyl methyl ether, and maleic anhydride and its n-butyl ester,
Copolymers of butyl acrylate and acrylic acid, cellulose, acetate hydrogendiphthalate, and the like.

The polymer acid can be used as a mixture with a hydrophilic polymer. Examples of such a polymer include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred.

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

The amount of the polymer acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymer acid to the alkali per unit area is preferably from 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye changes, or a stain occurs on a white background, and the hue changes even when the amount is too large.
Otherwise, inconveniences such as a decrease in light resistance occur. A more preferred equivalent ratio is 1.0-1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The weight ratio of the hydrophilic polymer to the polymer acid is 0.
It is 1-10, preferably 0.3-3.0.

Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardeners well known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. In addition, if necessary, an antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof can be added.

The timing layer used in combination with the neutralizing layer may be a polymer that reduces alkali permeability such as, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, etc .; acrylic Latex polymers made by copolymerizing a small amount of a hydrophilic comonomer such as an acid monomer to increase the activation energy of alkali permeation; polymers having a lactone ring are useful.

Among them, JP-A-54-136328, U.S. Pat.
No. 4,009,030, 4,029,849, etc .; timing layer using cellulose acetate;
Nos. 8335, 56-69,629, 57-6,843, U.S. Pat.
Nos. 56,394, 4,061,496, 4,199,362, 4,250,24
3, 4,256,827, 4,268,604, etc., a latex polymer produced by copolymerizing a small amount of a hydrophilic comonomer such as allylic acid; US Pat. No. 4,229,51
6, a polymer having a lactone ring disclosed in JP-A-56-25735, JP-A-56-97345, JP-A-57-6842, and European Patents (EP) 31,957A1, 37,724A1, 48. Four
The polymers disclosed in, for example, No. 12A1, are particularly useful.

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

U.S. Patent Nos. 3,421,893, 3,455,686, 3,575,701
Nos. 3,778,265, 3,785,815, 3,847,615,
4,088,493, 4,123,275, 4,148,653, 4,2
01,587, 4,288,523, 4,297,431, West German Patent Application (OLS) 1,622,936, 2,162,277, Research Disc
losure 15, 162 No. 151 (1976) The timing layer using these materials can be used as a single layer or as a combination of two or more layers.

In addition, for example, US Pat. No. 4,009,029 and West German Patent Application (OLS) 2,913,164
No. 3,014,672, JP-A-54-155837, and 55-13874
No. 5, etc., and a development inhibitor disclosed therein and / or a precursor thereof, or a hydroquinone precursor disclosed in U.S. Pat. No. 4,201,578, and other photographic useful additives or precursors thereof can also be incorporated. .

Further, as a layer having a neutralizing function, JP-A-63-16-16
Providing an auxiliary neutralizing layer as described in JP-A Nos. 8648 and 63-168649 is effective in that the change in transfer density with time after the treatment is reduced.

I) Others The sensitivity of the photosensitive layer can be adjusted by adding a filter dye to the cover sheet. The filter dye may be added directly to the support of the cover sheet, or may be applied as a separate layer.

III.Alkali treatment composition The treatment composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is disposed on the back surface of the support or on the side opposite to the processing solution of the photosensitive layer and the light-shielding layer. As a pair, 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 thickening agent, a light-blocking agent, a developer, and further, a development accelerator for controlling development, an antioxidant for preventing deterioration of the developer, and the like. It contains. The composition always contains a light-shielding agent.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide) and alkali metal phosphates (eg, potassium phosphate). , Guanidines,
Examples include quaternary amine hydroxides (eg, tetramethylammonium hydroxide, etc.), and among them, potassium hydroxide and sodium hydroxide are preferable.

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

As the light-shielding agent, any of dyes and pigments can be used as long as they do not diffuse to the dye image-receiving layer and produce stains.
Also, a combination thereof can be used. A typical example is carbon black.

Preferred developers cross-oxidize the dye image-forming substance,
Any material that does not substantially generate stain even when oxidized can be used. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor form. These developing agents may be contained in an appropriate layer of the photosensitive element, or may be contained in an alkaline processing solution. Specific examples of the compound include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain.

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

(Examples) Example 1 Preparation of photosensitive sheet A photosensitive material I was prepared by applying the following layers in the listed order on a 150 μm transparent polyethylene terephthalate film support.

(1) The following polymer mordant 3.0 g / m ² and gelatin 3.0 g /
the image-receiving layer containing a m ^2.

(2) White reflecting layer containing titanium dioxide 22 g / m ² gelatin 2.75 g / m ² (3) opaque layer containing carbon black 1.7 g / m ² gelatin 1.7 g / m ² (4) of the following structure cyan dye 0.5 g of released redox compound
/ m ² , 0.1 g / m ^{2 of} tricyclohexyl phosphate, 2,5-
Layer containing 0.01 g / m ^{2 of} di-t-pentadecyl hydroquinone and 1.0 g / m ² of gelatin Cyan dye releasing redox compound (5) Titanium dioxide 3.0 g / m ² gelatin 0.8 g / m isolation layer comprising a ² (6) in an amount of internal latent image type direct positive silver bromide emulsion (silver octahedral particle size 1.0 .mu.m 0.15 g / m ² ) Red-sensitive sensitizing dye, gelatin 0.4 g / m ² , the following nucleating agents (NA) 5.0 μg / m ² and 2
A low-sensitivity red-sensitive emulsion layer containing 0.02 g / m ² of sulfo-5-n-pentadecylhydroquinone sodium salt.

(7) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (0.5 g / m ^{2 in} silver), red-sensitive sensitizing dye, same as gelatin 0.8 g / m ² layer (6) A high-sensitivity red-sensitive emulsion layer containing 5.0 μg / m ^{2 of a} nucleating agent (NA) and 0.04 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

(8) 2,5-di-t-pentadecylhydroquinone 1.2 g /
m ^2, polymethyl methacrylate 1.2 g / m ² and color mixing prevention layer containing gelatin 0.7 g / m ^2.

(9) A layer containing 0.3 g / m ² of gelatin.

(10) The following magenta dye releasing redox compound 0.5 g / m
^2, tricyclohexyl phosphate 0.1 g / m ^2, 2,5-di -t- pentadecylhydroquinone 0.009 g / m ² and gelatin 0.9 g / m ² containing layers.

(11) titanium oxide 1 g / m ² and the light reflective layer containing gelatin 0.25 g / m ^2.

(12) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.0 μm (silver amount: 0.25 g / m ² ) Green-sensitive sensitizing dye, gelatin: 0.50 g / m ² , layer (6) 4.4μg / m of the same nucleating agent (NA)
A chemically sensitive green-sensitive emulsion layer containing 0.03 g / m ² of ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

(13) An octahedral internal latent image type direct positive silver bromide emulsion having a grain size of 1.6 μm (0.80 g / m ^{2 in} silver), a green-sensitive sensitizing dye, gelatin 1.0 g / m ² , layer (6) 2.5 μg / m ^{2 of the} same nucleating agent (NA)
And a highly sensitive green-sensitive emulsion layer containing 0.08 g / m ^{2 of} sodium sulfo-5-n-pentadecylhydroquinone sodium salt.

(14) 2,5-di-t-pentadecylhydroquinone 0.8 g /
m ^2, color mixing inhibitors including polymethyl methacrylate 0.8 g / m ² and gelatin 0.45 g / m ^2.

(15) A layer containing 0.3 g / m ² of gelatin.

(16) A yellow dye-releasing redox compound (0.53 g / m ² ) having the following structure, tricyclohexyl phosphate (0.13 g / m ² )
g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014g / m ²⁾ and a layer containing gelatin (0.7g / m ^2).

(17) A light reflection layer containing 0.7 g / m ^{2 of} titanium oxide and 0.18 gm ² of gelatin.

(18) An octahedral internal latent image type direct positive silver bromide emulsion having a grain size of 1.1 μm (silver amount: 0.25 g / m ² ) Blue-sensitive sensitizing dye, gelatin: 0.4 g / m ² , layer (6) The same nucleating agent (NA) 8μg /
m ^2, and 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.045 g / m low-speed blue-sensitive emulsion layer containing a ^2.

(19) Octahedral internal latent image type direct positive silver bromide emulsion having a grain size of 1.7 μm (silver amount: 0.60 g / m ² ) Blue-sensitive sensitizing dye, gelatin 0.70 g / m ² , layer (6) The same nucleating agent (NA) 6.8μg / m
² and a high-sensitivity blue-sensitive emulsion layer containing 0.03 g / m ^{2 of} 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

(20) Each of the following ultraviolet absorbers was used in an amount of 4 × 10 ^-4 mol /
m ^2, and the ultraviolet absorbing layer containing gelatin 0.5 g / m ^2.

(21) A protective layer containing a matting agent and 1.0 g / m ² of gelatin.

Preparation of a cover sheet (comparative) The following layers were provided on a polyethylene terephthalate transparent support containing a light-piping preventing dye subbed with gelatin.

(1) Acrylic acid-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000 was 10.4 g / m ² and 1,4-bis (2,3-epoxypropoxy) -butane 0.1 g / m ^2. Neutralizing layer containing.

(2) Acetyl cellulose having a degree of acetylation of 51% 4.3 g / m ² , poly (methyl vinyl ether-co-monomethyl maleate)
Neutralization timing layer containing 0.2 g / m ^2.

(3) Styrene-butyl acrylate-acrylic acid-N
A polymer latex obtained by emulsion polymerization of methylol acrylamide at a weight ratio of 49.7 / 42.3 / 4/4 and a polymer latex obtained by emulsion polymerization of methyl methacrylate / acrylic acid / N-methylol acrylamide at a weight ratio of 93: 3: 4 are solidified. A layer containing 2.5 g / m ^{2 of the} total solid content, blended so that the mold ratio becomes 6: 4.

(4) A layer containing 1 g / m ² of gelatin.

Preparation of Cover Sheet (Invention) The following layer was applied instead of layer (4) on the cover sheet.

(4) below the polymer latex mordant 1 g / m ² and gelatin 1 g / m ² comprising a dye trapping layer.

Preparation of Cover Sheet (Invention) The following layer was applied instead of layer (4) on the cover sheet.

(4) A dye capturing layer containing 1.5 g / m ² of the following polymer latex mordant and 1.5 g / m ² of gelatin.

Preparation of Cover Sheet (Comparative) The following layer (5) was further applied on the cover sheet.

(5) 1 g / m ² of acetyl cellulose having a degree of acetylation of 55%.

Alkali treatment composition 1-p-tolyl-4-methyl-4-hydroxymethyl-
3-pyrazolidone 10g methylhydroquinone 0.18g 5-methylbenzotriazole 3.0g sodium sulfite (anhydrous) 0.2g benzyl alcohol 1.5cc carboxymethylcellulose Na salt 58.0g carbon black 150g potassium hydroxide (28% aqueous solution) 20cc water 680cc Each 0.8 g of the composition liquid was filled in a “container that can be broken by pressure”.

The photosensitive sheet was exposed through a color test chart, overlapped with the cover sheet, and the alkali treatment composition was developed between the two sheets with the help of a pressure roller to a thickness of 75 μm. The treatment was performed at 25 ° C., and the change of the transfer density up to 10 minutes was measured with the filters of blue (B), green (G) and red (R).

Table 1 shows the results for each cover sheet.
The time required to reach 80% of the transfer density after 1 minute and the reflection density after 1 hour is shown.

In the cover sheet of the present invention, the transfer density after 10 minutes is reduced, but the time to reach 80% is remarkably shortened, and the three colors of yellow, magenta and cyan are transferred in a well-balanced manner.

As described in JP-A-50-142233, a timing layer (here, acetylcellulose) is used as a scavenger mordant layer.
It is evident that the cover sheet positioned at the rear of the sheet has substantially no useful effect on the transfer behavior in a short time after the development processing.

Example 2 Preparation of photosensitive sheet In the photosensitive sheet, layers (4), (6) and (7)
Double, layer (11), (12), (13) 1.4 times each, layer (16)
(18) (19) was prepared in the same manner as the photosensitive sheet except that the coating amount was 1.6 times.

Preparation of cover sheet The following layers were coated on the same support as the cover sheet.

(1) Cover layer sheet (1) and the same layer (2) following polymer 2.9 g / m ² and poly (methyl vinyl ether - co - monomethyl maleate) 0.29 g / m ² neutralization timing layer containing (3) The same layer as the cover sheet layer (3) The photosensitive sheet is exposed through a color test chart, is superposed on the cover sheet, and the alkali treatment composition used in Example 1 is 83 μm thick between both sheets. Deployed with the help of pressure rollers. The treatment was carried out at 25 ° C. and measured in the same manner as in Example 1. The results are shown in Table 2.

Although the value of the 80% arrival time becomes longer than that of Example 1 due to the increase in the coating film thickness, the decrease in the transfer density observed in Example 1 is almost recovered. It is shorter than R in the comparative experiment of Example 1.
Again, it can be seen that the balance for transferring the three colors is well-balanced, and as a result, the image completion time is significantly shorter than in the comparative example.

Example 3 After exposing the photosensitive sheet through a fine wedge for evaluating sharpness, the cover sheet was overlaid on the photosensitive sheet, and the alkali treatment composition used in Example 1 was developed between the two sheets with the help of a pressure roller. After processing at 25 ° C. and leaving it as it was for one day, Sharpness through a green filter was measured with a microdensitometer. CT
When the spatial frequency at which F. was 0.5 was obtained, the results shown in Table 3 were obtained.

In the cover sheet of the present invention, the value of the spatial frequency at which the CTF is 0.5 is large, indicating that the sharpness is clearly improved.

(Effect of the Invention) With the laminated integrated film unit of the present invention, the image completion time is shortened, and at the same time, high image quality, particularly Sharpness, is achieved.
Excellent color image can be obtained.

Claims (1)

(57) [Claims] 1. A photosensitive sheet having an image-receiving layer, a white reflective layer, a light-shielding layer, and at least one silver halide emulsion layer combined with at least one dye image-forming substance on a transparent support. A color diffusion transfer photographic film unit comprising at least a neutralizing layer, a transparent cover sheet having a neutralizing timing layer, and a light-shielding alkali treatment composition which is developed between the photosensitive sheet and the transparent cover sheet. At
A color diffusion transfer photographic film unit having a dye capture layer as an outermost layer of the cover sheet in contact with the alkali treatment composition.