JPH0353248A - Color diffusion transfer photographic film unit - Google Patents

Abstract

PURPOSE:To shorten the time for perfection of images and to obtain color images having high image quality and particularly excellent sharpness by providing dyestuff capturing layer on the outermost surface with which the alkaline processing compsn. of a cover sheet comes into contact. CONSTITUTION:This film unit includes a photosensitive sheet having silver halide emulsion layers combined with an image receiving layer white reflecting layer, light shielding layer, and dyestuff image forming material, a transparent cover sheet having a neutralizing layer and neutralization timing layer on a transparent base and the light shieldable alkaline processing compsn, developed between the photosensitive sheet and the transparent cover on the transparent base. The dyestuff capturing layer is provided on the outermost layer with which the alkaline processing compsn. of the cover sheet comes into contact. The sharpness is improved in this way and the time for perfection of the images is shortened.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color diffusion transfer photographic film unit;
More specifically, a laminated, integrated color diffusion transfer photographic film unit that can be processed in a bright room (prior art).As a laminated, integral color diffusion transfer photographic film unit, an image-receiving layer, a white reflective layer, a light-shielding layer, an image-receiving photosensitive sheet having at least one silver halide emulsion layer in combination with at least one dye image-forming substance;
A unit in which a light-shielding alkaline treatment composition is spread between a transparent cover sheet and a transparent cover sheet is generally well known.

(Problem to be solved by the invention) Originally, the color diffusion transfer method involved developing according to exposure, and depending on the result of development, the dye was diffused from the dye image-forming substance-containing layer and fixed on the image-receiving layer. This is a method of converting images into colors so that they can be observed as color images. Therefore, compared to the color image pattern formed (diffused) in response to exposure in the dye image-forming substance-containing layer, the color image pattern finally obtained is blurred before it diffuses into the image-receiving layer. , the image quality, especially the sharpness, was significantly degraded.

In addition, the alkaline treatment composition is developed and then developed.

Accordingly, it takes time not only for the dye to begin to diffuse from the layer containing the dye image-forming substance, but also for the dye to be fixed in the image-receiving layer after the dye begins to diffuse, so it is difficult to use a so-called peel-off type color diffusion transfer film. Compared to units, the time required to complete an image has been delayed and improvements have been desired.

In order to compensate for these drawbacks, the development of highly diffusible dyes has been progressing, but highly diffusible dyes generally have a low immobilization ability in the image-receiving layer, and conversely cause a decrease in sharpness. This tendency was strong, and it was difficult to get out of the dilemma. In addition, we have developed mordants with excellent dye fixing ability and improved the image-receiving layer, but mordants with excellent fixation ability generally have a strong tendency to reduce the stability of color images against light. There were restrictions. Furthermore, since the laminated integral photographic unit observes a color image through a transparent support, the image quality is degraded, and it has been recognized that the degradation in image quality is particularly large in the case of a transparent support that prevents light piping.

Furthermore, in recent years, in order to improve photographic sensitivity, the grain size of silver halide emulsions has been increased or measures have been taken to increase sensitivity by using light-reflecting layers, which tends to further delay the image completion time. With the advent of electronic still photography and faster processing of conventional photography, competition in different fields has become fiercer, and color diffusion transfer photographic film units have been able to dramatically improve image quality (particularly sharpness) and shorten image completion time. It was hoped that the period would be shortened.

(Object of the Invention) An object of the present invention is to provide a laminated, integrated color diffusion transfer photographic film unit that has high image quality and shortens the time required to complete an image.

Another object of the present invention is to provide a novel monolithic laminated color diffusion transfer photographic film UniSoto which has high sensitivity and can be processed in a bright room.

(Means for Solving the Problems) The inventors have provided a silver halide emulsion of at least ■ layers on a transparent support in combination with an image-receiving layer, a white reflective layer, a light-shielding layer, and at least one dye image-forming substance. (1) a transparent cover sheet having at least a neutralizing layer and a neutralizing timing layer on a transparent support; and (2) a light-shielding sheet spread between the photosensitive sheet and the transparent cover sheet. In a color diffusion transfer photographic film unit comprising an alkaline processing composition of
The above objects have been solved by a color diffusion transfer photographic film unit having a dye capture layer in the outermost layer of the cover sheet which is in contact with the alkaline processing composition.

Diffusion of the dye in response to development initially begins to occur isotropically. That is, it diffuses both in the direction of the image-receiving layer and in the opposite direction, in the direction of the alkaline processing composition layer.

The dye that diffused toward the alkali-treated composition layer also
As the dye that has diffused toward the image-receiving layer is fixed by the mordant, it will begin to diffuse toward the image-receiving layer due to the difference in density, but the diffusion path for such dyes will become significantly longer, resulting in a longer image completion time. This causes a delay in image quality and a decrease in sharpness. By installing a dye-trapping layer on the outermost layer of the cover sheet, the dye that has diffused to the alkali processing composition layer side is captured and returns to the image-receiving layer to form a color image, delaying image completion time and reducing sharpness. This can be prevented. In addition, by installing a dye-trapping layer, it also captures development-inhibiting components (such as bromine ions) generated during development, thereby promoting development itself, which speeds up the completion of images. It seems certain.

The dye-trapping layer in the present invention is extremely effective when the color image in the image-receiving layer is made to be satisfactory, that is, when it is made to have sufficient color density, favorable color harance, sufficiently low minimum density, and favorable gradation. It can only give poor images, has no substantial function as an image-receiving layer, accelerates development, shortens image completion time, and improves sharpness (S).
This layer is used to achieve unexpected effects such as improving sharpness (harpness) and reducing changes in color balance.

The dye-trapping layer contains a polymer mordant in a hydrophilic colloid similar to the dye image-receiving layer described below, and 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-trapping layer may be the same as or different from the mordant used in the dye-receiving layer, and the image quality of the color image on the image-receiving layer can be changed by adjusting the amount of dye capture depending on the mordant power. can.

As the hydrophilic colloid, those known to those skilled in the art such as ceratin, polyvinyl alcohol, modified products thereof, polyvinylpyrrolidone, and polyacrylamide can be used, but gelatin is particularly preferred.

The coating amount of the dye capture layer can be freely set depending on the system, but generally the mordant is 0.1 g/rr? ~lOg
/rd preferably 0.2 g/rn' to 3 g/m', and the hydrophilic colloid has an O. Ig/rd~10g/
m is preferably 0.2 g/po to 3 g/rr{.

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. Patent Nos. 2,548,564 and 2,484
, No. 430, No. 3,148,061, No. 3,756,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat. No. 814 and others; vinylimidazolium cationic polymers disclosed in US Pat. No. 4,124,386;
625,694, 3,859,096, 4,128,538, British Patent No. 1,277,453, and other polymer mordants capable of crosslinking with gelatin; US Pat. No. 958,995, 2.7
No. 21,852, No. 2,798,063, Japanese Unexamined Patent Publication No. 1973
-115,228, 54-145,529, 5
No. 4-126.027, No. 54155.835, No. 5
Aqueous sol-type mordants disclosed in US Pat. No. 6-17,352, etc.; water-insoluble mordants disclosed in US Pat. No. 3,898,088, etc.; US Pat. No. 4,168.9
No. 76, US Pat. No. 4,201,840, etc., reactive mordants capable of forming a covalent bond with the dyes;
No. 3,642,482, No. 3,488,706, No. 3,557,066, No. 3,271,147, No. 3
, No. 271.148, JP-A No. 53-30328, No. 5
No. 2-155528, No. 53-125, No. 5 3 -
Examples include mordants disclosed in J024, No. 53-107,835, British Patent No. 2,064,802, and the like.

Others: U.S. Patent Nos. 2,675,316 and 2,882
, No. 156 can also be mentioned.

Among these mordants, those that are difficult to migrate to other layers are preferred, such as mordants that crosslink with a matrix such as ceratin, water-insoluble mordants, and aqueous sol (or
Latex dispersion) type mordants are preferred. Particularly preferred is a latex dispersion mordant, with a particle size of 0. Ol~2μ
Preferably, the thickness is 0.05 to 0.2μ.

Regarding the dye-trapping layer, Japanese Patent Application Laid-Open No. 50-142233 discloses a scavenger mordant layer, which is located on one side of the alkali processing composition material and emulsion layer, and a dye image-receiving layer is located on the other side of both said layers. A similar concept is disclosed in which a scavenger mordant layer is located within the timing layer or after the timing layer with respect to the alkaline treatment composition layer. The scavenger mordant layer described in JP-A-50-142233 is
Essentially located in the timing layer or after the timing layer with respect to the alkaline processing composition layer to scavenge unwanted processing reaction products and excess dye after a predetermined period of time, preferably 20 to 30 seconds. It is characterized by the fact that the change in Dmax is small depending on the processing temperature.
Alternatively, the change in Dmax from the time of completion of processing to 4 weeks later is small, and furthermore, if a diffusive dye image-forming material is used from the beginning, such as an oxychromic developer, the change in Dmax from the time of completion of processing to four weeks later is small. Past? It is claimed to have effects such as reducing the production of dyes.

In the example of JP-A-50-142233, it is stated that it is necessary to take a timing of 20 to 30 seconds before the scavenger function is expressed, and that if there is no timing, it will interfere with dye diffusion into the image-receiving layer. There is. However, in the case of a photosensitive sheet in which a light-reflecting layer is provided adjacent to a silver halide emulsion layer to improve sensitivity, as in a preferred embodiment of the present invention, as a result, the dye image-forming substance containing layer closest to the image-receiving layer Since the distance of the dye image-forming substance-containing layer furthest from the image-receiving layer is greater than that of the image-receiving layer, the ratio of the diffusion distance of the dye and hence the time required for transfer of the dye shifts. In such a case, the change in color balance will become very large until the color image is completed.

For this reason, in such cases, even if the dye diffusion into the image-receiving layer is hindered without proper timing, the color image density in the image-receiving layer may decrease if the color image density in the image-receiving layer is reduced. I found it to be much more advantageous.

In the present invention, if the timing is set as shown in the examples, the desired effect will not be achieved. The dye-trapping layer of the present invention is characterized in that it is in direct contact with an alkaline processing composition containing a light-blocking agent, thereby promoting development sharpness (S).
sharpness), reduced image completion time, and reduced color balance changes.

On the other hand, for color diffusion transfer photographic film units having two dye-receiving layers or two dyeable layers,
In addition to the above-mentioned JP-A-50-142233, JP-A-57-
No. 58650 and US Pat. No. 3,620,731. Japanese Patent Publication No. 57-58650 discloses a color diffusion transfer photographic film unit in which a dyeable layer is provided on each of two transparent supports.

However, as shown in the Examples, preferred embodiments include a first dyeable layer and a light-sensitive silver halide layer in combination with a dye image-forming material coated on a first support. Including a light-reflecting white layer and a light-shielding layer in between,
Furthermore, by incorporating a white pigment into the alkaline developing composition, any dyeable layer can be observed as a reflective print through the support.

The alkaline processing composition in the present invention is a substantially black liquid containing carbon black, and cannot be said to be a photosensitive composition.
They are completely different.

Additionally, U.S. Pat. No. 3,620,731 discloses a color image-forming material having two dye-receiving layers to obtain two color images using a dye-imaging material that releases dye by intramolecular ring opening. A diffusion transfer photographic film unit is disclosed. However, the above-mentioned patent does not describe any means for stabilizing the image after peeling off, such as the provision of a neutralizing layer or the light-shielding method, and the dye image-forming material is also different from that of the present invention.

Other structural elements will be sequentially explained below.

(2) Photosensitive sheet A) Support The support for the photosensitive 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. It is preferable to provide an undercoat layer. The support usually preferably contains trace amounts of a dye or pigment such as titanium oxide to prevent light piping.

The thickness of the support is 50-350 μm, preferably 7
0-210 μm, more preferably 80-150 μm.

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

Furthermore, 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 one on top of the other. Regarding this, JP-A No. 61-25255
1.

As the mordant, a polymer mordant is preferred.

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

The amount of mordant applied varies depending on the type of mordant, the content of quaternary cation groups, the type and amount of mordant-specific dye, the type of binder used, etc., and is preferably 0.5 to 10 g/d.
．． O to 5.0 g/m, particularly preferably 2 to 4 g/m.

Hydrophilic colloids used in the image-receiving layer include ceratin,
Polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, etc. are used, but gelatin is preferred.

The white reflective layer, which forms the white background of the Tachi-L Kyōhōsō Handanshoku image, usually contains a white pigment and a hydrophilic binder.

As the white pigment for the white reflective layer, barium sulfate, zinc oxide, halium stearate, silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide, etc. are used.

Further, these may be used alone, or may be mixed to the extent that 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 pigment, the mixing ratio of the pigment and binder, and the amount of pigment applied, but it is desirable that the light reflectance is 70% or more. Generally, the whiteness improves as the amount of pigment applied increases, but when the image-forming dye diffuses through this layer, the pigment acts as a resistance to the diffusion of the dye, so it is important to have an appropriate amount of applied pigment. is desirable.

5 to 40 g/rrr of titanium dioxide, preferably
10~25g/rrr coating, light reflectance 540o+
A white reflective layer having 78-85% of the +n wavelength light is preferred.

Titanium dioxide can be selected from various commercially available brands.

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

Many commercially available products are surface-treated with alumina, warpage, zinc oxide, etc., and in order to obtain high reflectance, it is desirable that the surface treatment amount be 5% or more. Commercially available titanium dioxide includes, for example, DuPont's Ti-pu
In addition to re R 9 3 1, there are those described in Research Disclosure No. 15162.

As a binder for the white reflective layer, an alkali-permeable polymeric matrix such as gelatin, polyvinyl alcohol, or a cellulose derivative such as hydroxydiethylcellulose or carpoquinylmethylcellulose can be used.

A particularly preferred binder for the white reflective layer is ceratin. The ratio of white pigment to seratin is l/1 to 20/l (weight ratio), preferably 5/1 to 10/1 (weight ratio).

In the white reflective layer,
It is preferable to incorporate an anti-fading agent such as that disclosed in No. 62-30621.

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 can be used, but carbon black is preferably used.

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

As a carbon black raw material, for example, Donnel V
oet"Carbon Black"Marcel D
ekker, Inc. (1976), any manufacturing method can be used, such as the channel method, thermal method, and furnace method. The particle size of carbon black is not particularly limited, but is preferably 90 to 1,800 particles. The amount of black pigment added as a light-shielding agent may be adjusted depending on the sensitivity of the light-sensitive material to be light-shielded, but an optical density of about 5 to 10 is desirable.

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 light-shielding layer. Its components will be described below.

+1+ Dye-Image-Forming Substances The dye-image-forming substances used in this invention are either non-diffusible compounds that release diffusible dyes (which may also be dye precursors) in conjunction with silver development, or their own diffusivity is altered. The theory of photographic process "T116"
711eory of ihe Photography
Described in icProcess 4th edition. All of these compounds can be represented by the following general formula (I).

DYE-Y (r) Here, DYE represents a dye or a precursor, and Y represents a certain amount that gives a compound having 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 Y include those that oxidize and cleave as a result of development to release a diffusible dye.

Specific examples of Y are U.S. Pat. Nos. 3,928,312 and 3,9.
No. 93,638, No. 4,076,529, No. 4,15
No. 2,153, No. 4, 055, 428, No. 4
, No. 053, 312, No. 4, 1.98, 235, No. 4
, No. 179,291, No. 4,149,892, No. 3,
No. 844,785, No. 3,443,943, No. 3,7
No. 51,406, No. 3,443,939, No. 3,44
No. 3,940, No. 3,628,952, No. 3,980
, No. 479, No. 4,183.753, No. 4, 14
No. 2, 891, No. 4,278,750, No. 4,1
No. 39,379, No. 4,218,368, No. 3,42
No. 1,964, No. 4,199,355, No. 4,199
, No. 354, No. 4,135,929, No. 4,336,
No. 322, No. 4,139,389, JP-A-5 3-5
0 7 3 6, 51-104343, 54
-130122, 53-110827, 56-
No. 12642, No. 56-16131, No. 5 7-4
04 No. 3, No. 57-650, No. 57-20735
No. 53-69033, No. 54-130927,
Of Y in the negative dye-releasing redox compounds described in Nos. 56-164342 and 57-119345, a particularly preferable group is an N-substituted sulfamoyl group (the N-substituted group is an aromatic hydrocarbon ring). and groups derived from heterocycles). Typical groups for Y are illustrated below, but are not limited to these.

NHSO21C. For He(t) OH 0H positive type compounds, please refer to Argevante Hemi International Edition English (Ang
ev. Chem. [nst. Ed. Engl. ), 2
2, 191 (1982).

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

Another type is one that releases a diffusible dye by self-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.
54-130927, U.S. Patent No. 3,421,964,
4,199,355, etc.

Another type is one that does not itself release any pigment, but
This type of compound, some of which releases a dye when reduced, can be used in combination with an electron donor to release a diffusible dye in an imagewise manner by reaction with the remaining electron donor which is imagewise oxidized by silver development. I can do it. Regarding atomic groups with such functions, for example, U.S. Patent 4,
183, 753, 4,142,891, 4,
278, 750, 4,139,379, 4, 2
18, 368, JP 53-110827, U.S. Pat. No. 4,278,750, U.S. Pat.
58,525, JP 53-110827, JP 54-1
30927, 56-164342, Public Technical Report 87-6
199, European Patent Publication No. 220746A2, etc.

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

O CH, C H h O 11h7 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. 4,263,39
No. 3, No. 4,273,750, JP-A-56-1387
It is described in No. 36, etc.

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

C. ．． H. (In the formula, DYE represents a dye having the same meaning as mentioned above or a precursor thereof.) Details of this can be found in U.S. Pat.
No. 8,783.

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

Examples of yellow dyes: U.S. Pat. No. 3,597,200, U.S. Pat. No. 3,309,199
No. 4,013,633, No. 4,245,028, No. 4,156,609, No. 4,139,383,
No. 4,195,992, No. 4,148,641, No. 4,148,643, No. 4,336,322. JP-A-51-114930, JP-A No. 56-71072: R
searchDisclosure 1 7 6
30 (1978), No. 16475 (197
7) Items listed in item 7).

Example of macenta dye U.S. Pat. No. 3,453,107, U.S. Pat. No. 3,544,545
No. 3,932,380, No. 3,931,144, No. 3,932,308, No. 3,954,476,
No. 4,233,237, No. 4,255,509, No. 4,250,246, No. 4,142,891, No. 4
, No. 207,104, No. 4,287,292; JP-A-52-106,727, No. 52-1067
2 No. 7, No. 53-23,628, No. 55-36,8
No. 04, No. 56-73,057, No. 56-71060
No. 55-134.

Examples of cyan dyes: U.S. Pat. No. 3,482,972, U.S. Pat. No. 3,929,760
No. 4,013,635, No. 4,268,625, No. 4,171,220, No. 4,242,435,
4,142,891, 4,195,994, 4,147,544, 4,148,642, British Patent No. 1,551,138; JP-A-54-99431; No. 52-8827, 5 3-4 7 8 2 3
No. 53-143323, No. 54-99431,
No. 5671061; European Patent (EPC) 53,
No. 037, 53, 040; Rese
arch Disclosure17,630 (19
No. 78) and No. 16,475 (1977).

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

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/Nel type" in which at least the photosensitive site of the coated silver halide inner core grain is covered with a silver halide outer shell.
There are emulsions, etc., which are described in U.S. Patent No. 2,592,
250, 3,206,313, British Patent 1,027,
146: U.S. Patent No. 3,761,276, U.S. Patent No. 3,935,
014, 3,447,927, 2,497,875
, 2,563,785, 3,551,662, 2,563,785, 3,551,662,
No. 4,395,478, West German Patent No. 2,728,108, and US Pat. No. 4,431,730.

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

As a nucleating agent for this purpose, U.S. Patent No. 2,563,78
5, hydrazines described in 2,588,982,
Hydrazides and hydrazones described in U.S. Patent No. 3,227,552, British Patent No. 1,283,835, JP-A-52-69613, U.S. Patent No. 3,615,615, No. 3
,719,494, 3,734,738, 4,0
Heterocyclic quaternary salt compounds described in US Pat. Sensitive dye, U.S. Pat. No. 4,030,925, U.S. Patent No. 4,03
1,127, 4,245,037, 4,255,5
11 4,266,013, 4,276,364, thiourea-bonded acylhydrazine compounds described in British Patent 2.012, 143, etc., and U.S. Patent 4,
080,270, 4,278,748, British Patent 2,
Acylhydrazine compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorption group as described in 011.391B and the like are used.

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

For specific examples, see JP-A-59-180550,
No. 60-140335, Research Disclosure (RD) 17029, U.S. Patent No. 1,846,300, No. 2,078,233, No. 2,089,129, No. 2,1
65,338, 2,231,658, 2,917,
516, 3,352,857, 3,411,916
, 2,295,276, 2,481,698, 2
,688,545, 2,921,067, 3,28
2,933, 3,397,060, 3,660,1
03, 3,335,010, 3,352,680,
3,384,486, 3,623.88L 3,7
18,470, 4,025,349, etc.

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

Further, the emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming material layer. For example, JP-A-60-17354
A layer containing the nucleating development accelerator described in 1, Japanese Patent Publication No. 1983-
It is also possible to provide a barrier layer as described in No. 15267 to increase the color image density, or to provide a reflective layer to increase the sensitivity of the photosensitive element.

The reflective layer is a layer containing a white pigment and a hydrophilic binder, and preferably the white pigment is titanium oxide and the hydrophilic binder is gelatin. The amount of titanium oxide applied is 0
, Ig/m~8 g/g, preferably 0.2 g/m
~4g/rr? It is. This is a preferred embodiment of the present invention.

An example of a reflective layer is described in JP-A-60-91354.

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

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

When a developer is used in combination with a non-diffusible dye image-forming material, the intermediate layer preferably contains a non-diffusible reducing agent to prevent diffusion of the developer oxidant. Specific examples include non-diffusible hydroquinone, sulfonamidophenol, sulfonamide naphthol, and more specifically, Japanese Patent Publications No. 50-21249, No. 50-23813, No. 49106329, No. 49-129535, and U.S. Pat. 2,336,327, 2,360,290, 2,4
03,721, 2,544,640, 2,732,
300, 2,782,659, 2,937,086
, No. 3,637,393, No. 3,700,453, British Patent No. 557, No. 750, Japanese Unexamined Patent Publication No. 57-249
4l, 58-21249, etc. Further, their dispersion methods are described in JP-A-60-238831 and JP-B-Sho 60-18978.

When using a compound that releases a diffusible dye with silver ions as described in Japanese Patent Publication No. 55-7576, it is preferable to include a compound that captures silver ions in the intermediate layer.

Also effective is the method described in Japanese Patent Publication No. 63-3300, in which a release layer is provided and the used emulsion layer, cover sheet, etc. are removed after processing.

The present invention may optionally include an ylang-enyon prevention layer, a UV
An absorbent layer, a protective layer, etc. are applied.

■, Cover sheet In the present invention, a layer having a neutralizing function (neutralizing layer and A transparent cover sheet having a timing layer) is used, and the outermost layer of the cover sheet on the side on which the processing solution is applied has the dye trapping layer of the present invention.

F) 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.
Preferably, an undercoat layer is provided.

The support preferably contains a trace amount of 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 brought in from the treatment composition. , a neutralization rate adjusting layer (timing layer), an adhesion reinforcing layer, and the like. Preferred acidic substances include substances containing acidic groups (or precursor groups that provide such acidic groups upon hydrolysis) with a pKa of 9 or less, and more preferably olein as described in U.S. Pat. No. 2,983,606. Higher fatty acids like acids, U.S. Pat. No. 3,362,81
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in FR 2,290,699; Acid ester copolymers: U.S. Patent No. 4,139.38:3 and Research Disclosure
)NCLl 6 1 0 2 (1 9 7 7)
Mention may be made of latex-type acidic polymers such as those disclosed in .

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, No. 541, No. 53-4,
Acidic substances disclosed in No. 542 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/hydrodiene phthalate, and the like.

The polymeric acid can be used in combination with a hydrophilic polymer. Examples of such polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), 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 0. 9-2. 0 is preferable. If the amount of polymeric acid is too small, the hue of the transferred dye may change or stain may occur on the white background, and if it is too large, problems such as a change in hue or a decrease in light resistance may occur. A more preferable equivalent ratio is 1. 0-1, 3.

If the amount of hydrophilic polymer mixed is too large or too small, the quality of the photograph will deteriorate. The weight ratio of hydrophilic polymer to polymeric acid is 0.1-10, preferably 0.3-
It is 3.0.

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

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

Among them, Japanese Patent Application Publication No. 54-136328, U.S. Patent No. 4,
No. 267,262, No. 4,009,030,
Timing layer using cellulose acetate disclosed in JP-A No. 4,029,849, etc.; JP-A-54-12833
No. 5, No. 56-69,629, No. 57-6,843, U.S. Patent No. 4,056,394, No. 4,061,49
No. 6, No. 4,199,362, No. 4,250,243
Latex polymers made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid, as disclosed in No. 4,256,827, No. 4,268,604, etc.;
Polymer having a lactone ring disclosed in U.S. Pat.
3 No. 5, No. 5 6-9 7 3 4 No. 6, No. 57-
No. 6842, European Patent (EP) 31,957A1
Particularly useful are the polymers disclosed in No. 37,724 Al and No. 48,412 Al.

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 application (○LS) l. No. 622,936, 2, 1
62, No. 277, Research Disclo
Sure l 5, l 6 2 No. 151
(1976) Timing layers using these materials can be used alone or as a combination of two or more layers.

In addition, timing layers made of these materials are covered by, for example, U.S. Patent No. 4,009,029, West German Patent Application (OLS)
, 913,164, 3,014,672, JP 54-155837, JP 55-138745, etc., and the development inhibitors and/or precursors thereof, as well as U.S. Pat. It is also possible to incorporate the hydroquinone precursor disclosed in , No. 578, and other additives useful for photography or their precursors.

Furthermore, as a layer having a neutralizing function, JP-A-63-1
Providing an auxiliary neutralizing layer as described in No. 68648 and No. 63-168649 is effective in reducing changes in transfer density over time after processing.

(2) In addition, it is also possible to adjust the sensitivity of the photosensitive layer by incorporating a filter dye into the cover sheet. The filter dye may be added directly into the support of the cover sheet or may be applied as a separate layer.

■． Alkaline Processing Composition The processing composition used in the present invention is spread uniformly on the photosensitive element after exposure of the photosensitive element, and is placed on the back of the support or on the opposite side of the photosensitive layer from the processing solution, so as to be paired with the light-shielding layer. Thus, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light shielding agent, a developer, a development accelerator and a development inhibitor to control development, and an antioxidant to prevent deterioration of the developer. Contains. A light shielding agent is always included in the composition.

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

Thickeners are used to spread the processing solution uniformly, and also to thicken the photosensitive layer/
Necessary to maintain close contact between cover sheets. For example, alkali metal salts of polyvinyl alcohol, hydroxyethylcellulose, and carboxymethylcellulose are used, and preferably hydroxyethylcellulose and sodium carboxymethylcellulose are used.

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

Preferred developing agents include any that cross-oxidizes the dye image-forming material and does not substantially stain when oxidized.

Such developers may be used alone or in combination of two or more, or may be used in the form of a precursor. These developing agents may be included in appropriate layers of the photosensitive element or may be included in the alkaline processing solution. Specific compounds include aminophenols and pyrazolidinones, and among these, pyrazolidinones are particularly preferred because they generate less stain.

For example, ■-phenyl-3-virazolidinone, 1-p-
h-lylu-4,4-dihydroxymethyl-3-birazolicinone, l-(3-methyl-methyl)-4-methyl-4
-hydroxymethyl-3-virazolidinone, l-phenyl-4-methyl-4-hydroxymethyl-3-virazolidinone, lp-tolyl-4-methyl-4-hydroxymethyl-3-virazolidinone, and the like.

EXAMPLE Photosensitive material I was prepared by coating the following layers in the order listed on a 150 micron transparent polyethylene terephthalate film support.

(1) Polymer mordant 3 below, Og/rr? and Seratin 3, Og/rr? an image-receiving layer containing

(2) Titanium dioxide 2 2 g/rd and gelatin 2.7
5g/rr? (3) an opaque layer containing 1.7 g/rrr of carbon black and 1.7 g/rrr of gelatin; (4) a cyan dye-releasing redox compound having the following structure: 0.
5g/rd, tricyclohexyl phosphate 0. lg
/rd, 2,5-di-t-pentadecylhydroquinone 0.0 lg/%, and gelatin 1.0 g/lT? A layer containing a cyan dye-releasing redox compound 0H C(C}13)8 (5) 3.0 g/m titanium dioxide and 0.8 g gelatin.
Difficult layer (6) containing lrd particle size l. 0 μm octahedral internal latent image type direct positive silver bromide emulsion (0.15 g/m in silver content)
Red-sensitive sensitizing dye, gelatin o. 4g,/m, 5.0μg/rd of the following nucleating agent (NA) and 2-sulfo-5
-n-pentadecylhydroquinone sodium salt 0.
A low-speed red-sensitive emulsion layer containing 0.02 g/m.

(7) Internal latent image type direct-bodied silver bromide emulsion with grain size 1.6 μm octahedron (silver amount 0.5 g/rrr) red-sensitive sensitizing dye, same structure as gelatin 0.8 glrd layer (6) Nucleating agent (
NA) 5.0 μg/rrr and 2-sulfo5-
n-pentadecylhydroquinone sodium salt o.
High-speed red-sensitive emulsion layer containing o4g/rn'.

(8) 2,5-di-L-pentadecylhydroquinone 1.2 glrd, polymethyl methacrylate l
, 2 g/rrr and gelatin 0.7 g 7'rr? Contains an anti-konshoku layer.

(9) Layer containing 0.3 g/m of gelatin.

(10) The following magenta dye-releasing redox compound 0.
5g/r&, tricyclohexyl phosphate 0.
lg/rd, 0.009 g/m of 2.5-di-t-pentadecylhydroquinone and 0.1 g/m of seratin. 9g/n
{Containing layer. OH (ID titanium oxide 1 g/d and gelatin 0.5
g/rr? A light-reflecting layer containing ′.

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

(11) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (silver amount 0.80 g/m), green-sensitive sensitizing dye, gelatin l.Og/rrr, layer (6) and Same nucleating agent (NA) 2.5 μg/rr? and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0
．． High-speed green-sensitive emulsion layer containing 0.08 g/m.

(1ω 2,5-di-t-pentadecylhydroquinone 0.8g/tn', polymethyl methacrylate 0.8
glr! and a color mixing inhibitor containing 0.45 g/m of gelatin.

(One layer containing 0.3 g/m' of gelatin.

(16) A yellow dye-releasing redox compound with the following structure (0.53 g/rd), tricycline phosphate (0.13 g/rr?), 2.5-di-tpentadecylhydroquinone (0.01 g/rr?) ) and gelatin (0.7 g/tr?).

(1. Light reflecting layer containing 0.7 g/rr? of titanium oxide and 0.18 g/rr of gelatin.

(] & Octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.1 μm (silver content 0.25 g/r)
ri') blue-sensitive sensitizing dye, gelatin 0.4 g/m, layer (
A low-speed blue-sensitive emulsion layer containing the same nucleating agent (NA) 8 μg/m' as in 6) and 0.045 g/rn' of 2-sulfo-5-n-bentadecylhydroquinone sodium salt.

(19) Particle size 1. 7μm octahedral internal latent image type direct positive silver bromide emulsion (silver amount 0.60g/♂) blue-sensitive sensitizing dye, gelatin 0.70g/rr? , a high-speed blue-sensitive emulsion layer containing 6.8 μg/rd of the same nucleating agent (NA) as layer (6), and 0.03 g/rrr of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

■ The following ultraviolet absorbers each at 4 x 10 mol/r
rr, and an ultraviolet absorbing layer containing 0.5 g/m of gelatin.

(2l) Protective layer containing a matting agent and 1.0 g/m of seratin.

Preparation of Cover Sheet (Comparison) The following layers were coated on a gelatin-subbed polyethylene terephthalate transparent support containing a light piping prevention dye.

(1) Acrylic acid-butyl acrylate (mole ratio 8:2) copolymer with an average molecular weight of 50,000 at 10.4 g/rr? and 1. 4-bis(2,3-epoxypropoxy)monobutane O. A neutralization layer containing lg/n{.

(2) Acetylcellulose with acetylation degree 5 1% 4.3
g/m, poly(methyl vinyl ether-comonomethyl maleade) - 0.2 g/rr? A neutralization timing layer containing.

(3) Styrene-butyl acrylate acrylic acid-N methylolacrylamide weight ratio 49.7/42
．． A polymer latex emulsion-polymerized at a ratio of 3/4/4 and a polymer latex emulsion-polymerized at a weight ratio of 93:3:4 with methyl methacrylate/acrylic acid/N-methylol acrylamide at a solid content ratio of 6:4. A layer containing a total solids content of 2.5 g/bo.

(4) A layer containing gelatin Ig/bo.

Preparation of cover sheet 0 (present invention) The following layer was coated in place of layer (4) of the cover sheet.

(4) A dye capture layer containing the following polymeric latex mordant at Ig/m and gelatin at lglrd.

The following layer was applied instead of layer (4) on the cover sheet.

(4) Add the following polymer latex mordant to I. Dye capture layer containing 5 g/d and gelatin 1.5 g/m.

The following layer (5) was further coated on cover root 0.

(5) Acetyl cellulose with a degree of acetylation of 55% 1 g/rr
r.

Alkaline treatment composition 1-p-Tolyl-4-methyl 4-hydroxymethyl 3-virazolidone log methylhydroquinone 0.18 g 5-methylbenzotriazole 3. Og
Sodium sulfite (anhydrous). 0.2g Benzyl alcohol 1.5cc Carboxymethyl cellulose Na salt 58.0g Carpon black 150g Potassium hydroxide (28% water solution) 200cc Water
0.8 g of 680 cc of the above-mentioned treatment composition liquid was filled into a "container breakable by pressure."

The photosensitive sheet was exposed to light through a color test chart, overlapped with the cover sheets 1 to 0, and the alkali treatment composition was spread between both sheets to a thickness of 75 μm with the help of a pressure roller. . Processing at 25℃
Changes in transfer density over time up to IO minutes are shown in blue (
B), green (G), and red (R) filters.

Table 1 shows the IO when processed with each cover sheet.
The transfer density after minutes and the time required to reach 80% of the reflection density after 1 hour are shown.

■(Comparison) 1.75 1.90 2.02
4.2 3.3 2.40 (present invention) 1.3
0 1.50 1,93 2.8 2.5
2.4O(l/) 1.29 1.48
1.93 2,8 2.6 2.4 With the cover sheet of the present invention, although the transfer density decreases after 10 minutes, the time to reach 80% is significantly shortened.
It can be seen that the three colors of magenta and cyan are transferred in a well-balanced manner.

As described in JP-A-50-142233, in the cover sheet 0, which is positioned behind the timing layer (here, acetyl cellulose) as a scavenger mordant layer,
It is clear that there is no substantially useful effect on the transfer behavior within a short period of time after the development process.

Kansudan 1: 2nd grade, 2nd grade! In the Tatsuri photosensitive sheet ■, layer (41 (6) (71) is added to l.
1x, layer (10) + 12) (131 each 1.
The photosensitive sheet was prepared in the same manner as the photosensitive sheet except that the coated amount of each layer (16+fl mark (19)) was 166 times.

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

(1) The same layer as layer (1) of the cover sheet ■ (2) The following polymer 2. 9g/rrl' and poly(methylvinyl di-terucomonomethylmaleate) 0.29
Neutralization timing layer CH.g/rrr.
CH. (3) The same layer photosensitive sheet (3) as layer (3) of cover sheet 0 was exposed through a color test chart, overlapped with the cover sheet 00, and the alkali treatment composition used in Example 1 was placed between the two sheets. was rolled out to a thickness of 83μ with the help of a pressure roller. Processing at 25℃
The measurement was carried out in the same manner as in Example 1. The results are shown in Table 2.

e 1.74' 1.91 2.01 3
．． 6 3.0 2.6 Although the time to reach 80% is longer than in Example 1 due to the thicker coating film, the decrease in transfer density observed in Example 1 is almost recovered, and still The time to reach 80% is shorter than in the comparative experiment of Example 1 except for R. It can be seen that the three colors are transferred in a well-balanced manner, and as a result, the image completion time is significantly shorter than in the comparative example.

After exposing the short-loss photosensitive sheet ■■ through a thin wire wedge for Sharpness evaluation, cover sheets ■ to [F] were overlaid and the alkali treatment composition used in Example 1 was applied between the two sheets under pressure. Unrolled with the help of rollers. 2
Sharpen was processed at 5°C and left for one day, then passed through a green filter using a cyclodensitometer.
ess was measured. C. T. F. When the spatial frequency at which 0.5 was determined, the results shown in Table 3 were obtained.

■ ■ 75μ 2.6 lines/mm Comparative example/l O 〃
2.7 lノ■
e 83 3.2 Present invention 1
/ O // 3.21/〃
E> Nol 3.
3 In the cover sheet of the present invention, C. T. F. 0. The spatial frequency value of 5 is thicker, indicating that the sharpness has clearly improved.

(Effects of the Invention) The laminated integrated film unit of the present invention reduces the time required to complete an image, and at the same time provides high image quality, especially sharp images.
Excellent color images of ess can be changed.

Claims (1)

[Scope of Claims] 1. A photosensitive sheet having, on a transparent support, an image-receiving layer, a white reflective layer, a light-shielding layer, and at least one silver halide emulsion layer in combination with at least one dye image-forming substance, 2. A transparent support. a transparent cover sheet having at least a neutralizing layer and a neutralizing timing layer on the body; and 3. a color diffusion comprising a light-blocking alkaline processing composition adapted to be spread between said photosensitive sheet and said transparent cover sheet. In the transfer photographic film unit,
A color diffusion transfer photographic film unit characterized in that the outermost layer of the cover sheet in contact with the alkali processing composition has a dye trapping layer.