JPH01289951A - Color diffusion transfer photographic film unit - Google Patents

Abstract

PURPOSE:To obtain the title unit which haws excellent sticking property between an image receiving layer and a timing layer adjacent to the image receiving layer, and is not tacky and has a high quality by mounting a specified timing layer and a color image receiving layer adjacent to the timing layer on a supporting body. CONSTITUTION:A photosensitive element is obtd. by combining at least a neutralizing layer (a), the timing layer (b) contg. an aqueous latex polymer and 1-9wt.% of gelatin, the color image receiving layer (c), a peeling layer (d) and at least one of silver halide emulsion layer (e) combined a color image forming substance in this order. The photosensitive element and a transparent cove sheet are mounted on a white supporting body. And, the film unit contains an alkaline processing composition contg. a light shielding agent evolved between the upper-most layer of the photosensitive element and the cover sheet, and also the layer having a light shielding function on the opposite side against the side evolved the processing composition of the emulsion layer. Thus, the sticking property between constituting elements such as the color image receiving layer and the timing layer, and the handling property of the film unit are improved, and both the excellent sharpness and color reproducibility of the film unit are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color diffusion transfer photographic film unit. More specifically, the present invention relates to a peelable color diffusion transfer photographic film unit.

[Conventional technology]

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

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

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

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

The second reason is that the white reflective layer, which serves as the bank ground for observing images, is a layer to which pigment is transferred by diffusing this layer. Therefore, in order to increase the reflectance, it is necessary to increase the density of the reflective material or If the thickness of the layer is increased, the diffusion of the dye becomes slower, making it impossible to obtain sufficient reflectance.

This increases the minimum density of the image.

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

There are two types of peelable types. One, as shown in U.S. Pat. No. 3,362.819, has a light-sensitive layer and a dye-receiving layer coated on separate supports, and after imagewise exposure, the light-sensitive element and the dye-receiving element are separated. A dye image transferred to the dye image-receiving layer is obtained by superimposing the dye image-receiving layer, spreading a processing composition therebetween, and then peeling off the dye-receiving element.

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

Another type is U.S. Patent No. 4. 328°301
As shown in No. 1, a dye image-receiving layer, a release layer, and a photosensitive layer are sequentially coated on a support, and after processing, the photosensitive layer is peeled off to obtain a print. In this case as well, the dye image formed on the dye image-receiving layer coated on the support is directly observed, resulting in very excellent color reproduction.

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

Patent application No. 62-2313 filed by the applicant of the present invention
As shown in No. 74, the following elements; a white support: a layer having a neutralizing function; a dye-receiving layer; the support, the layer having a neutralizing function, and the dye-receiving layer are separable from the rest of the element after processing; Release layer: A light-sensitive element having at least one silver halide emulsion layer in combination with a dye image-forming material:
Alkaline processing composition containing a light-shielding agent: A film unit is known which consists of a transparent cover sheet and has a layer having a light-shielding function on the side on which the processing composition is developed and on the reflective side of the emulsion layer.

Although this film unit is a peelable film, the processing liquid does not stick to it, there is no handling inconvenience associated with overlapping film sheets other than the peeling operation, and since the image is not observed through the support, This is a photo-developable film unit that can provide superior image quality compared to non-peel-required types that require observation through the lens. A dye-receiving layer is provided on a white support, and a layer with a neutralizing function is provided between the dye-receiving layer and the support to prevent undesirable fogging during image formation and to prevent staining during storage of prints. , can prevent discoloration of image dyes.

(Problems to be Solved by the Invention) Peel-off type diffusion transfer photographic film units are subjected to a stronger physical action of ``peel'' than non-peel type units, so the image-receiving element is subject to stricter film physical properties. ” is required. This is because if the interlayer adhesion between the layers constituting the image-receiving element is not good, a portion of the image-receiving element will peel off when the image-receiving element is separated from the photosensitive element.

There are also parts of the unit in which the treatment composition is spread and becomes wet, and parts where the treatment composition is not spread and remains in a dry state. If the image receiving element starts to peel off from the timing layer in the dry area, it will greatly affect the removability of the wet area. It would be fatal if the image peeled off when the tape was pasted and the tape was peeled off again, so it is required that the interlayer adhesion of each layer, especially the interlayer adhesion of the image receiving element, be strong. In particular, in the film unit described in Japanese Patent Application No. 62-231374, it is preferable to use a hydrophobic binder in order to fully exhibit the timing function as a timing layer. It is difficult to provide a hydrophilic layer such as a dye image-receiving layer and bring it into close contact. In order to improve the adhesion of these, surface treatment to improve the adhesion between the eyebrows and intermediate layer (patent application 1368-1983)
23) or a primer layer (Japanese Unexamined Patent Publication No. 59-107352), or a method of incorporating a hardening agent into the adjacent first timing layer of an image receiving element coated with an image receiving layer containing gelatin (Japanese Unexamined Patent Publication No. 59-107352). However, these often have an adverse effect on photographic properties, such as reducing the function as a timing layer and lowering Dmax or increasing Dmin, and the adhesive strength is still poor. However, providing an intermediate layer or the like is disadvantageous in terms of process or cost. Although it is a peelable type, it is strongly desired to provide a color diffusion transfer photographic film unit that is easy to handle, has excellent color reproducibility, and has excellent interlayer adhesion between layers.

(Object of the Invention) An object of the present invention is to provide excellent color diffusion in which the image-receiving layer and the timing layer adjacent to the image-receiving layer adhere to the glabella so that the image-receiving layer and the timing layer adjacent to the image-receiving layer do not peel off inside the image-receiving element when the image-receiving element and the photosensitive element are separated. The purpose of the present invention is to provide a transfer photographic film unit.

A further object of the present invention is to provide a color diffusion transfer photographic film unit that exhibits excellent glabella adhesion between the image receiving layer and the timing layer adjacent to the image receiving layer during storage after drying.

Another purpose is to provide high-quality color diffusion transfer photographs that do not sag after being peeled off.

Still another object is to provide a diffusion transfer image forming method that allows high quality color images without smearing to be obtained by processing in a bright room.

Yet another purpose is to remove used emulsion layers, bods, and cover sheets by cleanly peeling off the portion containing the support, reflective layer, and dye-receiving layer from the rest of the film unit at the location of the release layer after processing. It is an object of the present invention to provide a film unit similar to so-called conventional printing, which is free from adhering.

[Means to solve the problem]

The object is to provide a color diffusion transfer photographic film unit having, on a support, at least a timing layer containing a water-soluble Latinx polymer and 1 to 9% by weight gelatin, and a dye-receiving layer adjacent to the timing layer. (Hereinafter, it may be simply abbreviated as "film unit").

Furthermore, the object is to provide a color diffusion transfer photographic material having, on a support, at least a timing layer containing a water-soluble latex polymer and 1 to 9% by weight of gelatin, and a dye-receiving layer adjacent to the timing layer. This was achieved by a color diffusion transfer image forming method characterized by exposing the film unit from the cover sheet side and spreading the processing composition into the film unit.

In the above preferred embodiment, on the white support, at least:
(a) neutralization layer, (b) water-soluble latex polymer and 1-
A light-sensitive element and a transparent having sequentially a timing layer containing 9% by weight gelatin, (C) a dye-receiving layer, (d) a release layer, (e) at least one silver halide emulsion layer in combination with a dye-image-forming material. a cover sheet, an alkaline processing composition including a light blocking agent spread between the top layer of the photosensitive element and the cover sheet, on a side of the emulsion layer opposite to the side on which the processing composition is spread; This is a color diffusion transfer photographic film unit characterized by having a layer having a light shielding function.

Tokukai Showa 5! No. ll-107352 describes a method of providing a primer layer consisting of polymer latex and gelatin between a timing layer and an image-receiving layer, which is a two-sheet type diffusion transfer film unit;
It is not an integrated diffusion line film unit of the present invention.

In addition, the amount of gelatin used is 1/10 to 10 times the weight of the polymer latex, and as shown in the examples of the present invention, the gelatin ratio is increased (as the neutralization timing function decreases and the neutralization becomes faster). As a result, I) max decreases or the film formability of the layer is impaired. In addition, there is an example by the same applicant of the present invention in which gelatin and polymer latex are used in a layer adjacent to the image receiving layer at a ratio of 1:10, but this structure also has a timing layer, and if this If there is no other timing layer, the timing function will be insufficient and Dmax will decrease.

It was surprising that by practicing the present invention, the interlayer adhesion between the timing layer and the image-receiving layer was improved without providing an additional timing layer and without reducing the Dmax of the image.

After exposure, the film unit of the present invention is processed by a pressing member to spread the alkaline processing composition uniformly within the film unit and start development. After developing the treatment composition, the film Uniso I. may be placed in a bright room or under daylight.

By peeling off the part containing the support, reflective layer, and dye image-receiving layer from the rest of the film unit at the release layer position after processing, it is possible to remove used emulsion layers, pots, cover sheets, etc. from adhesion. A print similar to a so-called conventional print can be obtained.

Each of these components will be explained in turn below.

A) White support The white support referred to in the present invention refers to a support that is white at least on the side on which the dye image-receiving layer is coated, and may be any support as long as it has sufficient whiteness and smoothness. It can be used. For example, titanium oxide with a particle size of 0.1 to 5μ,
Polymer films made white by adding white pigments such as barium sulfate or zinc oxide or by forming microvoids by stretching, such as films made of polyethylene terephthalate, polystyrene, or polypropylene made by conventional sequential biaxial stretching, synthetic paper, and paper. A material laminated with polyethylene, polyethylene phthalate, polypropylene, etc. containing ditambowite on both sides is preferably used. The thickness of the support is 50-350 μm, preferably 7 C1-
210 μm, more preferably 80-150 μm.

Further, if necessary, a light-shielding layer can be provided in the support. For example, a support formed by laminating polyethylene containing a light shielding agent such as carbon black on the back side of a white support is used.

As a carbon blank raw material, for example, Donnei
Voet “Carbon Black” Mar
cel Dekker.

Any manufacturing method can be used, such as a channel method, a thermal method, and a furnace method as described in J.D., Inc. (1976).

The particle size of carbon black is not particularly limited, but 9
0 to 1800 A' is preferred.

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

Supplementary Live Bait 1 The neutralizing layer 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. Preferred acidic substances include substances containing an acidic group with a pKa of 9 or less (or a precursor group that provides such an acidic group upon hydrolysis), and more preferably oleic acid as described in U.S. Pat. No. 2,983.606. higher fatty acids such as polymers of acrylic acid, mecacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in U.S. Pat. No. 3,362.819; Copolymers of acrylic acid and acrylic esters as disclosed in U.S. Pat. No. 4,139,383 and Research Disclosure hv
16102 (1977).

In addition, U.S. Patent No. 4.0B8.493, Japanese Patent Application Laid-open No. 1987-
No. 153.739, No. 53-1.023°, No. 53-
No. 4,540, No. 53-4,541, No. 53-4, 5
Acidic substances disclosed in No. 42 and the like can also be mentioned.

Specific examples of acidic polymers include ethylene, vinyl acetate,
These include copolymers of vinyl monomers such as vinyl methyl ether and maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose acetate hydrogen phthalate, and the like.

The polymeric acid can be used in combination with a hydrophilic polymer. Examples of such polymers include polyacrylamide, 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 preferably 0.9 to 2.0. If the amount of polymeric acid is too small, problems such as a change in the hue of the transferred dye, staining on the white background, and a change in the hue or a decrease in light fastness may occur if the dye is used for a long time. A more preferable equivalent ratio is 1.0 to 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 from 0.1 to 10, preferably from 0.3 to 3.0.

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

The timing layer adjacent to the image-receiving layer, which is a feature of the present invention, contains a water-soluble latex polymer and 1 to 9% by weight of gelatin.

A technique has been disclosed in which a water-soluble latex polymer is used for the timing layer, but in that case, the adhesion with the image-receiving layer is poor, so an adhesion layer is required between the timing layer and the image-receiving layer. The adhesion layer is said to be a mixture of a timing layer and an image-receiving layer binder, but in order to fully demonstrate its timing function, a separate timing layer is required.
There was a problem that required a large number of layers. The object of the present invention is to provide a timing layer which has a timing function and has excellent adhesion by containing 1 to 9% by weight of gelatin in the timing layer.

As the water-soluble latex polymer used in the timing layer of the present invention, a latex polymer that is made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer and has a high activation energy for alkali permeation is useful.

Among them, JP-A-53-72622 and JP-A-54-1283.
No. 35, No. 54-138432, No. 54-13843
No. 3, No. 56-69629, No. 57-6843, U.S. Patent No. 4. 056. No. 394, 4,061,4
No. 96, 4. A latex polymer prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid as disclosed in US Pat. No. 250.243 is preferred.

Gelatins that can be used in this timing layer include alkali-treated gelatin, acid-treated gelatin, oxygen-treated gelatin, or gelatin modified with an acylating agent, such as acetylated gelatin, phthalated gelatin, maleated gelatin, or grafted with a vinyl polymer. gelatin, etc., and two or more of these gelatins can also be used in combination.

Among these gelatins, alkali-treated gelatin or acid-treated gelatin is preferred.

The solid content ratio of gelatin in this timing layer is 1 to 9.
wt% is preferred. If the amount of gelatin is too large, the film forming properties of the timing layer will be impaired, the timing function will be degraded, neutralization will be carried out too quickly, and the image density will become low. Moreover, if the amount of gelatin is too small, the adhesion improving function will not be expressed. A more preferred range is 2 to 5 wt%.

The timing layer can be used alone or as a combination of two or more layers. When two or more types of timing layers are used together, in addition to the compounds used in the timing layer, compounds used in the timing layer that are not adjacent to the image-receiving layer may include polyvinyl alcohol, a partially acetal compound of polyvinyl alcohol, cellulose acetate, etc. Polymers that reduce alkali permeability, such as hydrolyzed polyvinyl acetate, etc.; polymers having lactone rings as disclosed in US Pat. No. 4,229,516; and the like.

Others JP-A-56-25735, JP-A No. 56-97346
No. 57-684.2, No. 56-102852,
European Patent Publication No. 37.724A1, European Patent Publication No. 48.412A1
Particularly useful are the polymers disclosed in, et al.

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

U.S. Patent No. 3.4.21,893, U.S. Patent No. 3,455.6
No. 86, No. 3,575,701, No. 3゜778.26
No. 5, No. 3,785.815, No. 3.847. 61
No. 5, No. 4.088, 493, No. 4. ．． ], 23.2
No. 75, 4. ．． 1,1.8.653, 4,201
, No. 587, 4. 288. No. 523, 4. ,2
No. 97.431, West German Patent Application (OLS) 1,622,
No. 936, No. 2,162゜277, Re5earch
Disclosure 15162 m151
(1976).

In addition, for timing layers made of these materials, for example, U.S. Patent No. 4.009.029, West German Patent Application (OLS)
2,913,164, 3,014.672, JP-A-54-155837, JP-A-55-138745, etc., and the development inhibitors and/or precursors thereof, as well as U.S. Pat. It is also possible to incorporate the hydroquinone precursor disclosed in No. 201.578, and other additives useful for photography.

D) Dye image-receiving layer The dye-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 having different mordant powers are applied in layers. Regarding this, JP-A No. 61-25255
It is stated in No. 1. As the mordant, a polymer mordant is preferred.

The polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers having a nitrogen-containing heterocyclic moiety, polymers containing these quaternary cation groups, etc., and those having a molecular weight of 5.000 or more are particularly preferable. is 10,00
It is 0 or more.

For example, U.S. Pat. No. 2,548,564, U.S. Pat.
．． No. 430, No. 3,148.061, No. 3.756.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat. No. 814 and others; US Pat. No. 4,124. ．． Vinylimidazolium cationic polymers disclosed in US Pat. No. 386, etc.; US Pat. No. 3,
No. 625,694, No. 3,859,096, No. 4.1
Polymer mordants capable of crosslinking with gelatin, etc., as disclosed in U.S. Pat. No. 28°538, U.K. Pat.
No. 852, No. 2,798.063, Japanese Unexamined Patent Publication No. 1983-11
No. 5,228, 54. -145゜529, same 54-
No. 126,027, No. 54-155.835, No. 56
Aqueous sol-type mordant disclosed in U.S. Pat. No. 17.352, etc.; water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088, etc.; U.S. Patent No. 4,168.97
No. 6, US Pat. No. 4,201,84.0, etc., and reactive mordants capable of covalently bonding with dyes;
Same No. 3,642,482, No. 3,488,706, No. 3,557,066, No. 3,271.147
No. 3,271゜148, JP-A-53-3032
8, No. 52-155528, No. 53-125, No. 53-1024, No. 53-107,835, British Patent No. 2.064,802, etc. can.

Others: U.S. Patent No. 2,675.316, U.S. Patent No. 2.882
．． Mention may also be made of the mordants described in No. 156.

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

E) Release layer In the present invention, a release layer is provided between the emulsion layer combined with the dye image-forming material and the dye image-receiving layer, and the emulsion layer is peeled off after processing. Therefore, this release layer must maintain close contact between the image-receiving layer and the emulsion layer in an unprocessed state, and must be easily peelable after processing. Materials for this purpose include, for example, JP-A-47-8237, JP-A-56-65133,
No. 59-220727, No. 59-229555, Special Publication No. 49-4334, No. 49-4653, No. 45-
No. 24075, U.S. Patent No. 3,220,835, U.S. Patent No. 435
Those described in No. 9518, No. 3227550, No. 2759825, No. 4401746, No. 4366227, etc. can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethylcellulose, cellulose acetate-phthalate, plasticized methylcellulose, ethylcellulose, cellulose nitrate, and carboxymethylcellulose. Other examples include various natural polymers such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Further examples include water-soluble synthetic polymers.

For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, butyl methacrylate, or copolymers thereof.

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

In the present invention, a photosensitive element comprising a silver halide emulsion layer combined with a dye image-forming material is provided above the release layer. I will talk about its components below.

(1) Dye-image-forming substance The dye-image-forming substance used in the present invention is either a non-diffusible compound that releases a diffusible dye (which may also be a dye precursor) in conjunction with silver development, or it has its own diffusive property. ``The theory of photographic process''
Theory of The Photography
icProcess" 4th edition. All of these compounds can be represented by the following general formula (1).

(DYE)-Y (1) Here, (DYE)
E) represents a dye or its precursor, and Y represents a component that provides a compound with diffusivity different from that of the above compound under alkaline conditions. Depending on the function of Y, silver is roughly divided into negative compounds that become diffusible in the silver developed area and positive compounds that become diffusible in the undeveloped area.

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

Specific examples of Y include U.S. Patent Nos. 3,928.312 and 3,
No. 993.638, 4. ．． No. 076.529, same 4,
No. 152,153, 4. 055. No. 428, 4
, No. 053, 312, 4. , 198゜235, same 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. 142
．． No. 891, No. 4,278,750, No. 4,139
No. 379, No. 4,218.368, No. 3,421.
No. 964, No. 4,199,355, No. 4゜199.3
No. 54, No. 4,135,929, No. 4,336,32
No. 2, No. 4,139,389, JP-A-53-5073
No. 6, No. 51-104343, No. 54-130122
No. 53-110827, No. 56-12642,
No. 56-16131, No. 57-4043, No. 57-
No. 650, No. 57-20735, No. 53-69033
No. 54-130927, No. 56-164342, No. 57-119345, etc.

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

HctHqD-) For positive-type compounds, Angewante Hemi International Edition English (Ang
ev, Chem, In5t, Fd, Engl,
) + 22 +191 (19B2).

A specific example is a compound (dye developer) that is initially diffusible under alkaline conditions but becomes non-diffusible after being oxidized 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-closing under alkaline conditions, but substantially ceases to release the dye when oxidized during development. For specific examples of Y having such a function, see US Pat. No. 3,980°479, US Pat. No. 3,421,
No. 964, No. 4゜199.355, JP-A-53-69
No. 033, No. 54-130927, etc.

Another type is one that does not itself release any pigment, but
Some release dyes when reduced.

This type of compound is used in combination with an electron donor,
Diffusible dye can be released into the image by reaction with the remaining electron donor oxidized into the image by silver development. Regarding atomic groups having such functions, for example, US Pat. No. 4,183.753, US Pat.
No. 891, No. 4゜278.750, No. 4,139,3
No. 79, No. 4,218,368, No. 4,356,24
No. 9, No. 4,358,525, JP-A-53-1108
No. 27, No. 54-130927, No. 56-16434
No. 2, Publication Branch Axis No. 87-6199, European Patent Publication No. 220
746A2 etc.

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

H3 CI+3 0 C, □)lzsC12H
25CI+3 When this type of compound is used, it is preferably used in combination with a diffusion-resistant electron donor compound (known as an ED compound) or its precursor. E
Examples of compounds D include US Pat. No. 4.263. ．．
No. 393, No. 4,278.750, JP-A-56-13
It is described in No. 8736, etc.

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

C+ b H33 (In the formula, (DYE) represents a dye having the same meaning as mentioned above or its precursor.) Details of this can be found in U.S. Pat. No. 3,719,489 and U.S. Pat.
No. 98,783.

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

Examples of yellow dyes: U.S. Pat. No. 3,597,200, U.S. Pat. No. 3,309.19
No. 9, No. 4,013,633, No. 4゜245.028
No. 4,156,609, No. 4,139,383, No. 4,195,992, No. 4,148,641,
4,148.643, 4,336,322, JP-A-51-114930, JP-A-56-71072, R
e5earchDisclosure 7630 (
1978) and No. 16475 (1977).

Examples of magenta dyes: U.S. Pat. No. 3.453.107, U.S. Pat. No. 3.544.54
No. 5, No. 3,932,380, No. 3゜931.144
No. 3.932.308, No. 3.954,476, No. 4,233.237, No. 4,255.509,
No. 4,250,246, No. 4,142,891, No. 4. 207. No. 104, No. 4,287.292,
JP-A-52-106727, JP-A No. 53-23628,
No. 55-36804, No. 56-73057, No. 56
-71060 and those described in No. 55-134.

Examples of cyan dyes; U.S. Patent Nos. 3,482,972 and 3,929.76
No. 0, No. 4,013,635, No. 4゜268.625
No. 4,171,220, No. 4,242,435, No. 4,142,891, No. 4,195,994,
No. 4,147,544, No. 4,148,642, British Patent No. 1,551.138, JP-A-54-9943
No. 1, No. 52-8827, No. 53-47823, No. 53-143323, No. 54-99431, No. 56
-71061, European Patent (Publication>53037, same 5
No. 3040, Re5earch Disclosure
e17630 (1978) and e16475 (1978)
977).

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

Internal latent image type direct positive emulsions include, for example, so-called "conversion type" emulsions that are made by taking advantage of the solubility difference of silver halides, and emulsions that are doped with metal ions, chemically sensitized, or both. "Core/shell type" in which at least the photosensitive sites of the coated silver halide inner core grains are covered with a silver halide outer shell.
There are emulsions, etc., which are described in U.S. Patent No. 2,592.
．． No. 250, No. 3,206.313, No. 3, 761.
No. 276, No. 3,935,014, No. 3.447,9
No. 27, No. 2,497,875, No. 2,563,78
No. 5, No. 3,551,662, No. 4,395,478
No. 4. 431. No. 730, West German Patent No. 2,72
No. 8.108, British Patent Box No. 1.027.146, etc.

In addition, when using an internal latent image type direct positive emulsion, it is necessary to apply nucleation to the surface using light or a nucleating agent after imagewise exposure.

As a nucleating agent for this purpose, U.S. Patent No. 2.563.7
85 and 2.588,982; hydrazides and hydrazones described in U.S. Pat. No. 3,227.552; British Patent Box L 283.
No. 835, JP-A-52-69613, U.S. Patent No. 3.
No. 615.615, No. 3,719.494, No. 3,7
No. 34,738, No. 4,094,683, No. 4. 1
15. Heterocyclic quaternary salt compounds described in No. 122 etc.,
A sensitizing dye having a substituent with a nucleating effect in the dye molecule described in U.S. Pat. No. 3,718,470, U.S. Pat. No. 4,030,925, U.S. Pat. , No. 245,037, No. 4,255.511, No. 4
, No. 266.013, No. 4゜276.364, British Patent Box 2. 012. Thiourea-bonded acylhydrazine compounds described in U.S. Pat. No. 443, etc., and U.S. Pat.
080. No. 270, No. 4,278,748, British Patent Box No. 2゜011.391B, etc., acylhydrazine compounds bonded with a thioamide ring or a heterocyclic group such as triazole or tetrazole as an adsorption group are used. It will be done.

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

For specific examples, see JP-A-59-180550,
No. 60-140335, Re5earch Discl.
osure 17029, U.S. Patent No. 1.846.
No. 300, No. 2,078.233, No. 2゜089.1
No. 29, No. 2,165.338, No. 2.231,65
No. 8, No. 2,917,516, No. 3,352,857
No. 3,411,916, No. 2,295,276, No. 2. 481. No. 698, 2,688.545
No. 2,921゜067, No. 3.282.933, No. 3.397.060, No. 3,660,103,
3゜335.010, 3,352,680, 3.384,486, 3,623,881, 3
, No. 718,470, No. 4,025,349, etc.

(3) Structure of the light-sensitive element In order to reproduce natural colors by the subtractive color method, the dye image-forming substance provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized with the above-mentioned spectral sensitizing dye. A photosensitive layer consisting of at least two of the following combinations is used. The emulsion and the dye image-forming substance may be coated as separate layers, or may be mixed and coated as a single layer. A separate layer is preferable when the dye image-forming material 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
Layer containing a nucleating development accelerator described in No. 1, JP-A-60
It is also possible to increase the color image density by providing a barrier layer as described in Japanese Patent Laid-Open No. 15267, and to increase the sensitivity of the photosensitive element by providing a reflective layer as described in Japanese Patent Application Laid-Open No. 60-91354.

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

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

When a developer is used in combination with a non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent the oxidized form of the developer from diffusing. Specific examples include non-diffusible hydroquinone, sulfonamidophenol, sulfonamide naphthol, and more specifically, Japanese Patent Publications Nos. 50-21249 and 50-2381.
No. 3, JP-A-49-106329, JP-A No. 49-1295
No. 35, U.S. Patent No. 2.336,327, 2°36
No. 0.290, No. 2,403,721, No. 2.544
, No. 640, No. 2,732.300, No. 2,782.
No. 659, No. 2,937,086, No. 3,637,3
No. 93, same 3. 700. No. 453, British Patent Box 55
No. 7,750, JP-A-57-24941, JP-A No. 58-2
It is described in No. 1249, etc. Regarding those dispersion methods, Japanese Patent Application Laid-Open No. 60-238831, Japanese Patent Publication No. 60-1
No. 8978.

When using a compound that releases a diffusible dye with silver ions as described in Japanese Patent Publication No. 7576/1982, it is preferable to include a compound that captures silver ions in the intermediate layer.

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

G) Processing composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is applied to the light-shielding layer provided on the back side of the support or on the opposite side of the photosensitive layer from the processing solution. The photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light shielding agent, a developer, a development accelerator to control development, a development inhibitor, an antioxidant to prevent deterioration of the developer, etc. 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 lithium hydroxide are preferred.

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

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

As the light shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse into the dye image-receiving layer and cause staining. A typical example is carbon blank, but other combinations of titanium white and dyes are also used. This dye may be a temporary light blocking dye that becomes colorless after a certain period of time of treatment.

Preferred developing agents 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 cause less staining.

For example, 1-phenyl-3-pyrazolidinone, 1-I)-
Tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1-(3"-notyl-phenyl)-4-methyl-
Examples include 4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and -p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone.

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

After processing, the cover sheet is peeled off along with the processing solution and the used photosensitive layer. Therefore, it is preferable to perform a surface treatment or apply a suitable adhesive layer to ensure sufficient adhesion with the treatment liquid.

As an example of such an adhesive layer, Japanese Patent Publication No. 61-49658
The hydrophilic layer described in the above is particularly preferred. 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.

The support for the cover sheet used in the present invention may be any smooth transparent support commonly used for photographic materials, such as cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate, etc.
An undercoat layer may also be provided. For the undercoat layer, an undercoat liquid commonly used for photographic light-sensitive materials is used.

The cover sheet may include a layer having the above-mentioned neutralizing function.

The film unit of the present invention is disclosed in Japanese Patent Publication No. 48-33697, Japanese Unexamined Patent Publication No. 48-43317, No. 50-], 536
In the same manner as described in No. 28, No. 52-11027, and No. 56-48629, it is processed into a monosheet using a mask material, a rail material, a surplus liquid trap material, etc.

In particular, in order to facilitate peeling after treatment, Re5ea
rch Disclosure No. 23026 (
It is effective to make a slit as described in (1983). The shape, depth, etc. of the slit are selected depending on the physical properties of the white support used.

The size of the film unit is arbitrary, but in addition to the size of instant films currently available on the market, more compact film sizes and larger film sizes can be used.

In order to take a photograph using the film unit of the present invention, it is necessary to form a mirror image of the subject on the film. For this purpose it is necessary to use mirrors.

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

(Example) Example 1 A carbon blank layer (a carbon blank layer (
Carbon black 3.0g/rd, gelatin 4.5g/
n (including) and titanium oxide layer (titanium oxide 3, Og/
rd, gelatin (containing 1.0 g/I) was coated.

Next, the following layers were sequentially coated on the opposite side of the light-shielding layer of this support to prepare an image-receiving photosensitive sheet.

(1) Cellulose acetate (oxidation degree 55%) 6 g/r/, methyl vinyl ether-maleic anhydride copolymer (weight ratio 6:4) 4 g/n (, titanium dioxide 0.05 g/
m, and a neutralization layer containing 0.82 g/rd of the following compound.

Tortoise (2) Styrene-〇-butyl acrylate acrylic acid-methylol acrylamide 49.7 vs. 42.3
A 4:4 copolymer latex, a 93:3:4 copolymer latex of methyl methacrylate-acrylic acid-methylol acrylamide, and an acid-treated gelatin were mixed in a solid weight ratio of 2. A layer containing 1 g/m.

(3) 3 g/m of the following polymer latex mordant,
Image-receiving layer containing 3 g/rd of gelatin and 0.04 g/rd of formalin.

Furthermore, except that the solid content weight ratio of layer (2) was changed as shown in Table 1, the same films as those of the film unit were used, including Uniso) (8), O, Q, (E), [F], and 0 was created.

Table 1 The samples thus far were tested for adhesion. The purpose of this test is to examine the interlayer adhesion between the image-receiving layer and the timing layer in the area that is not treated with the processing composition in the unexposed area, so there is no need to have a complete photosensitive element; A tape test was performed on the layers. This tape test has a good correlation with the actual adhesion between layers. In this test, first, an image-receiving sheet is cut from the image-receiving layer side with a knife (NT cutter A-300, manufactured by Nippon Transfer Paper ■) to make 30 1 cm square squares. A knit polyester adhesive tape (lh31-AN, manufactured by NEC Corporation) was applied uniformly to the surface of the image-receiving sheet with squares, and then the adhesive tape was peeled off. At this time, the adhesion between the components of the image receiving sheet was evaluated by counting the squares of the image area that were torn off from the adhesive tape side. The smaller the value, the greater the adhesion between the constituent layers.

Furthermore, in order to test the respective maximum image densities pmax, the following layers were newly applied in sequence on top of layer (3) to form a complete photosensitive element.

(4) 0.1g/IT of the following compound? A first release layer consisting of.

CH3-(Clh-C1l)i--(CH2-C)-=
x/y=85/15Cool C00Ctl
lq(5) 51% acetylation cellulose acetate 0.7g
A second release layer consisting of /M.

(6) ethyl acrylate latex 1 g/r
rr, layer containing 2.5 g/m of gelatin;

(7) The following cyan dye-releasing redox compound 0°4.
4g/m, tricyclohexyl phosphate 0.09g
/%, 2.5-di-t-pentadecylhydroquinone 0
．． 008 g/rr+, carbon black 0.05 g/i and gelatin 0.8 g/ffl.

゛.

(8) Titanium oxide 2 g/rd and gelatin 0.5
A light reflective layer containing g/rd.

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

(10) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (silver amount 0.5 g/n (), red-sensitive sensitizing dye, gelatin 0.8 g/n (, layer Nucleating agent (NA) 3.0 μg/M and 2-sulfo-5-
n-pentadecylhydroquinone sodium salt 0.0
4. A highly sensitive red-sensitive emulsion layer containing g/n(,.

(11) 2. 5-di-t-pentadecylhydroquinone 1.2 g/m, polymethyl methacrylate],
, 2 g/n (and gelatin o, 7 g/m).

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

(13) 0.15 g/n (, tricyclohexyl phosphate) of the following magenta dye-releasing redox compound
．． 1 g/m, 2,5-di-t-pentadecylhydroquinone 0.009 g/rrr and gelatin 0.9 g/n
(Containing layer.

H (14) Titanium oxide Ig/m and gelatin 0°25
A light reflective layer containing g/m.

(15) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.0 μm (silver amount 0.12 g/n (),
Green-sensitive sensitizing dye, gelatin 0.25g/rd, layer aIJ
A low-sensitivity green-sensitive emulsion layer containing the same nucleating agent (NA) 1.1 μg/r+ (and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.02 g/%).

(16) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (silver content: 0.35 g/rd),
Green-sensitive sensitizing dye, gelatin 0.7 g/%, nucleating agent (NA) 1.7 μg/n (and 2-sulfo-5
-n-pentadecylhydroquinone sodium salt 0.
High-sensitivity green-sensitive emulsion layer containing 0.04 g/n (.

(17) 2. 5-di-t-pentadecylhydroquinone 0.8g/n (, polymethyl methacrylate 0
．． 8 g/r+ (and an anti-color mixing layer containing 0.45 g/m of gelatin.

(18) A layer containing gelatin o, 3 g/m.

(19) Yellow dye-releasing redox compound with the following structure (0.53 g/rrr), l-lycyclohexylphosphate-1.(0.13 g/r+(), 2.5-
Di-t-pentadecylhydroquinone (0,014g/
rr+) and gelatin (0,7 g/m).

(20) Titanium oxide 0.7g/rrr and gelatin 0
Light reflective layer containing ゜18g/n.

(21) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.1 μm (silver amount 0.25 g/%), blue-sensitive sensitizing dye, gelatin 0.4 g/n (layer 011 Same nucleating agent (NA) 2pg/r+ (and 2-sulfo-
5-n-pentadecylhydroquinone sodium salt 0
．． Low-speed blue-sensitive emulsion layer containing 0.045g/n.

(22) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.7 μm (silver content: 0.42 g/r/);
Blue-sensitive sensitizing dye, gelatin 0.45 g/rd, nucleating agent (NA) same as layer αD 3.3 pg/n (and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.025 g/m A high-speed blue-sensitive emulsion layer containing

(23) 4x10 each of the following ultraviolet absorbers
-' mol/M and gelatin 0.5 g/r+ (ultraviolet absorbing layer).

(24) Protective layer containing 1.0 g/n of gelatin.

Next, an alkaline processing solution containing a light shielding agent was prepared as described below and filled into a processing solution pot.

Processing Cloth The above-mentioned photosensitive sheet and processing liquid pot were combined with transparent polyethylene terephthalate as a cover sheet and an undercoat to form a unit.

The photographic film units 1 to 0 were each exposed from the cover sheet side using a gray wedge, and then developed at 25°C by spreading the processing solution to a thickness of 70 μm using a pressing member. After developing the processing solution, each sample was peeled off with a peeling layer after 2 minutes and 30 seconds, and the density of the transferred image at this time was measured through red (R), green (G), and blue (B) filters, and the maximum image density value was determined. Dr, Dg and Db were obtained.

The above results obtained are shown in Table 2.

As can be seen from Table 2, in film unit O in which the timing layer did not contain gelatin, the adhesion between the timing layer and the image receiving layer was weak, and most of the image receiving layer was peeled off by the tape.

In addition, the film unit 0° [F] with a large amount of gelatin,
0 indicates excellent adhesion but low image density. In comparison, film units ①, 0, 0 of the present invention were excellent image sheets with high adhesion and high image density.

(Effects of the present invention) According to the present invention, a peelable film having excellent adhesion between the constituent elements of the layer having a neutralizing function and the dye image receiving layer, excellent handling properties, and excellent sharpness and color reproducibility. A type color diffusion transfer photographic film unit can be obtained.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment

Claims (1)

[Claims] A color diffusion transfer photographic film unit having, on a support, at least a timing layer containing a water-soluble latex polymer and 1 to 9% by weight gelatin, and a dye-receiving layer adjacent to the timing layer.