JPS5845695B2 - color - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic light-sensitive material, particularly to a diffusion transfer color photographic film and unit that simultaneously provides a positive transferred image and a negative fixed image.

A silver halide emulsion layer is used as a photosensitive element, and the image distribution of a diffusible dye image forming material such as a diffusible dye obtained by exposing and developing this layer is diffusely transferred to another layer, and the dye is fixed there. Photographic methods of forming images, ie so-called diffusion transfer color photography, are well known.

In this photographic method, the transferred dye image is formed in a layer separate from the silver halide emulsion layer, so there is no need to remove residual silver halide and developed silver through steps such as fixing and bleaching. A dye image can be obtained with just one development.

Further, a technique is well known in which a film unit containing a developing solution is loaded into the camera so that processing is started within the camera immediately after photographing, and a dye image can be quickly obtained.

One of these is an integrated film unit that allows the formation of images to be observed sequentially during processing in a bright place outside the camera, and does not require the hassle of peeling off the print layer containing the dye image from the film unit. has been newly announced.

In particular, a method for obtaining a transferred dye image using an aromatic primary amino color developer and a diffusion-resistant coupler that releases a diffusible dye through a coupling reaction with the oxide thereof, and a negative-working silver halide emulsion. Several chemical means of obtaining a positive image distribution of diffusible dyes for use in photosensitive elements are also known.

Furthermore, a dye image is transferred from a light-sensitive element in which a plurality of emulsion layers, in combination with a diffusible dye-donor for subtractive color reproduction, are coated one on top of the other on a single support to a common image-receiving layer. It is also well known.

However, in previously known diffusion transfer color photographic materials, the transfer is limited to producing only one dye image (often a positive image), and the processed light-sensitive element is either left unused or It was designed to be thrown away.

For example, U.S. Pat. No. 3,635,707 and U.S. Pat.
In the diffusible dye-providing light-sensitive element described in No. 27,551, the blue-sensitive, green-sensitive, and red-sensitive negative-working emulsion layers all contain cyan-forming couplers to facilitate development.

Although such photosensitive elements can provide cyan, magenta and yellow transferred color images, the developed photosensitive element contains only silver and cyan images and no color separated information.

Furthermore, U.S. Pat. No. 3,635,707 and French Patent No. 2,065,875 disclose diffusion transfer color photographic materials in which an image receiving element, an opacifying layer, and a light-sensitive element are sequentially coated on one support. Are listed.

It has been extremely difficult to separate and reuse processed photosensitive elements from such integrated films.

However, there is often a desire to use a single photograph as multiple prints.

With color photographic materials, such as those mentioned above, which give only one transfer image, two or more prints must be reproduced by the so-called positive-positive method.

This method involves photographing the required number of transferred images using reversal color photographic material and developing them to create individual duplicate positives, and methods of photographing the transferred images using negative color photographic material and developing them. There are methods such as obtaining a negative original image and printing the necessary number of copies on positive color photographic materials such as color positive film or color paper, but these methods require a lot of work and the reproductions obtained are The image quality of the prints was generally much worse than the original transfer image.

Because of these circumstances, there has been a need for a diffusion transfer color photographic system that can provide a single transferred image through processing immediately after photographing, and can also provide an original image for printing a large number of high-quality images at the same time.

The first object of the present invention is to provide a color photographic material that can provide a positive transferred dye image and a color-separated negative image immediately after photographing. To provide a diffusion transfer color photographic film unit capable of printing a large number of secondary prints with excellent image quality simultaneously with one transfer positive print, if desired.

A third object of the present invention is to provide a diffusion transfer color photographic film that makes it possible to simultaneously prepare a single transfer positive print and a secondary print that can be freely reduced, enlarged, or trimmed as desired. It is about providing.

A fourth object of the present invention is to provide a diffusion transfer color photographic film unit that has color correction capabilities and forms color negative images that provide excellent color separation.

The fifth object of the present invention is to provide a color paper that is designed for color negatives with normal automatic color correction (auto mask) and a color paper that provides a color negative image that can be used as is to obtain an excellent positive image. An object of the present invention is to provide a diffusion transfer film unit.

A sixth object of the present invention is to provide a film unit suitable for a photographic system that produces less waste during the image forming process, has a lower degree of waste dispersion, and has a higher degree of silver recovery.

The seventh purpose of the present invention is to bridge the gap between the conventional ordinary color photography system, which is commercially and technically established, and the diffusion transfer color photography system, which has the advantages of instant photography. The objective is to provide a film unit that is useful for establishing a total photographic system that takes advantage of the characteristics of both.

Other objects of the invention will become apparent from the following detailed description and examples.

It has been found that these objects of the invention are achieved by using a color diffusion transfer material and film unit as described below.

That is, the color photographic material of the present invention contains, on a transparent support, i) a diffusion-resistant coupler that reacts with an oxide of an aromatic primary amino color developer to form a non-diffusible dye; 11) substantially adjacent to the photosensitive silver halide emulsion layer, as a result of development of the photosensitive silver halide emulsion layer, a positive image distribution is obtained; a substantially non-light-sensitive layer containing a diffusion-resistant coupler which reacts with an oxidized aromatic primary amino color developer to form a diffusible dye; and the photosensitive emulsion layer (1
) In order to color correct (mask) unwanted absorption of dyes with a negative image distribution occurring in the non-diffusion layer (11), a non-diffusible dye is provided in the non-photosensitive layer (11) in which dyes with a positive image distribution are formed. It is characterized by containing a sexual coupler.

A preferred embodiment of the color photographic light-sensitive material of the present invention includes the following three elements and produces a positive image transferred by being developed by the action of a pressure tool, and a negative image for color printing by a subsequent desilvering process. A diffusion transfer film unit capable of providing an original image is included in the present invention.

(1) Photosensitive element; the photosensitive material described above (11) Image-receiving element: a colloid layer containing a mordant that receives the formed diffusible dye (iiD processing liquid element; developed in a layer on the photosensitive element and developed Alkaline processing liquid for causing dye formation and diffusible dye transfer A specific example of the light-sensitive material of the present invention comprising three units is as follows.

It has the following three photosensitive units on a transparent support. a blue-sensitive negative developable silver halide emulsion layer containing a diffusible coupler;
(11) A non-photosensitive layer located substantially adjacent thereto and containing a diffusion-resistant coupler which reacts with the oxide of the developer to provide a diffusible yellow dye.

(b) green-sensitive unit (iii) a green-sensitive negative developable silver halide emulsion containing a diffusion-resistant coupler that reacts with the oxide of an aromatic primary amino color developing agent to produce a non-diffusible magenta dye; and ([■) a non-photosensitive layer containing a diffusion-resistant coupler located adjacent thereto which reacts with the oxide of the developer to provide a diffusible magenta dye.

(c) red-sensitive unit M: a red-sensitive negative-working silver halide emulsion layer containing a diffusion-resistant coupler that reacts with an oxidized form of an aromatic primary amino color developer to provide a non-diffusible cyan dye; (■1)
a non-light-sensitive layer located substantially adjacent thereto and containing a diffusion-resistant coupler which reacts with the oxide of said developer to provide a diffusible cyan dye; further a dye having a positive image distribution of each unit; At least one of the non-photosensitive layers to be formed is formed with a non-diffusible dye that absorbs in unnecessary absorption portions of the dye with a negative image distribution occurring in the photosensitive layer, and the exposure amount is reduced in one unit. This is a photosensitive material containing a suitable diffusion-resistant coupler so that the color density of the unnecessary absorption portion is constant regardless of the color density.

A typical route in which the light-sensitive material of the invention is used is as follows: (1) The light-sensitive element is exposed imagewise in a camera either directly from the side opposite the support or through a transparent support from the support side.

([1) The photosensitive element and the image receiving element are arranged so that their surfaces are in contact with each other, and a pressure tool applies pressure to the processing liquid container to break the container, and the processing composition is supplied to both elements in a layered manner.

(by the action of the alkali provided by the 110 processing composition and the aromatic primary amino color developer (or the same developer hydrolytically released from the precursor in the photosensitive element by the alkali)) The photosensitive silver halide emulsion layer is developed depending on the amount of light received.

At this time, the development is negative type.

In other words, the amount of developed silver increases with the amount of light received. ○As the silver halide in the photosensitive emulsion layer is reduced, the color developer is oxidized.
Reacts with the diffusion-resistant coupler in the layer to provide a non-diffusible dye.

(1v) In each photosensitive unit, the result of development of the photosensitive emulsion layer is
Due to the action of the image distribution transfer agent released from the same layer in an imagewise manner, reduction of the silver salt with a positive image distribution from the non-photosensitive layer occurs, and along with this, the diffusion-resistant coupler and the developing agent in the same layer are reduced. A coupling reaction with the oxidant occurs.

The same layer contains a coupler that provides a diffusive dye and a coupler that forms a non-diffusive dye that color-corrects the dye formed in the photosensitive layer of the same unit. The dye diffuses through the layer and/or the processing liquid layer and reaches the image-receiving layer, where it is fixed to form a first-order positive dye image.

Non-diffusible dyes for color correction are immobilized in the photosensitive element.

Here, color correction will be explained.

The term "color correction" used here has the same meaning as the term "masking" or "auto mask" used in normal color negative film, and the principle is based on P, S, A Journal, Vol. 13, 94 Pages (1947) J, Pnot, Sci 14.
(5) 260-277 and 304-310 (1966)
, J, 0. S, A44 (2) 129-134 same 40 (3
) 166-172 (1950), this means that the unnecessary sub-absorption density of the coloring dye is constant in one unit regardless of the exposure amount.

Specifically, in accordance with the present invention, a magenta coupler is included in the light-sensitive emulsion layer in, for example, a green-sensitive unit.

The magenta dye develops color (negatively) according to the amount of exposure, and at the same time as the green density increases, the blue density, which is unnecessary sub-absorption of the magenta dye, also increases.

In order to keep this blue density constant regardless of the exposure amount,
Yellow dye must be generated in inverse (positive) proportion to the amount of exposure.

That is, by adding a coupler that provides a non-diffusible yellow dye to a non-light sensitive layer that is positively developed in the same unit.

It is well known from the above-mentioned literature that such color correction produces a negative image that provides excellent color separation during positive print printing, which will be described later.

Such color correction can also be achieved by using colored couplers in the photosensitive layer, such as those used in color negative films, but colored couplers usually have -N=N-
However, depending on the processing conditions, N2 gas may be generated, making it difficult to achieve uniform development.

M. When transfer of the desired dye image is substantially completed, development in the photosensitive element is stopped either by depletion of the active ingredients of the processing composition or by a development stop timing mechanism incorporated in the film unit. do.

(Depending on the intended use of the vD film unit, sooner or later the light-sensitive element is separated from the image-receiving element.

(The primary positive dye image in the receiver sheet is utilized as is.) The photosensitive element undergoes bleaching (oxidation of developed silver), fixing (solubilization and removal of remaining silver salts), and removal of remaining diffusible dyes. After undergoing post-processing, the final image contains a color-corrected color negative image made of non-diffuse dyes.

M. A color negative image obtained by post-processing a light-sensitive element is used as a transparent original, and is printed on a positive material such as a color positive film or color paper, and developed, and enlarged, reduced or trimmed as desired; In addition, a secondary positive dye image exhibiting excellent color separation that can be printed in large numbers can be obtained.

Some of the terms used in the detailed description of the invention will now be explained.

Regarding diffusivity, a substance is diffusible when an amount of the substance in each layer of a film unit or in a layer formed by processing diffuses into other layers to produce a photographic effect. , the material is said to be non-diffusive when the amount of movement is such that it does not produce substantial photographic effects.

Useful ingredients that have been made non-diffusible by means such as association or polymerization are also called diffusion-resistant. This terminology is in line with the common usage in the field of color photography, and the degree of diffusion depends on the processing. It is appropriate to take the conditions of the photographic layer impregnated with the composition as a standard, and more specifically, in the film unit of the present invention, the conditions of the hydrophilic colloid such as gelatin containing an alkaline aqueous solution with a pH of 10 or more are used as the standard. It is appropriate to judge based on the degree of diffusion.

Color sensitivity and dye absorption are understood according to the widely accepted conventions of subtractive color reproduction.
The present invention can also be applied to a system having auxiliary color correction means in addition to the three primary colors.

The coupler that provides the diffusive dye contained in the non-light-sensitive layer has no absorption that would significantly reduce the sensitivity of the light-sensitive emulsion in the wavelength range to which the unit to which it belongs is sensitive, and furthermore, It is colorless in the sense and to the extent that the element has no absorption that would significantly degrade its performance as a color printing master negative.

The image distribution transfer agent used in the present invention refers to the image distribution transfer agent that moves from the photosensitive emulsion layer that is developed into a negative image to the combined non-photosensitive layer in each photosensitive unit, and by its action causes the negative image of the emulsion layer to be transferred. It plays the role of transmitting information governing the image distribution to the adjacent layer to cause a positive image-like silver reduction corresponding to to appear.

The image distribution forming agent may be a development product that forms a negative image distribution upon development of the photosensitive layer ([);
1) It is contained somewhat uniformly in the photosensitive emulsion layer, but
It may be consumed with the development of the photosensitive emulsion and remain as a result of a positive image distribution, which can be made diffusible by the processing composition.

A positive image-forming agent is added to the non-photosensitive layer of each photosensitive unit so that iron reduction of a positive image appears or is facilitated by the action of an image distribution transfer agent.

Image reversal methods using such an adjacent layer effect include a method in which the development inhibiting effect of a development product from a photosensitive layer is made to act on an adjacent substantially non-photosensitive fog emulsion layer number, and Particularly useful in the film unit of this invention is a method in which developed silver halide emulsion grains are dissolved with a complexing agent and transferred to an adjacent layer containing physical development nuclei.

A positive diffusion transfer dye is produced by treating a non-photosensitive layer containing a diffusible dye-releasing coupler and physical development nuclei provided adjacent to a negative-working silver halide emulsion layer with a developer containing a silver halide solvent. An image is obtained.

As a reversal dye image forming technology using this physical development,
The one disclosed in British Patent No. 904.364 can be used.

Furthermore, it reacts with the oxide of the developing agent, and
- Adjacent to a negative-working silver halide emulsion layer containing a development inhibitor-releasing compound (DIR compound) such as a mercaptotetrazole, a diffusible dye-releasing coupler and a spontaneously reducible metal salt, especially for poorly water-soluble silver Photosensitive elements provided with a layer containing salt are disclosed in U.S. Pat. No. 3,227,551, U.S. Pat. No. 3,227,554, U.S. Pat. gives a positive diffusion transfer dye image as published in No.

Suitable spontaneously reducible, sparingly water-soluble silver salts include light,
Halogens such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodobromide, etc. that have been fogged by the action of radiation such as X-rays and gamma rays, or by the chemical action of reducing agents, active sulfur compounds, etc. Silver chloride dispersion: includes a sparsely soluble sulfide or a silver salt coexisting with a colloidal dispersion of a metal such as silver or gold, such as a dispersion of silver chloride or silver thiocyanide.

The diffusion-resistant coupler that provides the non-diffusible dye contained in each light-sensitive silver halide emulsion layer of the light-sensitive element of the present invention has the condition that it provides a dye that has main absorption in the spectral sensitization wavelength range of the combined emulsion. These couplers are substantially the same as the diffusion-resistant couplers conventionally used in conventional color photographic materials and can be selected from those previously described for conventional color photographic materials. .

The diffusion-resistant couplers which provide the color-correcting non-diffusible dyes of the present invention are substantially the same as the diffusion-resistant couplers also used in conventional color photographic materials, and in each unit:
It can be selected from couplers that provide a dye corresponding to the unnecessary sub-absorption portion of the dye produced by the coupler used in the light-sensitive emulsion layer.

Normally, a yellow coupler is used in a green-sensitive unit, and a magenta coupler is used in a red-sensitive unit, but they are not limited to this. For example, in a green-sensitive unit, a magenta coupler is used.
It is also possible to use a mixture of two or more couplers, such as a yellow coupler and a cyan coupler.

The amount used is about 0.05 to 0.5, preferably about 0.1 to 0.3 in molar ratio to the coupler used in the photosensitive layer.

Color-correcting diffusion-resistant couplers are preferably used in addition to the same layer as the non-light sensitive layer that is normally positively developed, but may also be used in addition to a layer substantially adjacent to the non-light sensitive layer. It is possible.

Diffusion-resistant couplers that provide non-diffusible dyes used in the present invention include coupler core residues and carbon atoms that can react with oxides of aromatic primary amino color developers to form dye structures. It is a compound that has eight or more hydrophobic residues.

Coupler core residues include phenol residues, aniline residues, linear or cyclic active methylene group-containing residues, C, E, Mees, T, H, J
ames: 6 The Theory of the Photographic Process”
Photographic Process) 3rd edition (
3rd, ) Ed, (Macmi Han.

1966) P2S5-394, and W, Peltz (Pel
z): “Farbkuppler” Akfa Mitutilesian Leverkusen (Farbkuppler)
AgfaMitteilungen Lever
kusen) I [[, 111-175 (Spring
er, 1961) and Ircono et al. can be used.

Hydrophobic residues reduce the solubility of couplers in aqueous media, increase the cohesive force between coupler molecules or with oily substances, and increase intermolecular association, etc. in the photographic layer. decreases the diffusivity of

Useful hydrophobic residues include straight chains such as n-octyl, 2-ethylhexyl t-octyl n-nonyl triisopurpur, decyl, n-dodecyl, 1,1-dimethylhexadecyl, stearyl groups, or branched alkyl groups, cycloalkyl groups such as 2,4-di-n-amylcyclohexyl; alkenyl groups such as oleyl; aryl groups such as terphenyl; 8,9-dichloro-heptadecyl, perfluorooctyl; a haloalkyl group such as 3-n-dodecyloxypropyl, or an alkoxyalkyl group such as 2-n-dodecylthiopropyl, or an alkylthioalkyl group; 4-t-
Amylphenyl, p-n-octylphenyl, 2.4-
Alkylaryl groups such as di-t-butylphenyl group, 2,4-di-t-amylphenyl group, 3-n-pentadecylphenyl group; 3-n-hexyloxyphenyl; 3-
Examples include alkoxyaryl groups such as n-dodecyloxyphenyl and 2-n-dodecyloxyphenyl groups.

These hydrophobic residues may be bonded directly to the coupler core group, or alkylene groups; arylene groups; oxymethylene groups.

Oxyalkyl groups such as α-oxyethyl, α-oxypropyl, γ-oxypropyl, and ω-oxybutyl groups (
-〇-alkylene group-); amido group, carbamyl group; sulfonamide group; sulfamyl group; ureido group: imide group such as group; carbonyl group; carbonyloxy group; oxycarbonyl group; sulfonyl group; sulfonyloxy group; oxy In a coupler core that does not have a water-solubilizing group such as a C sulfo group or a carboxyl group that may be bonded via a divalent linking group such as a sulfonyl group, the hydrophobic group is located at the coupling position, and the aromatic It may also be included in the substituents that can be removed by the oxide of the Group primary amino color developer.

Diffusion-resistant couplers used in the present invention may contain water-solubilizing groups such as sulfo groups, carboxyl groups, and sulfonamide groups.

The so-called Fis-
In cher (Fisher) type couplers, the hydrophobic residue preferably contains 12 to 32 carbon atoms, and in new oil-based so-called protected type couplers that do not have such hydrophilic groups, the hydrophobic residue contains 12 to 32 carbon atoms. 8 to 32
Specific examples of diffusion-resistant groups (ballast groups) comprising a hydrophobic residue and a linking group that are particularly preferable for the diffusion-resistant couplers used in the present invention preferably contain 0 carbon atoms: n-lauroylamide group, fatty acid amide group such as stearoylamide group, oleoylamide group; N-laurylcarbamyl group, N-methyl-N-
Carbamyl group substituted with an alkyl group such as stearylcarbamyl group, oleylcarbamyl group, or alkenyl group; US Pat. No. 3,337,344, US Pat.
, 418,129; α-(2°4 di-t-amylphenoxy)acetamide groups as illustrated in U.S. Pat. No. 2,600,788, UK; α-(2,4-di-5ec-amylphenoxy)acetamide group described in U.S. Pat. No. 1,149,514, U.S. Pat. No. 2,908,5
α- or γ-(3-pentadecylphenoxy)butyramide group, α-dimethyl-α-
Aliphatic amide group substituted with an alkylaryloxy group such as (3-pentadecylphenoxy)acetamido group: substituted with a water-solubilizing group such as 1-octadecenyl-succine-monoamide group, α-sulfo-stearoylamide group aliphatic amide group; alkoxy group such as octadecyloxy group; US Pat. No. 3,409,439
and sulfamyl groups such as N,N-dioctylsulfamyl.

As the coupler nucleus that provides the yellow dye used in the present invention, α-acylacetamide residues are useful, and α-acylacetanilide residues are particularly useful.

These residues are bonded to the anti-diffusion group containing the above-mentioned hydrophobic residue at the acyl, amide (anilide), and releasable residue at the coupling position.

In addition to the above, the coupler core includes a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkoxycarbonyl group, a sulfamyl group, an acylamido group, a sulfonamide group, an amino group,
It may be substituted with a substituent such as a nitro group or a cyano group.

Diffusion-resistant couplers that provide non-diffusible, yellow dyes advantageously used in the present invention include Mees Jamesl, supra.
It can be selected from the conventionally known ones described in ``Line Skin'' and Pe1z.

BIO81901, FIAT 943, and Special Publication Showa 4
α with a water solubilizing group described in No. 0-6,030
-Benzoylacetamide coupler; US Patent 2, 4
No. 07.210, No. 2,875,057, No. 3,40
No. 9,439, No. 3,551,155, No. 3.551
, No. 156, No. 3,649,276, No. 3.685,
995, the lipophilic α-benzoylacetamide couplers described in British Patent No. 1,286.411;
α-pivaloylacetamide type couplers such as those described in US Pat. No. 3,265,506 are particularly useful in the practice of this invention.

Furthermore, one α-1 hydrogen atom of these α-acylacetamide groups is an arylthio group, a heterocyclic thio group; a halogen atom such as fluorine described in U.S. Pat. No. 3,277.155; 253,924; U.S. Pat. No. 3,447,928
Acyloxy group described in US Pat. No. 3,40
Aryloxy groups as described in US Pat. No. 8,194; Sulfonyloxy groups as described in US Pat. No. 3,415,652; and West German Patent Application (OLS) 2,31
It may be substituted with a residue capable of forming an anion and leaving it off, such as the diacylamino group described in No. 3,461.

Representative preferred yellow couplers include:
The following can be mentioned.

Y-1) α-(4-stearoylaminobenzoyl)-aceto-3,5-dicarboxyanilide Y-2) α-[4-(α-octadecenylsuccine-monoamide)-benzoylioaceto-2 -Methoxy-
5-Carboxyanilide Y-3) α-(4-octadecyloxybenzoyl)-aceto-2-methoxy-5
-Sulfoanilide potassium salt Y-4) d, -(3-Cα-(2,4-di-t-
amylphenoxy)butyramideiobenzoyl)-acet-2-methoxybenzoyl Y-5) α-(4-methylbenzoylcet-2-chloro-5-[α-(2,4-di-t-amylphenoxy)- butyramide]-anilide Y-6) α-benzoyl-aceto-2-chloro-5
-dodecyloxycarbonylanilide Y-7) α
-(2-methylbenzoyl)-aceto-2-chloro-5
-tetradecyloxycarbonylanilide Y-8) α-(2-methylbenzoyl)-aceto-
2-chloro-5-(N,N-bis-(2-ethylhexyl)sulfoamylcoanilide Y-9) α-(2-
methoxybenzoyl)-α-(5,5-cy)f-3
-hydantoinyl)-aceto-2-chloro-5-[α-
(2,4-di-t-amylphenoxy)-butyramidetuarylide Y-10) α-pivaloyl-α-(4-carboxyphenoxy)-aceto-2-chloro-5-[α-(3-
pentadecylphenoxy)-butyramide]-anilide The coupler core that provides magenta dye used in the present invention includes 5-pyrazolone, pyrazolobenzimidazole, indacilone, 1-H-pyrazolo(3,2-c
)-s-triazole residues are useful, especially 1
-Aryl-5-pyrazolones are particularly useful.

The 1st position is unsubstituted or substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, a carbamyl group, a sulfamyl group, an alkoxycarbonyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, etc. 5- with phenyl group
Pyrazolone compounds; and 5-pyrazolone compounds in which the 3-position is substituted with an alkyl group, an alkoxy group, an aryloxy group, an amino group such as anilino, an acylamino group, a sulfonamide group, a ureido group, a carbamyl group, an alkoxycarbonyl group, etc. are particularly preferably used according to the invention.

In addition, acylated 5-pyrazoles corresponding to these can also be used in the same manner.

Advantageously, the diffusion-resistant group containing a hydrophobic residue is included in the 1- or 3-position substituent of the 5-pyrazolone.

Diffusion-resistant couplers providing non-diffusible magenta dyes advantageously used in the present invention include Mees-James, supra.
and Pe1z's line skin, etc., which are known from the literature.

BIO81901. l-phenyl-3-alkyl couplers with water-solubilizing groups as described in FIAT 943; 3-alkoxy-5-pyrazolone couplers as described in U.S. Pat. No. 2,439,098; Patent No. 2,600,788, Patent No. 3,062,6
3-acylamino-5-pyrazolone couplers described in British Patent No. 956,261 and West German Patent Application (OLS) No. 2,015,867; Coupler: 3-arylureido-5-pyrazolon cuff described in U.S. Pat. No. 3,558,319.

are particularly useful in the practice of the present invention.

Furthermore, one hydrogen atom of the active methylene group at the 4-position of these 5-pyrazolones is an arylazo group; a heterocyclic ab group; an arylthio group; a heterocyclic thio group;
Thiocyano groups as described in U.S. Pat. No. 924; aryloxy groups as described in U.S. Pat. No. 3,419,391; acyloxy groups as described in U.S. Pat. No. 3,311,476; Triazolyl group described in US Pat. No. 415,652; and alkoxycarbonyloxy group; US Pat. No. 2,706.683, US Pat.
Nos. 618,641 and 3.468,666 may be substituted with a residue capable of being eliminated by an oxide of an aromatic primary amino color developer such as an arylidene group or an alkylidene group. .

Representative preferred magenta-forming couplers include the following.

M-1) 1-(3-sulfo-4-phenoxyphenyl)
-3-heptadecyl-5-pyrazolone potassium salt M-2) 1-phenyl-3-(α-octadecenylsuccine-monoamide-5-pyrazolone M-3) 1-phenyl-3-(2-chloro- 4-[β-N(4n-dodecylphenyl)acetylamino-p-carboxy-propylaminocoanilino)-5-pyrazolone M-4) 1-phenyl-3-(3-(α-(2゜4-
di-5ec-amylphenoxy)acetamide]benzoylamide)-5-pyrazolone M-5) 1-(2
,4,6-)lichlorophenyl)-3-(3-(α-(
2,4-di-t-amylphenoxy)-butyramide]benzoylami 4-5-pyrazolon M-6) 1-phenyl-3-(3-(α-(3-pentadecylphenoxy)-butyramide) phenylureido-
5-pyrazolone M-7) 1-(2,6-dichloro-4-methoxyphenyl)-3-(3-(α-(2,4-di-t-amylphenoxy)-butyramide] phenylureido-5-
Pyrazolone M-8) 1-(2,4,6-)lichlorophenyl)
-3-(2-chloro-5-myristoylamido-anilino)-5-pyrazolone M-9) 1-phenyl-3-(2-chloro-5-tetradecyloxycarbonylanilino)-5-pyrazolone M-10 ) 1-(2,4,6-drichlorophenyl)-3-(3-(α-(2,4-di-amylphenoxy)acetamitetrabenzamide)]-5-pyrazolonyl(4)-benzyl carbonate M -11) 1-(2,4,6-dolichlorophenyl)-3-(2,4-dichloroanilino)-4-(3-N
-octadecylcarbamylphenylthio)-5-pyrazolone M-12) 1-(2,4,6-)lichlorophenyl)-3-(3-(α-(2,4-di-amylphenoxy)-acetamide ) benzamide)-4-(4
-Methoxyphenylazo)-5-pyrazolone Compounds having a phenolic hydroxyl group, especially phenol-based and α-naphthol-based compounds, are useful as the coupler nucleus that provides the cyan dye used in the present invention, among which 〇 Particularly useful are phenol derivatives substituted in the 1- or m-position by an acylamino group, and α-naphthol derivatives substituted in the 2-position by a carbamyl group.

It is useful that the diffusion-resistant group containing a hydrophobic residue is introduced into the coupler molecule as an acylamino group or a carbamyl group.

In these couplers, the position para to the hydroxyl group is the site of reaction with the oxidized aromatic primary amino color developer, and this position can be unsubstituted or substituted by a residue that can be removed by the oxidized developer. can be done.

Other nuclear positions include halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, acylamino groups, sulfonamide groups, carbamyl groups, sulfamyl groups, alkoxycarbonyl groups, cyan groups, nitro groups, carboxyl groups,
It can be substituted with a sulfo group, a heterocyclic group such as 2-triazolyl or 2-imidazolyl, and the like.

The phenolic hydroxyl group may be acylated in a form that can be hydrolyzed by an alkaline aqueous solution.

Diffusion-resistant couplers giving non-diffusible cyan dyes advantageously used in the present invention can be selected from those known from the literature such as the Mees-James and Pe1z line tables mentioned above.

BIO81901゜2-Nututamide coupler with sulfo group described in FIAT943; US Patent 2,
367.531, 2,369,929, 2,4
Acylaminophenolic couplers described in U.S. Pat. No. 23,730; diacylaminophenolic couplers described in U.S. Pat. No. 2,772,162 and U.S. Pat. No. 2,895,826; U.S. Pat. Oil-soluble 2-natutamide couplers described in the issue;
N as described in U.S. Pat. No. 3,591,383,
N-disubstituted natutamide couplers and the like are particularly useful in the practice of this invention.

The 4th position of these phenol derivatives is a halogen atom such as fluorine or chlorine; an arylazo group; a heterocyclic azo group; an arylthio group; a heterocyclic thio group; an alkoxy group; an aryloxy group; described in U.S. Pat. No. 3,253,924. thiocyano groups; imido groups described in U.S. Pat. No. 3,458,315; and U.S. Pat. No. 3,419,39
It may be substituted with the aminomethyl group described in No. 0.

Representative preferred cyan-forming couplers include:
The following can be mentioned.

C-1) 1-hydroxy-4-sulfo-N-octadecyl-2-naphthamide-sodium salt C-2) 1-hydroxy-2'-(N-methyl-N-octadecylamino)-5'-sulfo-2 -Naphthamide, potassium salt C-3) 1-Hydroxy-N-Cβ-(α-sulfo-stearoylamido)ethyl]-2-naphthoanilide.
Sodium salt C-4) 1-hydroxy-N-(γ-(2,4-di-
t-amylphenoxy)propyl-2-naphthamideC-5)1-hydroxy-4-chloro-N-dodecyl-
2-naphthamide C-6) 1-hydroxy-2'-chloro-5'-[(β
-(2,4-di t-amylphenoxy)ethoxy)-carbonyl]-2-naphthoanilide C-7) 4.6-dichloro-5-methyl-2-[α
-(2,4-di t-amylphenoxy]-butyramide]phenol C-8)2-hebutafluorobutyramide-5-[α-(2
,4-di-t-amylphenoxy)-caproylaminocophenol C-9) 1-hydroxy-4-(2-ethoxycarbonylphenylaso)-N-(2-nyf-rhexyl)-2-naphthamide Development inhibitor-releasing compounds (so-called DI) used in the invention
R compound) is a coupler that releases a substituent that becomes a development inhibitor from the reactive position upon coupling reaction with the oxide of (1) aromatic primary amine color developer, or (1)
1) A compound that releases a development inhibitor in the form of a developed image, such as a compound that releases a development inhibitor through a second reaction with a processing acid such as hydroxide ion or sulfite ion in an oxidized state during development. It is a compound that donates.

The DIR compound used in the present invention must contain a hydrophobic residue having 8 or more carbon atoms in its molecule and be diffusion resistant.

The hydrophobic residues can be the same as those used in conventional diffusion-resistant couplers.

The detachable group of the DIR compound may already have a chemical structure having a development inhibiting effect before detachment, or may complete the development inhibiting chemical structure only after detachment.

Useful development inhibitors include iodo ions, alkyl mercaptans, aryl mercaptans, heterocyclic mercaptans, triazoles, imidazoles, and purine core compounds, particularly mercaptotriazoles, mercaptotetrazoles, and mercaptopyrimidine. mercaptothiazines, mercaptooxazoles,
Mercaptoimidazoles, mercaptothiazoles,
Benzotriazoles have a large suppressive effect.

A specific example is 4-nitrothiophenol 2-
Ethoxycarbonylthiophenol, 1-phenyl-5
-mercaptotetrazole, 2-mercaptobenzothiazole, 2-mercapto-4,6,6-)limethylpyrimidine 5-brombenztriazole, and the like.

Rather than being included in the DIR compound while already having a structure capable of exerting a development-inhibiting effect, these inhibitory bodies contain chemical bonds that block the development-inhibiting center (e.g., iodine, carbon bonds, thioether bonds, N-to-IJ It is preferable that the compound be introduced into the reaction position of the DIR compound via an azolyl bond (bond between a group and a carbon group) in order not to interfere with the development of unexposed areas.

DIR couplers advantageously used in the present invention include U.S. Pat.
, 227.551, 3.227.554, 3,
617,291, or colorless coupling products and development inhibitors as described in U.S. Pat. No. 3,632,345. It may also be something that gives

Representative preferred DIR couplers include the following.

DIRY-1) α-pivaloyl-α-(l-phenyl-5-tetrazolylthio)-2-chloro-5-[γ-
(2,4-di-t-amylphenoxy)butyramide]
Acedoanilide DIRY-2) α-(4-methoxybenzoyl)-
α-(1-phenyl-5-tetrazolylthio-2-chloro-5-[α-(2,4-di-t-amylphenoxy)butyramide]acedoanilide DIRM-1) 1-(4-(α-(2, 4-di-
1-amylphenoxy)butyramido)phenyl)-3-
(1-piperidino)-4-(1-phenyl-5-tetrazolylthio)-5-pyrazolone DIRM-2) 4-(2-benzotriazolyl)-
1-(2,4,6-dolichlorophenyl)-3-(3-
(α-(2,4-di-1-amylphenoxy)acetamylopentzamide]-5-pyrazolone DIRC-1) 1-Hydroxy-4-(1-phenyl-5-tetrazolylthio)-N-(γ-( 2,4-d
it-amylphenoxy)propyl-2-naphthamide DIRC-2) 1-hydroxy-4-(2-nitrophenylthio)-N-octadecenyl-3'.

5'-dicarboxy-2-naphthamide DIRU-
1) α-(l-phenyl-5-tetrazolylthio)
-2-Sulfo-4-n-hexadecyloxy-acetophenone potassium salt The DIR hydroquinones advantageously used in the present invention include U.S. Pat. 379,529, which are nuclear-substituted hydroquinone derivatives with development inhibitor groups.

These derivatives oxidized during development release development inhibitors by the action of nucleophiles such as hydroxide ions and sulfite ions in the processing solution. Representative examples of preferred DIR/hydroquinones include the following: Things can be given.

DIRH-1) 2-1-octyl-5-(l-phenyl-5-tetrazolylthio)-hydroquinone D, IRH-2) 2-n-pentadecyl-5-(1
-Phenyl-5-tetrazolylthio)-hydroquinone The coupler providing the diffusible dye used in the present invention is a reactive non-diffusible compound capable of a coupling reaction with an oxidized developing agent, and as a result of the coupling reaction, development A soluble and diffusible dye can be released into the treatment composition and is represented by the general formula below.

(Cp)-L-(Bl) Cp represents a coupling-active moiety in which the coupling position is substituted by a (Bl)-L-residue, and the color developer used in combination has a sulfo group, a carboxyl The Cp residue has at least one water solubilizing group (such as a sulfo group, a carboxyl group, a sulfonamido group) in a non-coupling position.
Examples of the coupling-reactive structural moiety used as the OCp having the molecule include many functional groups known to be capable of oxidative coupling with aromatic primary amino color developing agents.

Those described above as coupler cores for couplers that provide non-diffusible dyes can be used as well.

Examples include phenols, anilines, cyclic or chain active methylene compounds, or hydrazones.

Specific examples of particularly useful reactive structural moieties include phenol substituted with an acylamino group, ■-hydroxy-2-naphthoic acid amide, N,N-dialkylaniline aryl, alkoxy, aryloxy, amino, acylamino , ureido, 1-aryl-5-pyrazolones substituted by sulfonamide groups, pyrazolobenzimidazole, pyrazolotriazole α-cyanoacetophenone, α-acylacetanilide.

Linking groups whose bond with the coupler structure is broken by the oxidized oxidizing agent include azo group, azooxy group, mercury group (-Hg-), oxy group, thio group, dithio group, triazolyl group, and diacylamino group. , acylsulfone amino group (/\), A0=C802ゝ7' syloxy group, sulfonyloxy group, and alkylidene group.

Among these, oxy groups, thio groups, dithio groups, diacylamino groups, acyloxy groups, etc. that leave as anions are
It is useful because it releases a large amount of diffusible dye.

The coupling position of the coupling structure of phenol and naphthol is preferably substituted with a group bonded by an oxy group, thio group, or diacyloxy group, and the coupling position of pyrazolone is substituted with a group bonded with an azo group, thio group, or acyloxy group The coupling positions of acetanilide are preferably substituted with an oxy group, a thio group, or a diacylamino group, respectively.

The hydrophobic residue contained in the residue represented by f31 is essentially the same as the hydrophobic group of the coupler that provides the non-diffusible dye described above, and is capable of creating cohesive forces between coupler molecules in an aqueous medium. and non-diffusible in the hydrophilic colloids constituting the photosensitive material.

As the hydrophobic residue, substituted or unsubstituted alkyl groups, alkenyl groups, aralkyl groups, and alkylaryl groups having 8 or more carbon atoms are advantageously used.

For example, lauryl group, stearyl group, oleyl group, 3-
Examples include n-pentadecylphenyl group and 2°4-di-t-amylphenoxy group.

These hydrophobic residues bind to residues such as aryl groups or heterocyclic groups directly or through divalent bonds such as amide bonds, ureido bonds, ether bonds, ester bonds, and sulfonamide bonds to bind Bl. form.

The water solubilizing group contained in the residue represented by cp is
It is an acidic group that substantially dissociates in the treatment composition, or a precursor group that provides this upon hydrolysis.

In particular, acidic groups having a pKa of 11 or less are useful.

Such groups include sulfo group, lactic acid ester group (-
0-803H), carboxyl group, sulfonamide group, diacylamino group, cyanosulfonamino group, phenolic hydroxyl group, etc.

When the diffusible dye-releasing coupler used in the present invention reacts with an oxidized developing agent, the bond is cleaved, and the bond between CP-2 and the developing agent is cleaved.
1-1-li) gives a non-diffusible, substantially colorless separation product derived from 1-1-li).

This soluble dye diffuses into the image receiving layer to form a dye image.

Specific examples of diffusible dye-providing couplers useful in the present invention include the following.

α-(4-methoxybenzoyl)-α-(3-octadecylcarbamylphenylthio)-3,5-di-carboxyacedoanilide α-pivaloyl-α-(3-octadecylcarbamylphenylthio)-4 -Sulfoacedranilide potassium salt 1-phenyl-3-(3,5-di-carboxyanilino)-4-(3-octadecylcarbamylphenylthio)-5-pyrazolone 1-phenyl-3-(3, 5-di-sulfobenzoylamino)-5-(2-hydroxy-4-n-pentadecylphenylazo)-5-pyrazolone 1-phenyl-(4
-(3,5-di-carboxybenzamido)phenyl]-3-ethoxy-4-(3-octadecylcarbamyl-t)-5-pyrazolone 1-hydroxy-4-(3-octadecylcarbamylphenylthio)- N-ethyl-3,5-di-carboxy-2-naphthoanilide -hydroxy-4-(n-octadecylsuccinamide) -N-ethyl-3',5
Other examples and methods of synthesis of '-di-carboxy-2-naphthanilide diffusible dye-releasing couplers include:
British Patent No. 840,731, British Patent No. 904,364, 1,
No. 085,631, US Pat. No. 3,476.563, US Pat. No. 3,644,498, and US Pat. No. 3,419,391.

The aromatic primary amino developer used in the present invention includes p
-aminophenol and p-phenylenediamine and derivatives are advantageously used.

Especially 2-chloro-4-aminophenol, 2,6-diproro-4-aminophenol, 4-amino-N.

N-diethyl-3-methylaniline, N,N-diethyl-p-phenylenediamine, N-ethyl-β-methanesulfonamidoethyl-3-methyl4-aminoaniline, 4-amino-N-ethyl-N-( δ-sulfobutyl)
-Aniline, 4-amino-N-ethyl-N--(β-hydroxyethyl)aniline, 4-amino-3-methyl-
N-ethyl-N-(β-hydroxyethyl)aniline,
4-amino-N-ethyl-N-(β-carboxyethyl)aniline, 4-amino-N,N-bis(β-hydroxyethyl)-3-methyl-aniline, 3-acetamide-
4-amino-N, N-(β-hydroxyethyl)aniline, 4-amino-N-ethyl-N-(2,3-dihydroxypropyl)-3-methylaniline, 4-amino-N
, N-diethyl-3-(3-hydroxypropoxy)aniline, 4-amino-N-ethyl-N-(β-hydroxyethyl)-3-methoxyaniline, and hydrochloric acid, sulfuric acid 1, oxalic acid, Salts such as p-)luenesulfonic acid are useful.

Further, precursors of developing agents such as 5chiff bases of these anilines and phthalic acid imides are useful because they can be added to photosensitive elements.

The diffusion-resistant couplers used in the present invention can be dispersed in the hydrophilic colloid carrier in various ways depending on the type of donor.

For example, a coupler having a dissociable group such as a sulfo group or a carboxyl group can be dissolved in water or an alkaline aqueous solution and then added to the hydrophilic colloid solution.

Couplers that are difficult to dissolve in aqueous media and easy to dissolve in organic solvents are
A solution obtained by dissolving in an organic solvent is added to a hydrophilic colloid solution and dispersed into fine particles by stirring or the like.

Suitable solutions include ethyl acetate, tetrahydrofuran,
Methyl ethyl ketone, cyclohexane, β-butoxy-
Examples include β-ethoxyethyl acetate, dimethylformamide, dimethylsulfoxide, 2-methoxyethanol tri-n-butyl phthalate, and the like.

Among these dispersing solvents, those with relatively low vapor pressures either evaporate during drying of the photographic layer, or
2,027 and 2,801,171.

Among these dispersion solvents, those that are easily soluble in water are US Pat.
, No. 949,360 and No. 3,396.027.

In order to stabilize the coupler dispersion and facilitate the dye image forming process, it is advantageous to incorporate the coupler into the photosensitive element in a solvent that is substantially insoluble in water and has a boiling point of 200 DEG C. or higher at normal pressure.

Suitable high-boiling solvents for this purpose include triglycerides of higher fatty acids, aliphatic esters such as di-octyl adipate, phthalic acid imides such as di-n-butyl phthalate, tri-cresyl phosphate, tri-n
- Phosphate esters such as hexyl phosphate, N
, N-diethyl laurylamide, 2,4-
These include hydroxy compounds such as di-n-amylphenol.

In order to further stabilize the dispersion of the coupler and facilitate the dye image formation process, it is advantageous to incorporate a philic polymer with the coupler in the photosensitive element. Suitable philic polymers for this purpose include Schlag: Phenol/formaldehyde condensate; poly-n-butyl acrylate;
Copolymer of n-butyl acrylate and acrylic acid;
Examples include n-butyl acrylate and copolymers of styrene and methacrylamide.

These polymers may be dissolved together with the coupler in an organic solution and then dispersed in a hydrophilic colloid, or the hydrosil of the polymer prepared by emulsion polymerization or the like may be added to a hydrophilic colloid dispersion of the coupler. good.

Coupler dispersion is generally reduced more effectively under large shear forces.

For example, a high-speed rotary mixer, a colloid mill, a high-pressure milk homogenizer, the high-pressure homogenizer disclosed in British Patent No. 1,304,264, an ultrasonic emulsifier, etc. are useful.

Dispersion of the dye image donor is significantly aided by the use of surfactants as emulsifying aids. Surfactants useful in dispersing the dye image donor used in the present invention include sodium triisopropylnaphthalene sulfonate; Sodium dinonylnaphthalene sulfonate Sodium p-dodecylbenzenesulfonate, dioctyl sulfosuccinate, sodium salt, cetyl sulfate sodium salt,
There are anionic surfactants disclosed in Japanese Patent Publication No. 39-4,293, and the combination of these anionic surfactants and higher fatty acid esters of anhydrohexitol is disclosed in U.S. Pat. No. 3,676.141. It shows particularly good emulsifying ability.

The silver halide emulsion used in the present invention is a colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof, and the halogen composition is The iodide content is selected depending on the purpose of use and processing conditions of the photosensitive material, but the iodide content is 1 to 10 mol, and the chloride content is 30 mol.
Silver iodobromide or silver chloroiodobromide emulsions in which the molar ratio is less than or equal to 1, and the remainder is bromide are particularly desirable.

Those having an average particle diameter in the range of about 0.1 micron to about 2 microns are useful, and depending on the intended use of the photosensitive material, it is desirable that the particle diameter is uniform.

The particles can be cubic, octahedral, or mixed.

These silver halide emulsions are, for example, glafkides emulsions (P, Glafkides).
Author: Chimie Photography)
(2nd edition, 1957; Paul Montct, P.
aris) made by known and commonly used methods as described in Chapters 18 to 23.

That is, a soluble silver salt such as silver nitrate and a water-soluble halide such as potassium bromide are reacted in a protective colloid solution such as gelatin, and the presence of excess halide or a silver halide solvent such as ammonia is removed. cause crystal growth to occur at the source.

In this case, a precipitation method such as a single or double jet method or a pAg control double jet method can be used.

Removal of soluble salts from the emulsion can be achieved by washing the cooled and solidified emulsion with water, dialysis, addition of a precipitating agent such as an anionic polymer having a sulfone group, a sulfate ester group, a carboxyl group, or an anionic surfactant for adjustment or protection. This is achieved by using an acylated protein such as phthaloyl gelatin as a colloid, and by precipitation by conditioning.

The silver halide emulsion used in the present invention contains natural sensitizers contained in gelatin, sodium thiosulfate or N,
In combination with sulfur sensitizers such as N,N'-trimethylthiourea, gold sensitizers such as -valent gold thiocyanate complexes, thiosulfate complexes, or reduction sensitizers such as stannous chloride, hexamethylenetetramine. It is desirable that the film be chemically sensitized by heat treatment.

The present invention also includes emulsions that tend to form latent images on grain surfaces.
It is also possible to use emulsions that easily form latent images inside the grains, such as those described in No.

The silver halide emulsion used in the present invention includes 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene, 5-nitroimidazole, 1-phenyl-5-mercaptotetrazole, 8-chloromercuriquinoline, It may be stabilized by additives such as benzenesulfinic acid and pyrocatechin.

In addition, inorganic compounds such as complex salts of platinum group elements such as cadmium salts, mercury salts, and palladium chlorocomplex salts are also useful for stabilizing the photosensitive material of the present invention.

Furthermore, the silver halide emulsion used in the present invention may contain a sensitizing compound such as a polyethylene oxide compound. The silver halide emulsion used in the present invention may optionally contain an optical sensitizing dye. Can have expanded color sensitivity.

Useful optical sensitizers include cyanines, merocyanines, holopolar cyanines, styryls, hemicyanines,
These include oxanols and hemioxanols.

Specific examples of optical sensitizers include the aforementioned P. Grafkide (
Chapters 35-41 of P-Glafkides) and The Cyanili Dice and Related Compounder (Th) by F. M. Hamer.
e Cyanine Dyesand Re1ated
Compounds) (Interscience)
It is described in.

In particular, the nitrogen atom in the nucleus is a hydroxyl group, a carboxyl group,
Cyanines substituted with aliphatic groups having sulfo groups, such as U.S. Pat. Nos. 2,503,776 and 3
, 459,553 and 3,177.210 are particularly useful in the practice of the present invention.

The silver halide emulsion layer used in the present invention and the processing liquid permeable layers such as the layer containing the dye image donor, the protective layer or the auxiliary layer such as the intermediate layer contain a hydrophilic polymer as a binder. ing.

Suitable hydrophilic polymers include gelatin, casein,
Gelatin modified with acylating agents, proteins such as albumin grafted with vinyl polymers, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, partial hydrolysates of polyvinyl alcohol or polyvinyl acetate, Molecular non-electrolytes such as pyrivinylpyrrolidone, polyacrylamide, polyacrylic acid, partial hydrolysates of polyacrylamide, anionic polymers such as vinyl methyl ether-maleic acid copolymers, and also N-vinylimidazole, acrylic acid and acrylamide. There are also amphoteric synthetic polymers such as copolymers of polyacrylamide and Hofman reaction-treated polyacrylamide.

These hydrophilic polymers may be used alone or in combination.

Furthermore, these hydrophilic polymer layers may contain a latex-like polymer dispersion of hydrophobic monomers such as alkyl acrylates and alkyl methacrylates.

These hydrophilic polymers, especially polymers having functional groups such as amino groups, hydroxyl groups, and carboxyl groups, can be crosslinked with various crosslinking agents without losing their permeability to processing liquids.

Particularly useful cross-linking agents include formaldehyde,
glyoxal, geltaraldehyde, chloric acid,
Aldehyde compounds such as oricomer of acrolein; aziridine compounds such as triethylene phosphamide shown in Japanese Patent Publication No. 37-8,790; Japanese Patent Publication No. 34-7
, 133, 1,4-bis(2',
Epoxy compounds such as 3'-epoxypropoxy) diethyl ether; 2-hydroxyl-4,6-dichloro-5-) as published in U.S. Pat. No. 3,327,287;
Active halogen compounds such as riazine sodium salt; active olefin compounds such as hexahydro-1,3,5-triacryl-5-1 riazine; methylol compounds such as N-polymethylol urea or hexamethylol melamine; dialdehyde starch or US Patent 3,362
Examples include polymeric gelatin such as 3-hydroxyl-5-chloro-5-)ryanonylated gelatin disclosed in No. 1, No. 827.

Furthermore, these hydrophilic polymer single layers may contain a crosslinking reaction accelerator such as carbonate or resorcinol in addition to the crosslinking agent.

The photographic layer used in the present invention can be coated by various coating methods such as dip method, roller method, air knife method, U.S. Pat.
Coating can be carried out by a bead coating method as described in US Pat. No. 81,294, a curtain method as described in US Pat. No. 3,508,947 and US Pat.

Especially for photosensitive elements with multilayer construction, U.S. Patent No. 2,761,41
No. 7, No. 2,761,418, No. 2,761,419
It is convenient to apply multiple layers simultaneously using a multi-slit hopper as described in No. 2,761,791.

In order to facilitate the application of the photographic layers used in the present invention, the coating compositions advantageously contain various surface-active substances as coating aids.

Useful coating aids include saponins, exciethylene adducts of p-nonylphenol, alkyl ethers of sucrose,
Nonionic surfactants such as monoalkyl ethers of glycerin, anionic surfactants such as sodium dodecyl sulfate, p-dodecylbenzenesulfonate sodium salt, dioctyl sulfosuccinate, sodium salt,
and carboxymethyldimethyllauryl ammonium.
Hydroxide Internal Salt, “Deriphai, 15
1”, U.S. Patent No. 3,441,413, British Patent No. 1,1
Examples thereof include amphoteric surfactants such as betaine compounds described in Japanese Patent Publication No. 59,825 and Japanese Patent Publication No. 46-21985.

To facilitate coating of the photographic layer used in the present invention, the coating composition may contain various viscosity increasing agents.

In addition to those which increase the viscosity of the coating composition by their own viscosity, such as high molecular weight polyacrylamides, cellulose sulfate esters, poly-p-sulfostyrenes, potassium salts and those disclosed in U.S. Pat. No. 3,655,407 Also useful are anionic polymers that exhibit a thickening effect through interaction with the binder polymer in the coating composition, such as the acrylic acid-based polymers used in the present invention. A liquid composition containing processing components necessary for developing a silver oxide emulsion and forming a diffusion transfer dye image, the main solvent of which is water, and which also contains a hydrophilic solvent such as methanol or methyl cellosolve. There is also.

The processing composition contains an amount of alkali sufficient to maintain the levels necessary to cause development of the emulsion layer and to neutralize the acids formed during the development and dye image formation steps.

As the alkali, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine, etc. are used, and the composition preferably has a concentration of about 12 or more at room temperature. have.

More preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose.

These polymers may be present in the treatment composition at room temperature of 1 poise or more;
Practically 5 to 2000 poise, preferably 10 to 10
It provides a viscosity of about 0.00 poise and not only facilitates the uniform spread of the composition during processing, but also when the aqueous solvent moves to the photosensitive element and image receiving element during the processing process and the processing composition is concentrated. A non-flowing membrane is formed to help the film unit unite after processing.

This polymer film can also serve to prevent changes in the image by inhibiting further migration of colored components to the image receiving layer after the formation of the diffusion transfer dye body is substantially completed.

The processing composition may also contain light-absorbing substances such as carbon black to prevent fogging of the silver halide emulsion by external light during processing, as well as U.S. Pat.
It may be advantageous in some cases to contain desensitizers as described in No. 33.

In addition, the processing solution may include a developer such as an aromatic primary amino-color developer, an antioxidant such as sulfite or ascorbic acid, a halide or antifoggant such as 5-nitrobenzimidazole, thiosulfuric acid, etc. Examples include salts or silver halide solvents such as uracil.

Advantageously, the treatment composition used in the present invention is housed in a breakable container.

Such containers contain the treatment composition in a cavity created by folding a sheet of liquid- and air-impermeable material and sealing each edge so that when the film unit is passed through a pressure device, Advantageously, the internal pressure applied to the treatment composition causes it to rupture at a defined point to release its contents.

Materials such as polyethylene terephthalate/polyvinyl alcohol/polyethylene laminates, lead foil/vinyl chloride and vinyl acetate copolymer laminates are advantageously used as materials for forming the container.

Preferably, these containers are secured along the leading edge of the film unit and are adapted to spread the contained liquid substantially in one direction onto the surface of the photosensitive element.

Preferred examples of containers include U.S. Pat. No. 2,543,181;
No. 2,643,886, No. 2,653,732, No. 2,723,051, No. 3,056.491, No. 3
, No. 056.492, and No. 3,152,515,
No. 3,173,580, such a container is advantageous in carrying out the present invention.

The image-receiving element used in this invention immobilizes a dye image-forming substance, such as a diffusible dye, which is released in image distribution from a dye image donor in combination with a silver halide emulsion.

In cases where the dye image-forming substance is an anionic substance such as a dye developer having a hydroquinonyl group or a color forming dye having an acidic water-solubilizing group, the image-receiving element is a basic polymer,
Alternatively, it is advantageous to contain a basic surfactant.

As basic polymers, those containing tertiary or quaternary nitrogen atoms are excellent, specifically poly-4-vinylpyridine; vinyl methyl ketone aminoguanidine described in U.S. Pat. No. 2,882,156; Polymer of derivatives; poly-4-vinyl-N-benzyl-pyridium, para-toluenesulfonate, poly-3-vinyl-4-methyl-N-n-butylpyridium bromide; British patents 1, 2
Styrene/N-(3-maleimidopropyl)-N,N-dimethyl-N-(4-phenylbenzylammonium chloride copolymer);
-(2-methacryloylethyl)-N,N-dimethyl-
N-benzylammonium chloride] and the like.

As basic surfactants, those having both an onium residue such as ammonium, sulfonium or phosphonium and a hydrophobic residue such as a long-chain alkyl group are excellent, and specifically N-laurylpyridinium bromide ,
Cetyltrimethylammonium bromide, methylt'J
Examples include -n-lauryl ammonium, paratoluenesulfonate, methyl-ethyl-cetylsulfonium, iodide, henzine-torphenylphosphonium, chloride, and the like.

In addition to these basic compounds, compounds of polyvalent metals such as thorium, aluminum, and zirconium also have a fixing effect on anionic dye-forming substances.

These materials advantageously form films with polymers such as gelatin (particularly acid-treated gelatin), polyvinyl alcohol, polyacrylamide, polyvinyl methyl ether, hydroxyethyl cellulose, N-methoxymethyl polyhexyl methylene adipamide, polyvinyl pyrrolidone. be.

When the dye image-forming substance is a dye-forming component such as a diffusible coupler, the image-receiving layer contains other coupling components that react with this component to form the dye, such as p-phenylenediamine derivatives and oxidizing agents, or diazonium Contains compounds.

This type of image receiving element includes U.S. Pat. No. 2,647,0
No. 49, No. 2,661,293, No. 2.698, 24
No. 4, No. 2,698,798, No. 2.802,735
No. 3,676.124, British Patent No. 1,158,4
40, No. 1,157,507, etc. can be used.

The film unit of the present invention may contain a developing agent scavenger that reacts with the excess developer drug remaining after processing to provide a colorless product that is less susceptible to oxidation.

In particular, in a film unit in which the acidic substance-containing neutralizing layer, neutralization rate controlling layer, or neutralization layer of the image receiving element contains the above-mentioned scavenger, clear images with less staining can be obtained.

A film unit containing an aromatic-grade amine compound that is susceptible to staining is disclosed in West German Patent Application (OLS) 2.
, No. 201,392, No. 2,225,480, No. 2,
It is advantageous to incorporate as scavengers compounds with functional groups capable of condensation with amines, such as isocyanates, precursors of aldehydes, and vinylsulfonyl compounds, as described in US Pat. No. 225,497.

The diffusion transfer photographic film unit of the present invention preferably has the function of neutralizing alkali brought in from the processing composition.

A pH high enough to promote the image-forming process consisting of development of the silver halide emulsion, formation and diffusion of diffusible dye formers, etc.
The treatment composition contains an alkali to provide a - of 10 or more, preferably 11 or more.

After the formation of the diffusion transfer member is substantially completed, the - in the film unit is neutralized to around neutrality, 9 or less, preferably 8 or less, and further image formation process is virtually stopped, and the image is transferred. It prevents changes in tone over time and suppresses discoloration and fading of images caused by high alkalis and contamination of white background areas.

For this purpose, a sufficient amount of an acidic substance to neutralize the alkali in the processing solution to the above pH level, that is, a neutralization containing an acidic substance with an area concentration equal to or higher than that of the alkali in the developed processing solution. It is advantageous to incorporate the layers into a film unit.

Preferred acidic materials include those containing acidic groups with a pKa of 9 or less, particularly carboxyl or sulfonic acid groups, or precursor groups that provide such acidic groups upon hydrolysis, more preferably those described in U.S. Pat.
, 606, such as oleic acid,
Examples include fatty acids, as well as polymers of acrylic, methacrylic, or maleic acids and their partial esters or acid anhydrides as described in US Pat. No. 3,362,819.

Specific examples of polymeric acidic substances include copolymers of vinyl hexamers such as ethylene, vinyl acetate, and vinyl methyl ether and maleic anhydride, their esters such as n-butyl, and copolymers of butyl acrylate and acrylic acid. copolymer of
Cellulose, acetate, acid phthalate, etc.

In addition to these acidic substances, the neutralizing layer may contain polymers such as cellulose, nitrate, polyvinyl acetate, and may contain plasticizers as described in U.S. Pat. No. 3,557,237. You may do so.

Furthermore, the neutralization layer may be cured by a crosslinking reaction using a polyfunctional aziridine compound, an epoxy compound, or the like.

A neutralizing layer is disposed in the image receiving element and/or the photosensitive element.

It is particularly advantageous if it is located between the support of the image-receiving element and the image-receiving layer.

Acidic substances can be incorporated into the film unit in microencapsulation as described in OLS 2,038,254.

The neutralization layer or acidic substance-containing layer used in the present invention is
Preferably, it is separated from the developing treatment liquid layer by a neutralization rate regulating layer.

This neutralization rate adjusting layer prevents the density of the transfer material due to premature decrease in processing pl (PL) before the required development of the silver halide emulsion layer and formation of the diffusion transfer material. It serves to prevent undesirable drops and to delay the pH drop until after the required development and transfer have taken place.

In a preferred method of carrying out the present invention, the image receiving section has a multilayer structure in which a support, a neutralizing layer, a neutralization rate controlling layer, and a mordant layer (image receiving layer) are arranged.

The neutralization rate adjusting layer is made of gelatin, polyvinyl alcohol,
The main components are polymers such as polyhinylpropyl ether, polyacrylamide, hydroxypropyl methylcellulose, isopropylcellulose, partially polyvinyl butyral, partially hydrolyzed polyvinyl acetate, and copolymers with β-hydroxyethyl methacrylate. configured.

These polymers are useful if they are cured by a bridging reaction using an aldehyde compound such as formaldehyde, or an N-methylol compound.

The neutralization rate controlling layer preferably has a thickness of 2 to 20 microns.For the film unit of the present invention, a preferable multilayer structure includes a blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion sequentially from the exposure side. In particular in the case of high-speed emulsions containing iodide, a layer of yellow filter may be arranged between the blue-sensitive emulsion and the green-sensitive emulsion.

The yellow filter contains a yellow colloidal silver dispersion, a dispersion of an oil-soluble yellow dye, an acidic dye mordanted with a basic polymer, or a basic dye mordanted with an acidic polymer.

Advantageously, the emulsion layers are separated from each other by interlayers.

The interlayer prevents undesirable interactions between emulsion layer units of different color sensitivities.

The intermediate layer is formed from hydrophilic polymers such as gelatin, polyacrylamide, and partially hydrolyzed polyvinyl acetate, as well as latexes of hydrophilic and hydrophobic polymers as described in U.S. Pat. No. 3,625,685. Polymers with pores that become increasingly hydrophilic with treatment compositions, such as calcium alginate described in U.S. Pat. No. 3,384,483.

The intermediate layer contains a reducing agent such as a diffusion-resistant hydroquinone derivative,
and reacts with oxidation products to solidify.

Diffusion-resistant couplers that can be defined are effective in preventing undesirable exchange of developer oxidation products between emulsion layer units.

Furthermore, in systems in which the reversal is performed by dissolution physical development, the intermediate layer is provided with physical development nuclei such as metal silver colloids, and in systems in which the reversal is performed using a developer inhibitor release (DIR) compound. It is useful to contain low-sensitivity, fine-grained silver halide grains in order to obtain good color reproduction.

The photosensitive materials of this invention are incorporated into various types of diffusion transfer Kalany photographic film units.

In addition to the photosensitive element, the main elements constituting the film unit include an image receiving element, a processing liquid element, a neutralizing function, and the like.

The photosensitive element of the present invention has a final positive image body made of a diffusive dye and a negative image body made of a non-diffusive dye.

can be combined with stiff film unit elements in a wide variety of forms, provided that they are easy to provide in separate form.

In one preferred embodiment, the emulsion layer unit of the present invention is coated on a support temporarily imparted with light-shielding properties to constitute a light-sensitive material.

The light-sensitive material imagewise exposed from the side opposite to the support is combined face-to-face with an image-receiving layer having a light-reflecting layer and a dye image-receiving layer on a light-shielding support, and an alkaline processing liquid is applied to the front side. As a film unit containing a tearable container, it is subjected to the action of a pressure tool.

As a result of the Calo pressure, the processing liquid is spread in a layer between the light-sensitive material and the image-receiving layer, causing development, dye image formation, and transfer.

After the formation of the positive transfer image and the negative fixed body have been substantially completed, the image-receiving layer is peeled off, and then the photosensitive layer is
8-105,235, and at the same time the light-shielding properties of the support and the adhering processing liquid layer are removed to provide a negative original for printing.

Another diffusion transfer film unit suitable for practicing the present invention is that disclosed in Japanese Patent Application No. 1986-63,157.

The film unit consists of (1) a light-sensitive material in which a light-shielding layer, in which one or more emulsion layer units are removable and permeable to a processing liquid, are sequentially coated on a transparent support; and a dye image on a transparent support; An image-receiving sheet having a receptive layer and a light-shielding sheet are combined at their edges to form an envelope-shaped combination having an opening into which a photosensitive material is inserted;
Advantageously, a tearable container containing an alkaline processing liquid is fixed to the leading edge of the combination.

In this film unit, the light-sensitive material is imagewise exposed from the support side.

The exposed light-sensitive material is inserted into the composite through the opening in such a manner that the emulsion layer of the light-sensitive material and the dye image-receiving layer of the image-receiving sheet are in face-to-face contact.

Next, a processing solution is spread between these two layers in a layered manner to cause development, formation of a dye image, and transfer.

As described above, the image-receiving sheet and the photosensitive material are separated, and the latter is subjected to desilvering treatment to remove the light-shielding layer permeable to the processing solution, thereby creating a positive color transfer body and a negative fixed image for color printing. can get.

In addition to those film units in which the emulsion layer and dye image-receiving layer are coated on separate supports, the present invention also relates to the British patent in which the emulsion layer and the dye image-receiving layer are coated on a single support. The present invention can also be applied to the film unit described in No. 1,330,524 by performing appropriate layer separation and layer fixing operations after processing.

The supports used in the present invention are planar materials that do not undergo significant dimensional changes during the time of treatment due to the treatment composition.

Although rigid supports such as glass can be used depending on the purpose, flexible supports are generally useful.

Flexible supports include those used in photographic materials;
For example, cellulose nitrate film, cellulose acetate film, polyvinyl acecool film, polystyrene film, polyethylene terephthalate film, polycarbonate, etc. are advantageously used.

Dimensionally stable and oxygen-barrier supports such as laminates in which a polyvinyl alcohol layer is sandwiched between polyethylene terephthalate layers or cellulose acetate layers,
It is particularly desirable because it has good dye image stability and little staining.

No. 3,573,04 to assist in wicking water from the developed treatment composition through the support after treatment.
It is advantageous to use water vapor permeable supports such as those described in No. 4.

When the film unit is processed in a bright place, the transparent support is used to prevent light from passing from the edge of the transparent support to the silver halide emulsion layer. It is desirable that the material be colored to the extent that it can prevent the transmission of light.

The support may optionally contain a plasticizer such as phosphoric acid ester or phthalic acid ester, an ultraviolet absorber such as 2-(2-hydroxy-4-t-butylphenyl)benzl-IJ azole, and an oxidation inhibitor such as hindered phenol. It may also contain an agent.

In order to maintain the adhesion between the support and the layer containing the hydrophilic polymer, it is advantageous to provide an undercoat layer or to subject the surface of the support to a pretreatment such as corona discharge, ultraviolet irradiation, flame treatment, or the like.

The support typically has a thickness of 20 to 300 microns.

In the film unit of the present invention, in order to form a white background for the dye image formed on the receptor layer, a light-reflecting substance is added between the receptor layer and the surface of the photosensitive unit at the latest by the end of processing. to be located.

Suitable light-reflecting materials include titanium dioxide, barium sulfate, zinc oxide, alumina, barium stearate, calcium carbonate, silicates, zirconium oxide, kaolin, magnesium oxide, etc., which may be used alone or in combination.

Even if such light-reflecting substances are formed in advance,
or Belgian Patent No. 768,110, Belgian Patent No. 768,111
may be formed in-situ from a precursor that is distributed in a film unit as described in the present patent application.

The light-reflecting substance may be contained in a layer using a hydrophilic polymer such as polyvinyl alcohol, gelatin, hydroxypropylcellulose, or polyvinylpyrrolidone as a binder, and may also be incorporated into a processing liquid composition before processing. It can also be fixed in a dispersed state in a layer of a film-forming polymer such as hydroxyethyl cellulose or carboxymethyl cellulose formed by liquid development.

Optical brighteners such as stilbenes, coumarins, triazines or oxazoles can be used in combination with light-reflecting substances to produce beautiful white backgrounds.

In order to protect the silver halide emulsion layer from ambient light during processing, Belgian patent 743,33 together with a light reflective substance is used.
As described in No. 6, No. 768,107, and No. 768,109, it is colored and p
It is advantageous to have a dye present which becomes colorless below a pH of Ka.

Advantageously, the layer containing the light reflective material has a light reflective material/binder polymer (weight ratio) composition of from about 0.5 to about 100 and a dry film thickness of from 5 microns to 50 microns. and has a light reflectance of 50φ or more, preferably 70φ or more.

The film unit of the present invention has a breakable container containing the treatment composition.

When this container is pressed by the pressure tool, it ruptures due to internal pressure and releases the treatment composition in a defined manner.

Although various types of pressurizing tools can be used, those consisting of at least one pair of members juxtaposed with a certain gap are particularly suitable for processing the film unit of the present invention.

The pair of members are fixed with a fixed gap or pressed together with a fixed force by an elastic body such as a spring, and the members may be rod-shaped, freely rotating rollers, or driven rollers.

As the film unit passes between the juxtaposed pair of Calo pressure tools, the container ruptures and the treatment composition is released and further spread in a layer between the two sheets.

As a juxtaposed pressure tool, U.S. Patent No. 3,647.4
G as described in No. 41, No. 3,652,281.
something is used to advantage.

In the film unit of the present invention, development processing is continued in a bright place outside the camera.

The silver halide emulsion layer is protected from external light until development and dye image transfer are substantially completed.

For this purpose, it is advantageous to arrange a light-shielding layer containing a light-absorbing substance on the side surface of the silver halide emulsion layer.

Depending on where it is placed, the light-blocking layer has a permeability to the treatment composition (
Hydrophilic) or impermeable to processing compositions (dimensionally stable).

The treatment composition permeable light-shielding layer is a single layer of a water-permeable polymer such as gelatin, polyvinyl alcohol, polyacrylamide, polyhydroxyethylcellulose, carboxymethylcellulose, sodium salt, methylcellulose, etc. containing a light-shielding substance and is applied as a pre-formed layer. You can also
It may be developed as a treatment liquid layer during treatment.

The dimensionally stable light-shielding layer is a single layer of polymer containing a light-absorbing substance, and is disclosed in Japanese Patent Publication No. 43-24,547 and U.S. Pat.
No. 07.818 D, and is incorporated into the film unit as a support or light-shielding sheet.

Dimensionally stable light-blocking layers can also be made of metal foils such as aluminum, tin, and laminate films of metal foils and polymers, or films in which aluminum is vapor-deposited on polyethylene terephthalate, and laminate films.

It is preferable to cover the light-shielding layer with a light-reflecting substance such as titanium dioxide from the viewpoint of increasing light-shielding properties and aesthetic appearance.

Various light-absorbing substances can be used for the light-shielding layer, but
Especially carbon powder such as carbon black, silver colloid,
Particularly useful are organic pigments such as azo lakes or steel phthalocyanines, water-insoluble azo dyes, dispersions of anthraquinone dyes, polymers reacted with reactive dyes, micelle-forming hydrophilic dyes, and the like.

Although it varies depending on the purpose of use of the film unit, the light shielding layer has an absorbance (scattered light) of about 3 or more, preferably 5 or more over the entire wavelength range from 350 to 650 millimicrons, preferably from 300 millimicrons to 750 millimicrons. This is often necessary.

The dimensionally stable light-shielding layer can advantageously be used as an adhesive tape to light-shield the edges of the transparent support in order to prevent light leakage from the edges of the film unit into the silver halide emulsion layer.

From the film unit of the present invention, a positive image can be obtained immediately after photographing, and if necessary, a color negative with color compensation can be obtained only by simple desilvering treatment.

Obtaining a color positive image from a color negative is technically and industrially established, and can be easily carried out using existing systems.

In this way, the drawback of conventional diffusion transfer color photography that only one print could be obtained was solved by this film unit in the form of a combination with ordinary color photography.

2 with good image quality by the film unit of the present invention.
It is now possible to duplicate the next print.

It is possible to reprint many copies of secondary prints,
Adjustments at the time of printing made it possible to perform trimming, change the screen size, correct excess or deficiency in exposure, etc.

The secondary print obtained by using the film unit of the present invention can enjoy the advantages of improved conventional color photography, such as stability of the pigment bodies and sharpness of color.

These features of the invention are made possible by a new relationship between the photosensitivity of photosensitive silver halides and the spectral absorption of the two types of couplers with which they are associated.

The film unit of the present invention is desirable from the viewpoint of environmental conservation and resource conservation, since the photosensitive element portion is also reused, so there is less waste, and silver is recovered.

Other features will become apparent from the text description and the examples.

FIG. 2 shows a cutaway view of a specific example of a photosensitive element, a receptor element, and a processing liquid container that constitute the film unit of the present invention.

FIG. 2 is drawn to clearly show the arrangement of the constituent elements, and the dimensions are not proportional and may be significantly deformed in some cases.

In the photosensitive element 1, on one side of a transparent support 51 are a non-photosensitive layer 52 which releases a diffusible yellow dye, a blue-sensitive silver halide emulsion layer 53 which provides a non-diffusible yellow dye, a yellow filter 54, a diffusing emits a color magenta pigment,
A non-photosensitive layer 55 that produces a non-diffusible yellow dye, a green-sensitive silver halide emulsion layer 56 that provides a non-diffusible magenta dye image, an intermediate layer 57 that releases a diffusible cyan dye and produces a non-diffusible magenta dye. There is a photosensitive element 61 consisting of three photosensitive units coated sequentially with a non-photosensitive layer 58 providing a non-diffusive cyan dye image and a red-sensitive silver halide emulsion layer 59 providing a non-diffusive cyan dye image; A light shielding layer 6 containing
0 covers it.

A back layer 50 is coated on the opposite side of the support.

In the receiver element 2, a neutralizing layer 71 containing an acidic substance, a neutralization rate adjusting layer 72 and an image receiving layer 7 are disposed on a transparent support 70.
There is a receiving element 74 consisting of three pieces.

The processing liquid container 4 is a bag made of a laminate film, such as a lead foil 92 and a single layer of alkali-resistant polymer 91, and contains a processing liquid 93.

A) When pressure is applied to the container, the adhesive layer is peeled off by the internal pressure of the processing liquid and the processing liquid is released.

Fig. 3 shows one specific example of the film unit of the present invention, Fig. 33 shows the appearance of the photosensitive surface, and Fig. 3b shows the appearance of the transferred image side.

In the figure, 1 represents a photosensitive element, 2 represents an image receiving element, 3 represents a light shielding sheet, 4 represents a processing liquid container, 8 represents a white border sheet for the transferred image, and 9 represents a paint layer for shielding the edges from light. .

In the film unit shown in Figure 4, the photosensitive element 1 is
is supported by a pressure plate 100 and joined to the leader paper 5 at the front end.

The image receiving element 2 and the light shielding sheet 3 are connected to leader papers 6 and 7 at their front ends, respectively.

These leader papers 5, 6, 7 are connected to each other, and by pulling the tip of 5, the three elements are aligned and overlapped, and the processing liquid container 4 is placed between the photosensitive element and the image receiving element. placed on the leader paper for release.

When the three elements are closely stacked, the silver halide emulsion layer of the photosensitive element is protected from external light by both its light blocking layer 60 and light blocking layer 3.

FIG. 5 shows a sectional view of the film and unit of FIG. 4.

The photosensitive element is arranged so that the back layer 50 and the transparent support 51 are placed on the outside, and the photosensitive element 61 and the light shielding layer 60 are placed on the inside, and the image receiving element is placed so that the transparent support 10 is placed on the outside and the image receiving element 74 is placed on the inside. Furthermore, the light-shielding sheet is placed so as to cover the back layer of the photosensitive element and the transparent support, and the processing liquid container is placed between the leader paper 5 for the photosensitive element and the leader paper 6 for the image-receiving element. It is shown that

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A photosensitive material was prepared by sequentially coating the following three layers on a triacetylcellulose transparent support having a thickness of 120 microns.

(1) Diffusible magenta dye-donor layer: unchemically sensitized silver chlorobromide (bromide content 15 molar,
Average particle size: 0.42 microns) is equivalent to 7.8711g of silver.
/ 100 c: trt, colloidal silver sulfide nuclei (particle size approximately 5 millimicrons) as a 0.09 m'j/m silver equivalent diffusive magenta dye-forming coupler 1-(l-methylphenyl)-3-( 3,5-dicarboxyanilino)-4
-(3octadecylcarbamylphenylthio)-5-pyrazolone at 91W! /100criL1 2-methyl-benzoyl, aceto-3 as a diffusion-resistant coupler for color correction
-n-dodecyloxycarbonyl-6-chloroanilide at 1.8η/100i, N-N-diethyl laurylamide at 13/100cyyf and gelatin at 37/100i.
A layer containing 7.

(2) Photosensitive layer A silver iodobromide emulsion (4.2 mol of iodide, average grain size 0.78 microns) made green-sensitive with the following ortho sensitizer has a silver conversion T: 15.1 rIII/ 100ffl,
1-(4-[α-(2,4-di-tert-amylphenoxy)-butylamidoyophenyl)-3-N-hypericino-4-(1-phenyl-5-tetrazolylthiono-5-pyrazolone) 8.5■/100i, 1- (
2,4,6-)lichlorophenyl)-3-(3-(α-
(2,4,-di'-tert-amylphenoxy)-butyramide]benzoylamide)-5-pyrazolone with 6
．． 0”// 100cr/l, n-pentadecylhydroquinone at 1.5772!?/100-, ternary copolymer of vinyl acetate and N-vinylpyrrolidone at 3.
Oyny/ 100 cr? t.

Tory〇-talesyl phosphate 15”?/10
0 cr (layer consisting of D gelatin 26ml/100d).

(3) Protective layer ortho sensitizer A 0.7 micron thick layer made of gelatin.

Next, one side of a paper support coated on both sides with polyethylene was coated with 35 μm of poly-4-vinylpyridine, 15 μm of poly(2-methacrylethyl i-limethylammonium methyl sulfate) and 80 μm of polyvinyl alcohol per 100 μm. A receiving element with a formaldehyde hardened dye image receiving layer was prepared.

After exposing the photosensitive element to 20 CMS through an optical wedge for sensitometry and a green filter, the element was placed face-to-face with the receiving element, and a viscous processing solution having the following composition was heated to a thickness of 80 microns at 25°C. After developing and holding in the same greenhouse for 5 minutes, the receiving element was peeled off in a 1.5% acetic acid aqueous solution, washed with water for 2 minutes, and dried to obtain a positive print with a magenta inversion.

Viscous treatment liquid Ascorbic acid 0.293-Methyl-4-amine-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 30.09 Potassium bromide 1.4g Trisodium phosphate, dodecahydrate 20. 09 Sodium hydroxide
40.09Hydroxyethylcenoloin 30.0g water
880rrli! (Viscosity: 30.0 at 25℃
OOCP) The characteristic curve of the obtained positive print is shown in FIG. 1a.

The photosensitive element was then processed as described below.

Post-treatment 1, alkaline treatment bath 24℃ for 5 minutes 2, bleaching bath
The composition of the processing solution used was as follows: 24°C for 6 minutes3, fixing bath at 24°C for 4 minutes4, and water washing for 10 minutes at 16°C.

1. Alkaline Processing Bath 1 Characteristic curves of the processed photosensitive element were determined using blue, green, and red filters (shown in Figure 1, c and d).

As shown in Figure 1, a good negative gradation of magenta dye can be obtained,
Furthermore, as shown in FIG. 1C, the yellow coupler is colored non-photosensitively, so that the blue density remains constant regardless of the exposure amount, and good color correction (mask) is performed.

FIG. 1d shows the red density, and it can be seen that the red density increases as the magenta dye density increases.

Example 2 A laminate in which both sides of a 25 micron thick polyvinyl alcohol film were covered with a 38 micron thick triacetylcellulose film, the following sequence was applied sequentially onto one side of the film's transparent support. A photosensitive element was prepared.

(1) 1.6 x 10-5 mole/100 cyyt of α-hybaroyl-α-(3-octadecylcarbamylphenoxy) 3.5-di-carboxyacetanilide as a diffusible yellow dye-donating coupler.

t-octyl-hydroquinone 17IIg/100
crillN, N-diethyllauramito 12mg/1
00ffl, Carrie, Ri-type gold sol o, i■/1
A diffusible yellow dye-donor layer containing 0.00 cril and gelatin 16/1007, where the gold sol was pink in color, was obtained by reducing chloroauric acid with sodium, polyhydride in the presence of gelatin.

(2) As a yellow-forming coupler, α-(2-methylbenzyl)-2-chloro-5-n-dodecyloxycarbonylacedoanilide 2.4×10 −5 . mol e
/ 100 ff11 di-n-butyl phthalate 4
7Ilf// 100 Cr11. Gelatin 187I1
11/1o.

dl and silver 14.6X10-5mole/100ff1
Blue-sensitive negative type silver iodobromide emulsion grains with a coverage of 1 (
Iodide 3.07), average particle size 0.9 microns)
A blue-sensitive emulsion layer containing.

(3) α-pivaloyl-α-(3-octadecylcarbamylphenoxy) as a diffusible yellow-donating coupler
-3,5-dicarboxyacedoanilide 0.8
10-mole / 100ct! , t-octylhydroquinone 0.6N/100cri11N
.

N-dienal lauramide 6η/100Cr! , Carey-Lee type silver zo'#0.05
7Q/1007, and gelatin 87IIg/100cy
A second diffusible yellow dye-donor layer comprising tt, where the silver sol was a yellow colloid of silver nitrate reduced with sodium polyhydride in the presence of gelatin.

*(4) Carey-Lee type silver colloid 7, OT1g/100cri112.5-
Di-t-octylhydroquinone 57M@/100ff
1, and a layer containing 13 μ/100 d of gelatin.

(5) As a diffusible magenta dye-donating coupler, 1-phenyl-3-[2-chloro-5-(γ-sulfobutyramide)-anilino, l-4-(3-N-methyl-N-octadecylcarbamyl) phenylthio)-5-pyrazolone 1,0 0.5X10-5 mol/100i1Nr
N-diethyl laurylamide 7/100ffl, Carey-Lee type sol 0
．． 17IIIi/100cI/L and gelatin 13m'i
// Layer containing 100ffl.

(6) As a magenta-forming coupler, 1-(2,6-dichloro-4-methoxy)-3-43-1α-(2,4-
di-t-amylphenoxy)butyramido)phenyl]
-Ureido-5-Hirazolone 1.6X10-'mol/1
00cIfL1 tree 0-cresyl phosphate 5”l
'W/ 100 ff1s gelatin 16'1l11/
100 cIil, and silver 93X10'mol/10
Silver iodobromide emulsion grains sensitized with the following sensitizers at a coverage of 0d (2.0 moles more iodide, average grain size 0.7
green-sensitive emulsion layer (7) containing 1-phenyl-3-[2-chloro-5-(γ-sulfurylamide)-anilino)-4-(3-N- Methyl-N-,d
-phtadecylcarbamylphenylthio)-5-pyrazolone 0.6X10-5 mol/100ffl, t-octylhydroquinone 0.6m'il/100cIIL,
N, N-diethyl laurylamide 4/100c
I/L, layer containing Carey-Lee type steel sol 0.06 x 7100 and gelatin 7 x/100 i.

(8) Carey-Lee type silver colloid 4.0■/100a/i, 2.5-t
-Octylhydroquinone 5'Ir1f! , / 100
cyrt, and gelatin 13WtIi/100cri
An intermediate layer containing L.

(9) As a diffusible cyan dye-donating coupler, 1-hydroxy-4-(3-N-methyl-N-octadecylcarbamylphenylthio)-N-ethyl-2Lmethoxy-S
/(γ-sulfobutyramide)-2-nututamide 1.2
X10'mol/100u, 1-(2,6-dichloro-4-methoxy) as non-acidic magenta-forming coupler
-3-[3-fα-2,4-di-t-amylphenoxy)butyramido)phenylioreido-5-pyrazolone 0.5X10-'mol/100cff11N tN
-Diethyl laurylamide 8■/100cr! , Carey-Lee type record JL'0.1
”@/ 100 cyi togelatin 1611v'lOO
Layer containing sludge.

(10) As a cyan-forming coupler, 1-hydroxy-N-[γ-(2,4-di-t-amylphenoxy)-propyl-2-natutamide 1.8×10-'to4''@/100 cr , gelatin 147'1
19/100d, and silver 10,8X10-'mol/10
A red-sensitive emulsion layer containing silver iodobromide emulsion grains (2.0 moles more iodide, average grain size 0.7 microns) sensitized with the following sensitizers at a coverage of 0i.

01) As a diffusible cyan dye-donating coupler, 1-hydroxy-4-(3-N-methyl-N-octyldecylcarbamylphenylthio)-N-ethyl-27-medoxy S/(γ-sulfobutyramide)- 2-naphdoanilide 0.6X10-5/100att, h n-pentadecylhydroquinone 0,4η/100i1N, N
-Diethyl laurylamide 4111g/l 00i1C
arey-Lee type steel sol 0.05
”F/ 100crl and gelatin sW/ 100cri
A cyan dye-donor layer comprising t.

Each of the layers from (1) to αυ above is described in U.S. Pat.
4-chloro-6-oxy-5-triazinyl (2) gelatin, prepared as described in Example 1 of No. 362.827, was hardened by adding 8 weights of gelatin.

A further layer containing no hardener was applied over this coating as described below.

(1 layer of gelatin 7 monks/100i.

(13 Carbon black (furnace type, average particle size mμ
) 509, α-(4-octadecyloxybenzoyl)
-2-methoxy-5-sulfo-acedoanilide, potassium salt 2.5 g, sodium hydroxide 0.5.9, water 15
The mixture consisting of 0- was kneaded with a colloid mill to form a paste.

Add to this a 500% lo% aqueous solution of gelatin. ! 9 was added thereto, and a 5% citric acid solution was added while stirring to adjust the pH to 5.5, and the coating was applied to a dry film thickness of 4.5 microns to complete a photosensitive element.

A laminate of 25 micron thick polyvinyl alcohol covered on both sides with a 25 micron thick polyethylene terephthalate film, the receiver element was prepared by sequentially applying the following layers onto one side of a transparent support of the film. .

(1,) Half ester obtained by treating a copolymer of vinyl methyl ether and maleic anhydride with n-butyl alcohol.
Qq/100ffl, and hexahydro-1,3.

5-Triacryl-5-triazine 2.1 mg/10
A transparent film was applied to provide a coverage of 0d to form a neutralizing layer.

(2) Copolymer of n-butyl acrylate and β-hydroxyethyl methacrylate (monomer ratio approximately 1:1)
Null neutralization rate control layer from 451ftg/100d.

(3) Cetyl-tri n-butylammonium chloride 18η/100. ! i21 gelatin 40■/
100 CIrLs and tetramethylolurea 2■/
Image-receiving layer coated to a thickness of 100 cuts.

(4) The surface was treated with a 1% acetone solution of polyethylene glycol 1000 monocetyl ether to form a coating of about 0.5 microns.

1 rni of treatment liquid with the following composition! A breakable container was prepared containing the .

The container was made from a polyethylene, aluminum, cellophane, and polyethylene laminate film that was folded and heat-sealed to form a cavity that contained the processing solution.

Water 100wn
Ascorbic acid 201rI94
-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline, sulfate (monohydrate)
2.896-nidrobensimitazole, nitrate 15111g Sodium hydroxide
4.0g carboxymethyl cellulose.

Sodium salt 3.5g Sodium, thiosulfate 0.69 Titanium dioxide 45.09 Preparation of the treatment solution and storage in a container are carried out using Freon gas (Freon 1
2) It was carried out in an atmosphere.

The photosensitive element and image-receiving element produced as described above are each
Cut into pieces 10 crr long and 8 cm wide, press them together so that the coating films face each other, and apply polyethylene terephthalate containing titanium dioxide with a thickness of 115 microns to the periphery of the image-receiving sheet to form the border of the image. A perforated sheet was attached and the processing liquid container was fixed to the front opening of the assembly so that the contents could be spread between the photosensitive element and the image receiving element.

It also has dimensions along the front edge of the photosensitive element to cover the photosensitive surface, and has a thickness of approximately 50% by weight, containing 5% carbon black by weight.
A light-shielding sheet of micron polyethylene terephthalate was attached, and an ethyl acetate solution of polyvinyl acetate containing carbon black was applied to the edges of the film assembly to prevent light leakage from the edges, resulting in a structure as shown in Figure 3 a and b. Completed film unit.

Sensitometric graded illumination exposures were applied to the film unit through the transparent support of the photosensitive element, with the light-blocking sheet removed.

After combining the light shielding sheets, the processing liquid is spread through a film unit between a pair of juxtaposed pressure rollers,
Then, the treatment was continued by leaving it in a bright room at 25°C.

Formation of a transferred dye image was observed through the support of the image receiving layer.

When the reflection density was measured, the maximum blue light density was 1.1 and the minimum 0.2; the maximum green light density was 1.3 and the minimum 0.2; the maximum red light density was 1.1 and the minimum 0.2.

On the second day after processing, the photosensitive element was separated from the film unit, treated in hot water at 45° C. for 5 minutes to remove the light-blocking layer, and processed as described in Example 1.

After processing, a negative tone color image was observed to form on the dried photosensitive element.

The photosensitive element having the obtained masked color negative image was printed on commercially available color paper and developed according to a conventional method.

A beautiful positive result was obtained. Example 3 A photosensitive element was prepared with 20 μ/100 d of gelatin and 4-chloro-6-oxy-5-
Triazinyl (2) gelatin 1.6■/100cIIL
It was prepared with a protective layer consisting of:

The image receiving element was coated with 30η/100d of titanium diacid and 15η/100cI of gelatin on the third layer of the image receiving element of Example 2.
A white light-reflecting layer consisting of 1/L was prepared by treating the surface with a solution of polyethylene glycol 1000 monocetyl ether in 1/2 acetone to provide a coating of approximately 0.5 microns.

The titanium dioxide after the treatment in Example 1 was mixed with carbon black 18. O,! Prepared by replacing ii'.

A film and a unit were assembled in the same manner as in Example 2 except for using these materials.

Exposure and processing using a pressure tool were performed in the same manner as in Example 2.

As a result, the blue light density was maximum 1.2 and minimum 0.2; the green light density was maximum 1.4 and minimum 0.2; and the red light density was maximum 1.2 and minimum 0.2.

After stripping the photosensitive element, a masked color negative was obtained by processing it in an alkaline bath, a bleach bath, and a fixing bath as described in Example 1.

Example 4 Triphenyl phosphate with a 3 micron thick gelatin layer containing a dispersion of stearamide and 2-(2-hydroxy-4-t-j tylphenyl)benz I-IJ azole was used as the back layer. A light-sensitive element was prepared by sequentially coating the following layers on a 90 micron thick transparent cellulose acetate film base containing as a plasticizer. (1) α-hibaroyl-α-( 3-octadecylcarbamylphenylthio)-3,5-dicarboxyacedoanilide.
5 X 10-5mole/100i.

t-Octylhydroquinone 2”?/100 i.

to! J-n-hexyl phosphate 20/100
ffl, silver 1.4 x 10-'mole/100c
A yellow dye-donor layer containing a chemically fogged silver iodobromide emulsion with a coverage of ril and a yellow dye-donor layer containing gelatin, 20g/100crlt, with an iodide content of 2 molar width and an average grain It consists of silver iodobromide grains with a size of 0.9 microns and is subjected to excessive chemical ripening at 70° C. for 120 minutes in the presence of sodium thiosulfate so that it can be developed without exposure to light.

(2) As a yellow-forming coupler, α-(2-methylbenzoyl)-α-(N-phthalimido)-2-chloro-5
-Dodecyloxycarbonylacetanilide 3.5 X
10-'mole/100cal, α-pivaloyl-α-(1-phenyl-5-tetrazolylthio)-2-chloro5 (T
(2,4-di-amylphenoxy)butyramide]acedoanilide 4. OX 10-'mole/
100crlts di-n-butyl phthalate 3/1
00ffl, silver 7.5 x 10-5 mole/10
A blue-sensitive emulsion layer containing a blue-sensitive highly sensitive negative-type silver iodobromide emulsion (5.0 moles of iodide, multi-average grain size of 1.t microns) with a coverage of 0 cy/i1 and gelatin of 16η/100 cTL.

(3) Carey-Lee yellow colloidal silver 7.0 m'i/100i ultra-low dust silver iodobromide emulsion (25.0 moles of iodide, average grain size o, i micron) 2.2”9/100 crtt in silver terms,
2.5-di-t-octylhydroquinone 37V/1
00d, middle layer containing 13 μ/100 cffl of gelatin.

(4) As a diffusible magenta dye-donating coupler, 1-
(2,4,6-dolichlorophenyl)-3-(3゜5-
dicarboxyanilino)-4-(3-octadecylcarbamylphenylthio)-5-pyrazolone 2.5 X 1
．． 0-5e/100 cut, α-pivaloyl-α(3-octadecylcarbamylphenylthio)-3,5-carboxyacetanilide 1, OX 10-6 mol/100 as non-diffusible yellow dye-donating coupler
cr/L1N, N-diethyl laurylamide 7/1
00 cntl and a layer containing silver iodobromide emulsion, gelatin 16 .mu./1oo=, fogged similarly to layer (1) with a coverage of silver 1, I.sub.X 10-' mol/100 ffl.

(5) 1-phenyl-3 as a magenta-forming coupler
-(3-(α-(2,4-di-5ec-amylphenoxy)-butylamido]phenylureido)-5-pyrazolone 3.0X10-'mol/100 CrfL1 current suppression current suppression current inhibitor release coupler 1(α−(2,4
-di-t-amylphenoxy)-butylamido]-phenyl)-3-piperidino-4-(1-phenyl-5-tetrazolylthio)-5-pyrazolone 3.0X10-6e
Le/100crtl, Tory-Cresyl Phosphine 12.5/100ffl, Silver 95X10-5 mol/100cIIL1 and Gelatin 18η/100c
rit (D coverage) sensitized with the following optical sensitizer, a green-sensitive, highly sensitive negative type silver iodobromide emulsion (iodide 5
．． 6 molar width, average grain size 0.9 microns).

(6) Carey-Lee type colloidal silver 3.5m9 silver/100CrIL ultra-low sensitivity silver iodobromide emulsion (25.0 mol of iodide, average grain size 0.1 micron) converted to silver 2.27%/10 oc11 yen, 2,5-
Di-t-octylhydroquinone 3"i'/100
Intermediate layer containing 13 μl/100 cIl of cutts gelatin.

(7) As a diffusible cyan dye-donating coupler, 1-hydroxy-4-(3-octadecylcarbamylphenylthio)-N-ethyl-37,5/-dicarboxy-2-naphthoanilide 2.8X10-mol/ 100 ffl, 1-phenyl-3-(3-(α-(2,4-di-5ec-amylphenoxy)-butyramido]phenylureido)-5-pyrazolone 0.3X10-6 mol as non-diffusible magenta dye-donating coupler / 100cI7L,
N-N-diethyl laurylamide 7■/100cy
tts Layer containing the same chemically fogged silver iodobromide emulsion as layer (1)*, gelatin 20 η/100 with a coverage of 1.1×10 − mol of silver/100 d.

(8) As a cyanogenic coupler, 1-hydroxy-4
-Chloro-3'-'70 rho 5'-dotesyloxycarbonyl-2-naphthanide 3.5X10-6 mol/1
00cyyf, as a development inhibitor-releasing coupler, 1-
Hydroxy-4-(1-'phenyl-5-tetrazolylthio)-N-(γ-(2,4-di-t-amylphenoxy)propylio2-nanotanlide 4.0X10-6 di-n-butyl phthalate 3rfIg/100d, silver 7, 5X10-5 mol/100d1 and gelatin 18■
Contains a red-sensitive highly sensitive negative type silver iodobromide emulsion (5.6 mol iodide strip, average grain size 0.9 micron) sensitized with the following optical sensitizer at a coverage of /1oo = Red-sensitive emulsion layer.

Each of the layers (1) to (8) above was prepared as described in Example 1 of Japanese Patent No. 3,362,827.

The film was hardened by containing 4-chloro-6-moxy-5-triazinyl-2-gelatin in an amount 8% heavier than gelatin.

A further layer containing no hardener was applied over this coating as described below.

(9) Zera fn 137'ZjF/ 100crit (0
layer.

00) Gelatin 50g, sorbitan monolaurate 0,
5g, ■-hydroxy-4-sulfo-N-stearyl-
500 rIII of an aqueous solution containing 0.5 g of 2-naphthamide, sodium salt! A small amount of 50 g of carbon black was added to the mixture, and the mixture was stirred at 35° C. for 12 hours to finely disperse the carbon black.

A 40-aqueous solution containing 1 g of carboxymethyldimethyldodecyl ammonium was added to this dispersion, and the mixture was coated to a dry film thickness of 5.0 microns.

A 60 micron thick transparent cellulose acetate film containing triphenyl phosphate and dimethyl xyethyl phthalate as plasticizers.

The image receiving element was prepared by sequentially applying the following four layers onto the base.

(1) Polyvinyl alcohol (saponification degree 99%, high viscosity product, manufactured by du Pont "' Evanol 72-610
(2) a copolymer of vinyl acetic acid and maleic anhydride (
Polymerization molar ratio 1:1) 100g to 60% methyl ethyl ketone
0.0 m7 of phosphoric acid (88'%) and then 40 g of n-lauryl alcohol were gradually added and kept at about 75 DEG C. for 72 hours with stirring.

After cooling, acetone 250- and ■,4-bis(2',3'
-epoxypropoxy)-30 liters of an acetone solution containing 1.5 g of butane! II! <! : Hexahydro 1.3.5
-1-Reacryl-8-) A hot solution containing 7 g of lyazine in 50-g of cyclohexanone was added and the dry film thickness was 25.
Neutralization layer applied to a micron thickness.

(3) A 10 micron thick layer of high molecular weight polyvinyl acetate with a degree of saponification of 50%.

(4) 2 parts by weight of acid-treated gelatin, 1 polymerized part of polyJ(N-(2-methacryloylethyl)-N,N,N-)-limethylammonium]-p-toluenesulfonate,
Polyethylene (20) sorbitan monooleate o, oi
A layer with a thickness of 8 microns consisting of parts by weight and 0.02 parts by weight of hexamethylolmelamine.

A breakable container containing treatment composition 1- having the following composition was prepared.

The container was made by coating one side of lead foil with a copolymer of vinyl chloride and vinyl acetate, then folding a laminate film with the coated side inward and heat-sealing it to form a cavity for storing the composition.

Water 100-Ascorbic acid 20ml11N-ethyl-N-(β-hydroxylethyl)-p-phenylenediamine sulfate.

l Water salt 3.3g Potassium bromide 150η Potassium hydroxide 3096-nidrobenzimidazole, nitrate 15rnfl Hydroxyethyl cellulose:X 5.0g Titanium dioxide 4.5g (viscosity; 25°C
(30,000 Cp) The treatment composition was prepared and stored in a preion gas atmosphere.

A film unit was constructed by connecting a light-sensitive element, an image-receiving element, and a processing composition container with a leader and paper as shown in FIG. 4, together with a light-shielding sheet made of cellulose acetate having a thickness of 70 microns and containing 3 weight φ of carbon black.

This film unit was placed in a camera equipped with a pair of pressure rollers, and after the image was taken, the leader and paper were pulled out of the camera and processed under direct sunlight, resulting in a reversed image with natural colors. .

When the reflection density was measured, the blue light density was 1.30 at the darkest part.
, the green light density is 1.21, the red light density is 1.50, and at the brightest part, the blue light density is 0.31, the green light density is 0.24, and the red light density is 0.
It was 21.

One month after transfer, the light-sensitive element is separated, treated with hot water to remove the shading residue as in Example 1, and then treated with an alkaline bath, a bleach bath, and a fixing bath, washed with water, and dried to form a color negative with a mask. I got it.

Preferred embodiments of the present invention are as follows.

(1) Diffusion transfer, which includes the following three elements and is a print of a positive image transferred through in-body processing using the action of a pressure tool, and which can also provide an original image for color printing through subsequent desilvering processing. film unit.

(i) Photosensitive element; photosensitive material of the claims.

(ii) Image-receiving element; a colloidal layer containing a mordant that receives the formed diffusible dye.

011) Processing liquid element: an alkaline processing liquid that is spread over the photosensitive element in layers to cause developer, dye formation, and transfer of diffusible dyes.

(2. Claims and Embodiment 0), consisting of the following three units, a) a blue-sensitive unit; (1) a non-diffusible unit that reacts with the oxide of an aromatic primary amino color developer; a blue-sensitive negative-working silver halide emulsion layer containing a diffusion-resistant coupler that provides a yellow dye;
A non-light sensitive layer containing a diffusion resistant coupler which reacts with the oxide of the developer to provide a diffusible yellow dye.

b) green-sensitive units; (lil) green-sensitive negative-working silver halide emulsion layer containing a diffusion-resistant coupler that reacts with the oxide of an aromatic primary amino coupler developer to give a non-diffusible magenta dye; and 0V) a non-photosensitive layer located substantially adjacent thereto and containing a diffusion-resistant coupler that reacts with the oxide of the developer to provide a diffusible magenta dye.

C) red-sensitive unit: M aromatic primary amino, a red-sensitive negative-working silver halide emulsion layer containing a diffusion-resistant coupler that reacts with the oxide of a color developer to form a non-diffusible cyan dye; , ~0 a non-photosensitive layer containing a diffusion-resistant coupler located substantially adjacent thereto which reacts with the oxide of the developer to provide a diffusible cyan dye.

Furthermore, a color photographic light-sensitive material and a diffusion transfer film unit containing a diffusion-resistant coupler forming a color-correcting non-diffusible dye in at least one of the non-sensitive layers of each unit.

(3) A frame transfer film unit according to embodiment (1), wherein the image receiving element is provided on a different support than the photosensitive element.

(4) A film unit according to embodiment (1), in which the image-receiving element is provided on the same support as the photosensitive element.

(5) In the claims and embodiment (1),
A coupler photographic light-sensitive material in which each unit of the light-sensitive material is developed with a non-light-sensitive layer having a positive image distribution due to the action of an image-distribution transfer agent released image-wise as a result of development of a light-sensitive silver halide emulsion layer; and diffusion transfer film unit.

(6) In embodiment (5), the photosensitive material is a development inhibitor in which the distribution transmitting agent is released from the photosensitive layer in a negative image distribution; that is, the photosensitive layer of the photosensitive unit is an aromatic primary amine, a color developer. containing a compound which reacts with the oxide of the compound to release a development inhibitor, and the adjacent non-photosensitive layer of the pair contains a substantially water-insoluble silver salt that is spontaneously developable without the action of radiation. color photographic materials and diffusion transfer film units.

(7) In embodiment (5), undeveloped (N) silver halide emulsion grains in the photosensitive layer are water-temperature silver released from the same layer in a positive image distribution by dissolving in a silver halide solvent. A color photographic light-sensitive material in which the complex is a dispersion type agent, and a diffusion transfer film unit.

(8) A color photographic light-sensitive material and a diffusion transfer film unit according to embodiment (7), wherein a silver halide solvent is included in the processing composition and physical development nuclei are contained in the non-photosensitive layer of the photosensitive unit.

(9) In the above embodiment (7), the non-photosensitive layer contains a physical coral nucleus, and the photosensitive element contains an acid (preferably with a pKa of about 8 or more) whose conjugate base anion serves as a silver halide solvent. Containing color photographic material and diffusion transfer film unit.

00) In embodiment (1), at least one of the light-sensitive element and the image-receiving element contains the necessary components to neutralize the alkali provided by the processing composition to a level where the chromophore is stable.
A diffusion transfer film unit with a neutralizing layer containing acidic substances.

01) In embodiment α0), the diffusion transfer film unit wherein the neutralizing layer contains an acidic substance in an amount at least equivalent to the amount per unit area of alkali provided by the spread processing composition.

(12+) A diffusion transfer film unit according to embodiment α0, wherein the neutralizing layer is located between the support of the photosensitive element and the photosensitive units.

Alpha Embodiment Alpha power is a diffusion transfer film unit separated by a neutralizing layer and a photosensitive unit or neutralization rate controlling layer.

04) A diffusion transfer film unit according to embodiment QO), wherein the neutralizing layer is located between the multi-carrier of the image-receiving element and the image-receiving layer.

In (151 Embodiment Q4), the diffusion transfer 1 film unit wherein the neutralizing layer and the image-receiving layer are separated by a plating rate controlling layer.

06) In embodiment (1), the surface of the light-sensitive element on the side of the repellent layer with the transparent support protects the light-sensitive silver halide emulsion from external light when the film unit is processed in a bright place outside the camera. Diffusion transfer film unit covered by a light-blocking layer that can be protected and removed after processing.

In the same embodiment (1), the light-sensitive silver halide emulsion is removed between the transparent support side of the light-sensitive element and the light-sensitive silver halide emulsion layer when the film unit is processed in the light outside the camera. Diffusion transfer soy/1 unit covered with a light-shielding layer that can be protected from light and that does not lose its light-shielding ability through post-processing.

αB In an embodiment, a diffusion transfer film unit in which the light-blocking layer contains a black colloidal silver.

In the H embodiment (1), the photosensitive element is exposed through its transparent support and then covered with its repellant layer side before being subjected to Calo pressure, and the film unit is processed in the light outside the camera. A diffusion transfer film unit sometimes equipped with a light-shielding sheet that can protect the photosensitive emulsion layer from external light.

(a) In embodiment α9), a diffusion transfer film unit comprising a light-shielding sheet having an opening for accommodating the exposed photosensitive element and coupled to the receiver element at its periphery with the image-receiving layer inside.

(21) In Embodiment 0), the aromatic primary amine developer is a diffusion transfer film unit, wherein the aromatic primary amine developer is a para-phenylenediamine compound.

'(2. In the claims and embodiment (1), aromatic primary amino as the diffusion-resistant coupler.

A color photographic light-sensitive material containing both a coupler core residue capable of forming a dye structure (conjugated electron silver) by a coupler reaction with an oxide of a color developer and a hydrophobic residue having 8 or more carbon atoms, and a diffusion material. Transfer film unit.

(2. In the claims and embodiments (+),
As a diffusion-resistant coupler that provides a diffusible dye, (i
) Aromatic primary amino, a coupler core residue that can react with the oxide of a color developer to form a dye structure (conjugated electron@) and has at least one water-solubilizing group; il) A compound containing a hydrophobic residue having 8 or more carbon atoms at the coupling position of the coupler mother core residue, and having an aromatic primary amino or a substituent that can be removed by a color developer. color photographic materials and diffusion transfer film units.

(24) In embodiment (23), a color photographic material and a diffusion transfer film unit in which the water solubilizing group is selected from a sulfone group, a carboxyl group, and a sulfonamide group.

(2. In the claims and embodiment (1),
A color photographic material containing an α-acylacetanilide compound as a coupler that provides a yellow dye, and a diffusion transfer film unit.

(2. In the claims and embodiment (1),
A color photographic material and a diffusion transfer film unit containing a 5-pyrazolone compound as a coupler giving a magenta dye.

(2. In the claims and embodiment (1),
Phenolic compounds as couplers that give cyan dyes,
A color photographic light-sensitive material containing an α-naphthol compound and a diffusion transfer film unit.

(28) In the above embodiment (6), the color contains a diffusion-resistant coupler that detaches and couples a mercapto compound (alkyl mercapto, aryl mercapto, heterocyclic mercapto) as a compound that releases a development inhibitor. Photographic materials and diffusion transfer film units.

(29) In embodiment (6), a color photographic material containing a diffusion-resistant halodroquinone whose nucleus is substituted with an alkylthio group, an arylthio group, or a heterocyclic thio group as a compound that releases a development inhibitor; Transfer film unit.

(30) In the claims and embodiment (1), a color photographic material in which the support of the receptor element is transparent;
and diffusion transfer film unit.

(31) In embodiment (30), the anti-support surface of the photosensitive element contains a light-absorbing material in an amount necessary to protect the silver halide emulsion from external light when the film unit is processed in the light outside the camera. and covered with a light-blocking layer through which the processing composition can penetrate.

(32) In embodiment (31), the processing composition contains a substantial portion of the light-reflecting material in an amount necessary to mask the light-blocking layer of the photosensitive element to form a white background of the transferred dye body. Transfer film unit.

(33) In embodiment (1), the surface of the image-receiving layer contains a light-reflecting substance in an amount necessary to block coloring of the photosensitive element and form a white background of the transferred color body, and the processing composition permeates the surface of the image-receiving layer. The diffusion transfer film unit is covered by a layer that can be

(34) In embodiment (33), a processing composition containing a light-absorbing substance in an amount necessary to protect the light-sensitive silver halide emulsion from external light when the film unit is processed in the light outside the camera. Diffusion transfer film unit with

(35) In embodiment (11), the diffusion containing an amount of anti-corrosive substance in the support of the image-receiving layer or between the image-receiving layer and the support in an amount necessary to form a white background of the transferred dye body. Transfer film unit.

(36) In embodiment 0), the support 75 of the photosensitive element
) ε A diffusion transfer film unit containing a release layer between the farthest light-sensitive silver halide emulsion layer surface and the image-receiving element to facilitate separation of the light-sensitive and image-receiving elements after processing.

(37) A color photographic light-sensitive material and a diffusion transfer film unit, which contain a diffusion-resistant coupler that provides a non-diffusible yellow dye to a non-light-sensitive layer of a green-sensitive unit, as defined in the claims and embodiment (1).

(38) A color photographic light-sensitive material and a diffusion transfer film unit, which contain a diffusion-resistant coupler that provides a non-diffusible magenta dye to a non-light-sensitive layer of a red-sensitive unit, according to the claims and embodiment (1).

(39) In the claims and embodiment (1), the diffusion-resistant coupler is attached to the photosensitive layer of the same unit by providing a non-diffusible dye attached to the non-photosensitive layer. A color photographic material and a diffusion transfer film unit in which a diffusion-resistant coupler is added in a molar ratio of 0.05 to 0.5.

[Brief explanation of drawings]

FIG. 1 is a characteristic curve diagram of the photosensitive element of Example 1 described herein. FIG. 2 is a cutaway view of a photosensitive element, an image receiving element, and a processing liquid container used in the present invention. FIG. 3 is a sketch of one film of the present invention. A is the view seen from the photosensitive element side fJ), and b is the view from the image receiving element. FIG. 4 is a sketch of the arrangement of another film unit of the present invention. FIG. 5 is a sectional view of the film unit of FIG. 4.

Claims (1)

[Scope of Claims] 1. A negative development type comprising, on a transparent support, 1) a diffusion-resistant coupler that reacts with an oxide of an aromatic primary amino color developer to form a non-diffusible dye; 1i) substantially adjacent to said light-sensitive silver halide emulsion layer, a development inhibitor released as a result of development of said light-sensitive silver halide emulsion layer, or said light-sensitive silver halide emulsion layer; reaction with an oxidized aromatic primary amino color developer formed in a positive image distribution by utilizing the undeveloped silver halide (by solution physical development) remaining as a result of development of a polychromatic silver halide emulsion layer; and a substantially non-photosensitive layer containing a diffusion-resistant coupler which provides a diffusible dye. The non-photosensitive layer (11) to be formed contains a diffusion-resistant coupler that provides a non-diffusible dye that color-corrects (masks) unnecessary absorption of dyes with a negative image distribution occurring in the light-sensitive emulsion layer (1). A color photographic material characterized by: