DE2334035A1 - LIGHT SENSITIVE FILM UNIT FOR THE PHOTOGRAPHIC DIFFUSION TRANSFER COLOR PROCESS - Google Patents

Description

TATENTANWXlTE

DR. E. WIEGAND DIPL-ING, W. NIEMANN DR. M. KÖHLER DIPL-ING. C GERNHARDT? 3 ^ Λ ΓΠ ζ MDNCHEN HAMBURG £. OQHUO $ TELEPHONE: 555 476 8000 MO NCH E N 2, TELEGRAMS! KARPATENT MATHILDENSTRASSE 12

W 41 705/73 - Ko / DE July 4, 1973

Fuji Photo Film Co., Ltd., Minam'i Ashigara-shi, Kanagawa / Japan

Photosensitive film unit for the photographic Diffusion transfer color process

The invention relates to a photographic film unit for a photographic diffusion transferί « color process, particularly a photographic film unit for a photographic diffusion transfer color process, where practically colorless and diffusible compounds are the developers of the silver halides and dyes in the reaction with the oxidation products of aromatic primary amine compounds, can be used, these being practically colorless in the following and diffusible compounds as "coupler developers" are designated.

The subject of the invention is a non-peelable, photographic film unit for diffusion transfer color processes, which are used for treatment under through ^ " Guide the unit between a pair of opposing pressure-applying components is suitable that a Image taking element with one on one clear Support formed mordant layer, a photosensitive element with at least one photosensitive silver. balogenide emulsion layer, a water-impermeable Web and a pressure sensitive container containing an alkaline treatment solution, the

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Unit in the photosensitive element or in the fragile one Container contains a colorless diffusible compound which develops and develops the silver halide the dye by reaction with the oxidation product of the aromatic primary amine compound.

As in U.S. Patents 3,415,644-4,3,415,645. and 3,415,646 is given contains a color photographic Diffusion transfer film unit has a dye developer, i.e., a dye which is a silver halide developing agent and provides a diffusion transferred visible positive image of the dye developer on an extra layer of the image pickup element of the film unit without stripping the image pickup element of this by treating the film unit after recording in a camera with the dye developer after Removing the film unit from the camera «However, the above system has the defect that, since in the System a dye developer that produces a colored material represents, in the film unit in combination with a Silver halide is used, due in part to the amount of light that can affect the silver halide the light absorption by the color developer is reduced when the film unit is exposed. Consequently the sensitivity of the film unit cannot be increased.

US Pat. No. 3,635,707 describes a system in which a diffusion transferred positive color image is formed on an image receiving sheet without stripping the image receiving layer from the light sensitive element of the film unit by treating the film unit with a virtually nondiffusible compound which is a diffusible dye bsi reaction with the oxidation product of the development} j ttils results.

However, this system essentially requires implementation reverse development of the photosensitive member of the film unit.

It is therefore an object of the invention to provide a photographic film unit for the diffusion transfer color process, which has a high sensitivity and provides diffusion-transferred positive color images, without the need to reverse develop the film unit.

Another object of the invention is a diffusion transfer photographic film unit color process which produces a visible diffusion-transferred positive color image on the image receiving element without removing the image receiving element from the photosensitive element of the film unit after processing is stripped.

As a result of extensive research, the above objects of the invention have been achieved, i.e. according to of the invention is a photographic film unit for a color diffusion transfer photographic process obtained which for treatment by passing the unit between a pair of opposing pressure applicators Components is suitable and which, in the following order, the combination of the individual components includes:

1.) An image recording element which contains a stain layer on a transparent substrate.

2.) A photosensitive element having at least one photosensitive silver halide emulsion layer.

3.) A waterproof arch, and 4 «) at least one of the materials

a) a fragile container which, after breaking, releases its contents between the Image pickup element (1) and the photosensitive element

(2) is suitable, and / or

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b) a breakable container, which after breakage to release its contents between the photosensitive member (2) and the waterproof sheet is suitable, the photosensitive Element (2) contains a practically colorless and diffusible compound which the silver halide develops and which form a dye upon reaction with the oxidation product of an aromatic primary Amine compound is suitable, with at least one of the frangible containers an alkaline treatment solution contains, where

A) the film unit comprises an aromatic primary amine compound and an oxidizing agent together or separately one or more components of the image recording element (1), the light-sensitive element (2), the water-impermeable Sheet (3) and at least one of the frangible containers (a) and (b), and

B) the Filro unit a shading agent (shading. agent) in

i) at least one of the following: one between the photosensitive silver halide emulsion layer the light-sensitive element (2) which is closest to the image pick-up element (1), and the pickling layer of the image receiving element and the fragile container (A) located layer, or

ii) at least one of the components of the impermeable sheet (3) and the fragile container (b)
contains.

The film units according to the invention are used to form monochromatic or multicolored positives Images used. In a three-color system, each silver halide emulsion layer is the photosensitive, according to the invention used element with a coupler developer, which has a complementary color

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material forms the main sensitive area of the silver halide emulsion. That is, a blue-sensitive emulsion layer is combined with a yellow dye-forming coupler developer, a green-sensitive silver halide emulsion layer is combined with a magenta dye-forming coupler developer, and a red-sensitive silver halide solution layer is combined with a cyan dye-forming coupler developer. Any coupler developer associated with the respective corresponding silver halide emulsion layer can be incorporated in the silver halide emulsion layer or in a layer adjacent thereto.

The silver halide emulsion layers of the multicolored Photosensitive emulsion layers are on the support in the manner commonly used in this art Sequence formed, i.e. from the exposure side, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. If desired, a yellow filter layer can be placed between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb the blue light which passes through the blue-sensitive emulsion layer. An intermediate layer can also be present between any two silver halide emulsion layers. The above listed layers can be formed on a suitable permeable support or can be on a Be superimposed image pickup element, which will be described below.

The silver halide emulsions of the invention used light-sensitive elements contain silver chloride, silver bromide, silver chlorobromide, Süberjodbromid, Silver chloroiodide, silver chlorobromoiodide or

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mix of this. Such silver halide emulsions can be prepared by any known method. Examples of these are single nozzle emulsions, double nozzle emulsions, Lipmann emulsions, emulsions according to the ammonia process, emulsions according to the conversion process and the like and they can be prepared according to the processes, for example, of TB patents 2,222,264, 3,320,069, 3,271,157, 2,592,250, 3 206,313 and 3,447,927.

The silver halide emulsions used according to the invention can also be chemically desired with sulfur, gold, platinum, palladium or tellurium compounds Ils are matured, as in the IB patent writings

1 623 497, 2 399 083, 3 297 447 and 3 297 446 is given . '

The color sensitization of the silver halide emulsions according to the invention can be carried out by any known method. For example, as indicated in IB Patent 1,154,781, the Silver halide emulsion by adding a solution of a sensitizing dye in an organic solvent to the emulsion and, after stirring, by allowing the mixture to stand.

Examples of for the color sensitization of silver halide emulsions suitable sensitizing dyes are cyanine, merocyanine, styry! compounds, hemicyanine , and hemioxonols as described in US patents

2,526,632, 2,503,776, 2,493,748 and 3,384,486 are given are. The above-mentioned sensitizing dyes can be used individually or, if desired, as a mixture of two or more can be used.

Examples of useful cyanine dyes are given, for example, by PM Hamer, "The Cyanine Dyes and Related Compounds", Interscience, and P. Glafkides "Chimie Photographique", 2nd edition, 1957, Paul Montel, Paris, chapters 35-41.

The silver halide emulsions used according to the invention can also use a development accelerator such as a polyalkylene glycol, a cationic one contain surfactant or a thioether. They can also help prevent the Increase fog and decrease sensitivity while the silver halide emulsion is in storage will contain a stabilizer such as those disclosed in US Pat. Nos. 2,131,038 and 2,694,716 Thiaζoniumverbindungen that in the US patents 2,886,437 and 2,444,605 azaindenes, the mercury salts disclosed in U.S. Patent 2,728,663, those disclosed in U.S. Patent 3,287,135 Urazoles, which are described in U.S. Patent 3,236,652 specified SuIfocatechins in British patent specification 623,448 specified oximes in US patents 2,403,927, 3,266,897 and 3,397,9B7 disclosed nitroindazole mercaptotetrazoles disclosed in U.S. Pat 2,839,405 polyvalent metal salts and those disclosed in U.S. Patents 2,566,263 and 2,597,915 Palladium salts, platinum salts and gold salts.

The matchmaker developer who is the most characteristic Component according to the invention is a developer for silver halides and forms a dye Reaction with the oxidation product of an aromatic primary amine compound. The coupler developer is diffusible in an alkaline treating solution, however its diffusibility is reduced when the coupler developer develops the silver halide. Palis the Coupler developer which develops silver halide, the coupler developer changes to the quinone form from the hydroquinone form and the quinone form of the coupler developer is practically insoluble in an aqueous solution and not diffusible. Furthermore, the quinone form of the coupler hardens

developer uses the gelatin as a binder or the gelatin binder. Such Euppler developers are practically colorless and completely different from those in the IB patents 3,415,644, 3,415,645, 3,415,646, 3,473,925, and 2,983,606 specified dye developers. The dye developers used in accordance with the invention also have the property that they are dissolved and diffused in alkaline treatment solutions and are therefore completely different from the compounds specified in TB patent specification 3 635 707, which practical in alkaline treatment solutions which are most preferable at a pH above 12, are not diffusible.

The coupler developers which can be used according to the invention include compounds according to the general formula

(Connection) -Coup

OH

1) (Coup) one on the color photographic method known coupler compound means which one for the formation of a dye by reaction with the Oxidation product of an aromatic primary amine bond has a suitable structure, the dye preferably having its main absorption area in the blue, green or red area, and off

a) phenols or naphthols,

b) active methylene-containing compounds such as benzoyl · acetanilides and i-phenyl-5-pyrazolones and

134

c) cyanoacetylene, phenylacetonitriles, pyrazoles, Pyrazole-benzimidazoles and indazolin-3-ones

can be chosen ^

the main nucleus of the coupler consists essentially of a phenol, aniline or a chain radical or cyclic Residue with an active methylene group and such materials are detailed in "The Theory of the Photographic Process "by C.E.K. Mees, 3rd edition, pages 383-394 and ¥. Pelz in" Farbkuppler "AGPA Mitteilungen, Leverkusen, Volume 3, pages 111-175 (1961) described?

2) (compound) for the group linking the group (Coup) and the hydroquinone means which is composed of an alkylene radical can be selected, a * m is most preferred an alkylene radical with Cj-CU, the linking group with the grouping (Coup) at a different position connected as the clutch position;

3) the radicals R ₁ , R ₂ and R each represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxyl group, the latter two most preferably consisting of Cj-C 1 groups.

The coupler developer can have a catechin ring (bound in the 4-division) instead of the hydroquinone core as the developer core, but it is preferred that the developer core contains a hydroquinone core.

"The coupler developers used in accordance with the invention can be produced by various processes. For example, you can easily react by the example in U.S. Patent Nos. 3,134,764, 3 134 765, 3 173 906, 3 208 991, 3 218 312, 3 135 734, 3,201,384, 3,262,924, 3,252,969 and 3,297,441

3LJO

- ίο -

Hydroquinone derivatives with those known as color couplers Compounds such as those in der.belgischen patent 616 867, the German patents

1,124,556 and 1,187,479, British patents 873 125 and 856 158, U.S. patent 3,062,653, British patents 872 886 and 918 128; German patent 1 103 761; British patent specification 890 305, Belgian patents 644 330 and 643 146, IB patents 2,311,082 and 2,619,419, German Patent 1 101 429, US Patent

2,983,608, British Patent 956,261, German Patent 1,176,478 and 1,187,478, the LB Patent 2,964,402, the German Patent 1 111 505f of British Patent 837 360, den UB patent lifts 2 350 812, 2 293 004 and 2 976 146, French patent 1 323 977, German patents 1 163 144, 1 109 522 and 1 137 311, den U.S. Patents 3,002,836 and 2,589,004, British Patent 833,596, Belgian Patents 613,328 and 590,403, British Patent 858 564, U.S. Patent 3,056,674, British Patent No. 3,056,674 Patent 808 276, the Belgian patents 636 700 and 61 ~ 1 885, British Patent 865 492, German patent specification 1,176,479 and Japanese patent publications 4085/59, 18 333/60, 21 711/61, 18 145/63, 6030/65, 27 563/64 and 2/64 are described.

It is preferred that the used according to the invention Coupler developer diffuses in the presence of an alkaline treatment solution, but in the light-sensitive Element prior to treatment with the alkaline treatment solution is not diffusible, i.e. in the photosensitive member in which an alkaline processing solution is absent. Palis in the photosensitive Element present coupler developers

after the treatment would be diffusible by an alkaline treatment solution, another coupler developer other than the coupler developer partially enters the above-mentioned one to form a dye which absorbs light in the range of the complementary color to the photosensitive main area of the emulsion layer having the above coupler developer Emulsion layer by diffusion, so that color mixing or a decrease in color reproducibility occurs. In order to prevent this failure from occurring, it is preferred that the coupler developer is dissolved in a high-boiling solvent and the solution is dispersed in a hydrophilic colloid for confining the coupler developer in fine particles of the high-boiling solvent in the dissolved state. The preferred solvents have boiling points above 120 ⁰ C. Examples of these are Alkylphtha-Iate whose alkyl group has 1 to 6 carbon atoms, such as methyl phthalate, Äthylphthalat, propyl phthalate, n-butyl phthalate, propyl phthalate, di-n-butyl phthalate, amyl, Isoamylphthalat and dioctyl phthalate, Phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, diphenyl monop-tert-butylphenylphosphate, alkylamides or acetoanilides such as Nn-butylacetanilide, n-methyl-p-methylacetanilide and the like. The preferred hydrophilic colloids are gelatin, polyvinyl alcohol and the like.

Although not limiting, the amount of silver in each layer is usually 0.1-10x10 "^ mol / 100 cm ² , the coupler developer is usually 0.5-50x10" mol / cm, while the ratio of Ag / Coupler developer is usually 1-10 (molar ratio).

309884/1134

Furthermore, in order to prevent the dispersed fine particles of the high-boiling solvent containing the coupler developer "mix with the binder (dispersed oil coagulates) of the photosensitive element combine to form the coupler developer before crystallization in the overcoat and the ease of peeling off the overcoat containing the coupler developer contains, to improve, various common additives are needed. For example, surface-active Agents such as saponins anionic compounds such as alkylaryl sulfonic acids described in DS Patent 2,600,831 are amphoteric bonds described in US Pat 3,133,816, and water-solubilizing agents Additions of glycidol and alkyl phenols as disclosed in US Pat. No. 3,133,816 are used will. Citric acid, boric acid and the like can also be added to adjust the pH will.

The photosensitive used according to the invention If desired, elements can be provided with a protective layer, Intermediate layers, filter layers, antihalation layers, Provided ultraviolet absorbing layers and the like will.

In the pixel units according to the invention, as Auxiliary development agent used to designate compounds e.g. silver halide developing agents of the benzoloid type, i.e., a silver halogen developing agent with a benzene nucleus or naphthalene nucleus with at least two substituents from the class of hydroxyl groups, Amino groups, alkyl! Amino groups which form an oxidation product of a silver halide developing agent of the quinoid type are useful in developing the exposed silver halide. Examples of such auxiliary silver halide developing agents are hydroxyphenylhydroquinone, pheny! hydroquinone, 4'-methylpheny! hydroquinone,

309884 / 1-134

p- (tert.) - butylcatechol, tert.-buty / hydroquinone and the like. Examples of further auxiliary developing agents are 3-pyrazolidones and preferred examples thereof are 1-phenyl-3-pyrazolidone and 1- (p-methyl) phenyl-3-pyrazolidone. The auxiliary developing agents can be in a protective layer, a silver halide emulsion layer, a coupler developer layer, an intermediate layer or in more than one, such a layer of the photosensitive element can be incorporated, as in IE Patents 3,266,842 and 1,243,539 and Japanese Patent Nos. 17,383/60 and 393/64. The main purpose of applying such Auxiliary means of development consists in acceleration the development of the exposed silver halide by the coupler developer. The application of the auxiliary developing agent also results in a reduction in the minimum density of the positive formed on the mordant layer Image, an increase in the maximum density of the same and an improvement in color separation. It will do this too British Patent 1,243,539 and Japanese Patent Publications 4839/60, 10240/69, 2241/62, 29130/64 and 13837/68 referenced. Usually 10 to 1/100 mole of auxiliary developing agent / mole of coupler developer used.

As a binder for the protective layer, the silver halide emulsion layer, the coupler developer layer, the intermediate layer and the like of the photosensitive elements according to the invention, gelatin, gelatin-containing calcium alginate and gelatin phthalate are mentioned as examples. Examples of further binders are given in IE patent 3 384 483 and further examples are Polyviny.lamid, polyacrylamide, polyvinyl alcohol, polyvinyl pyrolidone, Cellulose derivatives, polysaccharides and the like. The binders specified above can be used individually or used as mixtures. The binders can also be used together with various hardening agents.

-H-

In the photosensitive elements according to the invention, each can be provided with a coupler developer associated silver balogenide emulsion links on an alkali-permeable carrier, for example a transparent or opaque sheet of polyvinyl alcohol or gelatin, d.b. the Coupler developer is in a silver balogenide emulsion layer or an adjacent layer is incorporated into it.

Also needs, as in Pig. '2 of the accompanying drawing shown in the embodiment of the pilm unit according to the invention, where a photosensitive element is an image pickup element with a spacing between faces them so that an alkaline treatment solution is spread between the elements the support for the photosensitive element may not necessarily consist of an alkali-permeable support, but can also be a transparent carrier if the carrier is not attached to the side that faces the image pickup element. All up Supports known in the photographic art can be used as such transparent supports, for example Polyethylene terephthalate films, cellulose triacetate films, polycarbonate films and the like.

The silver halide emulsion layers can be applied to the support in several layers or can be incorporated in one layer as microcapsules containing each of them separately, as in FIG IB patents 2,800,457, 2,800,458 and 2,907,682 specified. The method of manufacturing such microcapsules for photosensitive members is for practical use in IB patents 3,466,662 and 3,276,869.

On the other hand, as a carrier for the image pickup element, which a stain layer on a transparent

Support comprises a dimensionally stable transparent support used. Examples of such supports are cellulose acetate films (cellulose triacetate films, Cellulose acetate films and the like), cellulose acetate butyrate films, Polyvinyl acetal films, polystyrene films, polyethylene terephthalate films, Polycarbonate films, glass plates, and the like.

As a pickling material for the pickling layer, all Materials are used, which puncture the pickling or fixation of the coupling of the coupling developer and the oxidation product of the aromatic primary amine compound.

For the image receiving material, it is necessary to use a material which has a layer which is hydrophilic and which is capable of pickling the diffusible dyes. It is preferred to use a hydrophilic, basic and film-forming polymer or a hydrophilic and film-forming polymer which contains a basic polymer. As specific examples of image receiving layers according to the invention, a mixture of polyvinyl alcohol and poly-4-vinylpyridine, as indicated in US Pat. No. 3,148,061, is preferably used, but other materials, for example a partially acetalized product of polyvinyl alcohol (degree of acetylation not more than 2 ^ %) and a quaternary trialkylammonium benzaldehyde salt, a copolymer of vinyl alcohol and N-vinylpyirolidone, where all copolymerization ratios can be used, condensed acetalization products (from about 4: 1 to about 2: 1 as molar condensates) of polyvinyl alcohol and poly-N vinylpyrrolidone and condensed acetalization products (from about 4: 1 to about 2: 1 as molar condensate) / of polyvinyl alcohol and 4-pyridinecarboxaldehyde can also be used as image-receiving layers. These

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the

List is illustrative only for materials / * the above meet general criteria.

Basic polymers such as polymers made from the aminoguanidine derivatives are further examples of such materials of vinyl methy! ketone according to the US patent 2 882 156 listed. Further examples of useful compounds for the pickling layer according to the invention are Poly-4-vinylpyridine and poly-2-vinylpyridine and those in in U.S. Patent 2,484,430. These compounds can be used together with an alkali-permeable polymer, such as N-methoxymethyl polyhexylmethylene adipic acid, a partially hydrolyzed polyvinyl acetate, Polyvinyl alcohol, cellulose acetate, gelatin and the like can be used.

The mordant layer can be an ultraviolet absorber contained in order to prevent the dyes formed thereon from fading, and may furthermore a stilbene, triazine or oxazole derivative and the like in order to obtain a vivid color image. Farther can be used to control the graduation of the development of the silver halide in the light-sensitive elements after penetration of the alkaline treatment solution the Pickling layer a development inhibitor, for example a mercaptotetrazole, benzotriazole, an iodine compound and the like contained in the alkaline treating solution can be solved.

Preferred primary aromatic amino compounds, as used according to the invention, are p-phenylenediamine derivatives, which are well known in the field of color photography. Examples of such derivatives are 4-Amino-N, li-diethyl-3-methy! Aniline, H, N-diethyl-p-phenylenediamine, N-ethyl-N- (ß-methanesulfonamido) -ethyl-3-methy 1-4-aminoaniline, 4-amino-N-ethyl-3-methyl-F- (ß-sulfoethyl) aniline, 4-Amino-N-ethyl-3-methoxy-IT- (ß-sulfoethyl) aniline, 4-amino-N-ethyl-N- (ß-hydroxyethyl) -aniline, 4-amino-N, IT-

30.9884 / 1134

diethyl-3-hydroxymethylaniline, 4-amino-li-raethyl-N- (ßcarboxyäthyl) -aniline, 4-amino-N, N-bis (ß-bydroxyäthyl) aniline, 4-amino-N, N-bis (ß-hydroxyethyl) aniline, 4-amino-Ν, ΪΤ-bis (ß-hydroxyethyl) -3-methylaniline, 3-acetamido-4-amino-N, lf-bis (ß-hydr oxy ethyl) aniline, 4-amino-N-ethyl-N- (2,3-dihydroxypropyl) -3-methylaniline sulfate, 4-amino-N, N-diethy1-3- (3-hydroxypropoxy) aniline and the like Materials. These amines are usually used in amounts of 0.1 to 5% by weight of the treatment solution.

These aromatic primary amine compounds can be incorporated into the image receiving element and In the pail of application, for example the pickling layer, the aromatic primary amine compound can be dispersed the same in the above alkali-permeable polymer as a solution thereof in an organic solvents are used. For example, the primary amine compound can be in an oil (discussed above high-boiling solvents) and then dispersed in the coating solution of the pickling layer. Or the primary amine compound is dissolved in an aqueous weakly acidic solution and then this is with the aqueous solution of the polymers mixed. But you can also by mixing a solution with the same an alkaline aqueous solution can be used. The aromatic primary amine compound can also be either can be incorporated into the breakable container of the film unit together with the alkali or can be incorporated into a layer adjacent to the mordant layer can be incorporated and further it can be incorporated into a layer of the photosensitive Element or a layer of the waterproof Arch, which are present in multilayer form can be incorporated into the pilm unit according to the invention.

The aromatic primary amine compound is therefore incorporated into one or more of the following layers:

3 0 988 4/1134

a) the pickling layer,

b) in one of the fragile containers,

c) in a layer adjacent to the pickling layer,

and in this EaIl there is a special layer for inclusion is the aromatic primary amine compound, for example by dissolving them in a solvent with a high boiling point, as discussed above, and emulsifying the same in aqueous gelatin;

d) in any layer of the photosensitive element,

e) in the impermeable arch.

According to the invention, an oxidizing agent is used for oxidizing the above-mentioned aromatic primary Amine compounds are used, preferably in a molar ratio of 1: 1 »Examples of oxidizing agents are potassium ferricyanide, hydrogen peroxide, potassium bicnromate, Ammonium persulfate, copper sulfate, exposed Silver halide, quinone, and the like as are known in the art. These oxidizing agents can may be incorporated into one layer of the image pickup element, or may be incorporated into any component other than incorporated into the image pickup element. For example the oxidizing agent can be in the breakable container or in a layer of the photosensitive Element can be added.

The aromatic primary amine compound and the oxidizing agent can be present together or separately. Any arrangement where the aromatic primary amine compound and the oxidizing agent the first time at the time of Mixing development is preferred. In the film unit according to the invention is the use of a pH lowering layer effective to increase the stability of the transferred image and the color reproducibility to improve.

309-984 / 11 SA

233A035

The pH lowering layer generally has the effect of lowering the pH of the image receiving layer, which has a pH of 11 to 14 upon penetration of the alkaline treatment solution, to a pH lower than 11, preferably 5 to 8 within a short period of time. It preferably has a dry starch from 5 to 20 microns. That disclosed in DS Patent 3,362 specified polymeric acids can be used as a pH lowering layer for example can be used. The polymeric acids lower the pH of the film arrangement the development, interrupt the further transport of the coupler developer and continue to stabilize the transferred color image. The polymeric acids contain an acid group, for example a carboxylic acid group or a sulfonic acid group, and forms the acid group usually a sodium salt or potassium salt or is with a quaternary ammonium salt, for example ammonium 4-methyl peroxide combined. The polymer can be partially anhydrated (acid anhydride form) or can be Xactone form or can be combined with a base.

Examples of such compounds are cellulose acetate hydrogen phthalate, Cellulose acetate hydrogen glutarate, cellulose acetate hydrogen succinate, ethyl cellulose hydrogen succinate, Cellulose acetate succinate hydrogen phthalate, the ether and ester derivatives of with sulfuric anhydride treated cellulose, polystyrene sulfonic acid, carboxymethyl cellulose, polyvinyl hydrogen phthalate, polyvinyl acetate hydrogen phthalate, Polyacrylic acid and acetals of polyvinyl alcohol that are substituted with a carboxy or sulfo Aldehyde treated. Other compounds disclosed in U.S. Patents 3,422,075 and 2,635,048 can also be used.

The pH lowering layer is usually between the mordant layer and the support of the image receiving layer

309884/1

attached to the imaging unit, but if the desired puncture is obtained, and can continue to be attached to each point of the film unit, such as in U.S. Patent 3,361,821, the polymeric Acid can be encapsulated by a polymeric material and added to the photosensitive element or can be dispersed in the alkali-permeable binder and added to the photosensitive element ^ - will be added. The alkaline treatment solution penetrates into this pail through and through the wall covering the dispersed particles of the polymeric acid the pH of the treatment solution is reduced, thereby stabilization of the color image formed on the mordant layer of the film unit occurs.

A photographically inactive timing layer or Spacer layer can be adjacent to the pH lowering layer be trained. The timing layer is used to control the pH of the film unit, see above. that this as puncturing the speed of penetration the alkaline treatment solution by the inactive Spacer layer sinks. It is preferred that after the coupler developer is imagewise diffused and the coupling of the diffused coupler developer with the Oxidation product of the aromatic primary amine compound is complete, the pH of the film unit drops rapidly and then remains at about 5 to 8. Has preferred they have a thickness of 2 to 20 microns (dry thickness). as such timing layer can be gelatin and polyvinyl alcohol and further that in U.S. Patent 3,455,686 specified polymers are used. Furthermore, the imagewise diffusion of coupler developer and the Coupling of the coupler developer and the oxidation product of the aromatic primary amine is a function of the temperature, so that also the neutralization of the alkali

309884/1134

is a puncture of temperature. That is why it is common use the following compounds individually or as a mixture for the timing layer or the spacer layer, i.e. hydratable polymers such as polyacetate, polyamide, Polyvinyl ethers and partial acetates of polyvinyl alcohol.

According to the invention, an alkaline treatment solution is housed in a frangible container. Examples of the alkaline treatment solution are aqueous alkaline solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, lithium hydroxide and diethylamine. The pH of the solution is preferably above 11. It is also preferred that the treatment solution contain a high molecular weight polymer to increase the viscosity of the solution, for example hydroxyethyl cellulose or carboxymethyl cellulose. The amount of the viscosity increasing agent is 1 to 5 # of the total amount of the treatment solution or is adjusted so that the viscosity of the treatment solution is 100 to 200,000 cps. .

To accelerate the development of the silver halide, to increase the maximum density of the stained color image on the posi-sheet, to lower the minimum density and to improve the color separation in color reproduction, an onium compound, for example a quaternary ammonium compound, quaternary sulfonium compound or quaternary phosphonium compound can be added to the treatment solution. Specific examples such onium compounds include 1-ethylpyridinium bromide, Lauryldimethylsulfonium cetyl trimethylammonium bromide, p-toluenesulfonic acid and 1-benzyl-a-picolinium tosylate tetraethylphosphonium bromide. Usually 0.1 to 2 wt .- 5 ^, based on the treatment solution, the Onium connection used.

309884/11-U

. - 22 -

All examples of shading agents according to the invention be carbon black, barium sulfate, zinc oxide, barium stearate, silver powder, silica powder, aluminum oxide powder, Zirconium oxide, zirconium acetylacetate, sodium zirconium sulfate, Kaolin, pumice, titanium dioxide and organic dyes like nicrosine are listed. If necessary, can two or more compounds, as listed above, can be used together to produce the desired To achieve shading effect.

The shading agent is used to follow the development of the film unit in a bright spot to allow exposure and removal of the film unit from the camera and consequently the shading agent be incorporated in any part of the film unit as far as the light-sensitive silver halide emulsion layers the photosensitive element are protected from exposure to radiation, thereby creating the emulsions be exposed. That is, 1.) the shading agent is divided into one or more layers, which between the pickling layer of the image pickup element and the photosensitive silver halide emulsion layer of the photosensitive element closest to the Image pickup element is attached and the frangible container spreads its contents therebetween the photosensitive element and the image receiving element, or 2.) the shading agent is in at least one of the materials is more impermeable to water Sheet and fragile container, which its contents between the waterproof sheet and the photosensitive Element spreads, incorporated.

If the shading agent is added to the alkaline treating solution in the breakable container will give good results when using the shading agent, for example carbon black or titanium dioxide, obtained in an amount of 5 to 40 wt.% of the treatment solution.

3Q9P «K / ■ 1 1? 4

When the shading agent is added to the alkaline treating solution, it can be dissolved or suspended in the solution. In the case of incorporating the shading agent in the coating of the film unit, the shading agent is finely dispersed in an alkali-permeable binder such as polyvinyl alcohol or gelatin, which is then absorbed and, for example, 10 $> carbon black based on the weight on the basis of the gelatin a dry thickness of 4 microns is used.

The shading agent is a material, which the light by absorption or reflection of the light shaded and in the film unit according to the invention it is preferred if the mordant layer on a transparent Support is formed to allow the shading agent to pass the light between the mordant layer and the photosensitive 'Reflects element. By adopting such a configuration, the transferred color image can be clear with high density due to the presence of the layer of light reflected by the shading agent can be seen at the back of the back of the mordant layer when the formed color image is on the mordant layer is observed through the transparent support.

Generally the density is above 4, preferably about 10, for the shading agent.

Specific examples of treatment solutions are given below, although those used according to the invention Treatment solutions are not limited to this. Solutions I and II are for the shading and the Solutions III and IV are for development:

I: water 100 ml

Hydroxyethyl cellulose 3 _t 2 g titanium dioxide 6.0 g

309884/1 134

II:

III:

IV:

water 100 ml 0.5 G Sodium hydroxide 3.0 7.0 G Hydroxyethyl cellulose e 3.2 3.0 G soot 0.6 water 100 ml G Potassium hydroxide 3.5 G Hydroxyethyl cellulose e 5.5 G 1-Benzy1-a-picolinium-
bromide 0.8 G Barium sulfate 10.0 water 100 ml G Sodium hydroxide 3.0 G 3rMethyl-4-amino-N "-ethyl-
N-ß-hydroxyethylaniline 3.0 G 1-ethyl-pyridinium bromide 0.8 G Benzotriazole G Titanium dioxide G Hydroxyethyl cellulose e

The waterproof sheet can be one of those according to the invention used transparent supports of the image pickup elements are selected.

Preferred film units according to the invention are shown in the accompanying drawings, wherein Like reference numerals indicate like components and each element is in a schematically enlarged view Cross section shown.

Pig. 1 is a perspective view of an embodiment a film unit according to the invention. In the Pig. 1 become a shading layer 2 and a photosensitive member therein Order formed on an image pickup element 3 and

/ 113Ä

a shading waterproof sheet 41 is hereby connected along the leading edge of the same. A fragile container 5 that holds the alkaline treatment solution contains, is attached to the leading edge of the photosensitive element. The reference number 6 denotes pressure application rollers.

The shading waterproof sheet 41 The film unit of this type is so constructed that it does not interfere with the exposure of the photosensitive Element 1 in the camera provides and is then on the light-sensitive element when passing through the film arrangement piled up by the rollers 6 after exposure in the camera. In this case it breaks Container 5 and its contents spread between the photosensitive element and the shading water-impermeable Bow out.

As a result, the photosensitive element 1 of the film assembly, which is peeled off on the camera, is in front unnecessary exposure through the shading waterproof sheet 41 and the shading layer 2 protected.

Fig. 2 is a perspective view of another embodiment of a film assembly according to the invention; wherein the photosensitive member 1 is an image pickup member 3 with a space therebetween faces and a fragile container 5, the contains an alkaline treatment solution, so appropriate is that the treatment solution is between the two Elements spreads when the container is broken.

Fig. 3 is an enlarged section of the film unit shown in Fig. 2. The photosensitive Element consists of an alkali-permeable carrier 171 which contains an oxidizing agent with a coated on it red sensitive emulsion layer 162, one layer

30988 4 /

with a cyan coupler developer, an intermediate layer 15, a green-sensitive emulsion layer 142, a layer 141 with a magenta coupler developer, a yellow filter layer 13, a blue-sensitive emulsion layer 122, a layer 121 containing a yellow coupler developer, and a Protective layer 11 contains. The image pickup element consists of a transparent carrier 34 with a mounted thereon Alkali neutralizing layer 33, a spacer layer 32 and a pickling layer 31. The fragile one Container 5 contains an alkaline treatment solution which contains the aromatic primary amine compound and the shading agent.

In this embodiment, the film unit of the side of the protective layer exposed in the camera. if the film unit is exposed, the protective layer not covered with a shading arc. After The film unit is exposed through the pressure application rollers 6 in the case of removal of the film unit from the camera, whereby the container 5 is broken and the treatment solution between which the oxidizing agent containing alkali-permeable support 171 of the light-T-sensitive Element and the pickling layer 31 of the image pickup element is spread and is simultaneously the shading waterproof sheet 41 on the Protective layer 11 is stacked. The treatment solution that spreads out penetrates the light-sensitive Element one and this gets the silver halide in each that exposed in the previous exposure step Silver halide emulsion layer through the one with the emulsion layer unified coupler developers. In this way for the development of the silver halide The developer couplers used are therefore not diffusible. On the other hand, the coupler developer diffuses, which was not consumed for the development of the silver halide, at least partially to the pickling layer and causes a coupling in it with the aro-

309884/113 *

matic primary amine compound in the by the in the oxidizing agents containing alkali-permeable carrier 171 oxidized treatment solution. The one through the clutch Dye formed colors the mordant layer 31 and forms a positive image. The one that has penetrated into the image pickup element alkaline treatment solution is juxtaposed through spacer layer 32 at an appropriate rate to the pickling layer 31 and the alkali neutralizing layer 33, and consequently has no harmful Influence on the color image in the Seizschicht due to the high pH value, creating a positive image of good Stability and the desired image density is obtained. The positive image formed in this way can be of the Side of the transparent carrier 34 without stripping off the photosensitive element can be observed.

Fig. 4 is a perspective view of another Embodiment of the film unit according to the invention, using a transparent waterproof sheet 4 and the film unit using two breakable containers 51 and 52. In this embodiment are the transparent waterproof sheet 4 that photosensitive element 1 and the image pickup element 3 are mounted with a space therebetween, and the fragile containers 51 and 52 are mounted so that their 'contents between the sheet 4 and the photosensitive Element 1 and between the photosensitive element 1 and the image pickup element 3 respectively.

Figures 5 to 10 are perspective views of various specific embodiments of the in Fig. shown film unit.

In the embodiment shown in FIG the reference number 4 the transparent waterproof sheet. The photosensitive element comprises one alkali-permeable carrier 17 with a drawn thereon

0 9 8 fU / 1 13 Ä

red-sensitive emulsion layer containing a Oyan coupler developer, an intermediate layer 15, a green-sensitive emulsion layer 14 containing a Magenta coupler developer, a yellow filter layer 13, a blue-sensitive emulsion layer 12 containing the content a yellow coupler developer and a protective layer 11. The image receiving element comprises a transparent support 34 with a coating thereon of an alkali neutralizing layer 33, a spacer layer 32, a Pickling layer 311- which contains an oxidizing agent, and a layer 211 which contains the aromatic primary amine compound and contains a shading agent. The container 51 contains the treatment solution mentioned above II and is attached so that its contents after breaking between the transparent water-impermeable Sheet 4 and the protective layer 11 is spread and the container 52 contains the above treatment solution II and is attached so that its contents when broken between the alkali-permeable carrier 17 of the photosensitive element and the layer 211 of the image receiving element, is spread and contains an alkaline treatment solution containing the Shading agent.

The film unit is in the camera from the side of the transparent opaque sheet 4 is exposed, and then the film unit is passed through the pressure applying rollers 6 guided upon removal from the camera, removing the contents of the fragile containers 51 and 52, respectively spread between the elements. Since the treatment solution in the container contains the shading agent, is the photosensitive element before exposure to light protected after the pilm unit is removed from the camera. This creates a positive image on the stain layer formed and the image can be viewed from the side of the trans-

309884/1134

* - 29 -

, parent carrier of the image pickup element can be observed.

In the embodiment shown in Pig x 6 are the positions of the green-sensitive emulsion layer 14 containing the magenta coupler developer and the red sensitive emulsion layer 16 containing the cyan coupler developer versus that in Pig. 5 shown Embodiment reversed and a layer 21 that the aromatic primary amine compound is formed on the alkali-permeable support 17. the Layer 212 of the image receiving element contains the oxidizing agent and the shading agent. The fragile one Container 51 contains a solution containing the shading agent and the breakable container 52 contains the alkaline treatment solution that contains the shading agent.

In Pig. 7 includes the embodiment shown the alkali-permeable support 117 of the photosensitive Element is a shading agent and is also a layer 212 containing an oxidizing agent and a shading agent is formed on the image pickup element. The breakable container 51 contains a shading agent and the breakable container 52 contains contains an alkaline treatment solution which is a contains aromatic primary amine compound.

In Pig. 8 are the embodiment shown an alkali neutralizing layer 33 and a spacer layer 32 in that order on a transparent waterproof sheet Arch 4 formed. The breakable container 51 contains an alkaline treatment solution, which contains a shading agent, and the fragile container 52 contains an alkaline treatment solution and an aromatic primary amine compound.

30988 / · / 1 1

In Pig. 9 is the embodiment shown a shading layer 2 on the stain layer 31 of the Image pickup element formed. The fragile one Container 51 contains an alkaline treatment solution, which contains an aromatic primary amine compound and a shading agent, and the fragile container 52 contains an alkaline treatment solution, which are an oxidizing agent and a shading agent contains.

Included in the embodiment shown in FIG the photosensitive element has an alkali-permeable support 17 having a layer coated thereon 18, the microcapsules containing a magenta coupler developer in a hydrophilic colloid as a binder and a green-sensitive emulsion and microcapsules containing a cyan coupler developer and a contains dispersed red-sensitive emulsion, a yellow filter layer 13, a blue-sensitive emulsion layer 12 containing a yellow coupler developer and a protective layer 111 containing the aromatic primary amine compound contains. The breakable containers 51 and 52 each contain an alkaline treatment solution, the contains a shading agent.

Pig. 11 is a perspective view of another embodiment of a film unit according to the invention. In this embodiment, a shading layer 2 and a photographic element 1 are therein Sequence formed on an image pickup element 3.

Pig. Figure 12 shows an enlarged section of that in Pig. 11 film unit. Like from Pig. 12 can be seen, is a shading layer 211 containing an aromatic primary amine compound between the mordant layer 311, which contains the oxidizing agent, and a red sensitive emulsion layer 16 attached. D * r fragile Container 5 contains an alkaline treatment

309884/1134

solution containing a shading agent.

Examples of fragile ones which can be used according to the invention Containers are disclosed in U.S. Patent Nos. 2,543,181, 2,634,886, 2,653,732, 2,723,051, 3,056,492, 3,056,491 and 3,152,515, such containers are indicated by double formation of a liquid and gas-impermeable sheet formed in such a way that two walls are formed and the long edges of the walls and both ends are sealed, leaving room for retention of the treatment solution results in · The longitudinal seal the container is weaker than the seals at the ends of the same so that if there is pressure on the walls of the container containing the treatment solution is applied the longitudinal seal of the container is broken by the liquid pressure.

The elements of the film unit according to the invention are connected to one another by means of a binding member and the binding member may consist of a pressure sensitive tape which covers the layers of each element attached or retained at the respective edges. The tape also acts to keep the treatment solution between to maintain the elements and also serves to prevent the treatment solution from seeping out of the Film unit.

In a film unit using a conventional dye developer, the photosensitive element is not stripped from the image pickup element it is necessary to use an optical system to invert the image in the camera. Furthermore, it is with one Film unit using a nondiffusible dye image which is a material used to form a diffusible dye is suitable in the reaction with an oxidized developer provides, such as specified in US Pat. No. 3,635,707, necessary

309884/113 / *

to get a positive image in order to obtain an image reversal eligibility of the photosensitive element, for example to use a direct positive silver halide emulsion.

On the other hand, in the film unit according to the invention, the exposure side faces the film unit attached to the side of observation of the positive image and therefore the application of an optical one Inversion system, as stated above, unnecessary. Furthermore, according to the invention, there is a diffusible and practically colorless compound which is a dye in the reaction with the oxidation product of an aromatic primary amine compound forms and the one. Developing agent for the silver halide is used and it is unnecessary to reverse the image Forming element, for example by applying a direct positive silver halide emulsion in the photosensitive Element.

In the foregoing, the invention has been described on the basis of preferred embodiments, without being subordinate to this is limited.

309884/113 / *

Claims (6)

Claims My Photographis ehe pilm unit for the diffusion transfer color process which is suitable for processing by performing the unit between a pair of opposing pressure applying members and which comprises the combination in this order of 1) an image pickup element placed on a transparent Carrier has formed a pickling layer, 2) a photosensitive element having at least one photosensitive silver halide emulsion layer, 3) a waterproof arch and 4) at least one of the following materials a) a frangible container capable of releasing, after rupture, its contents between the image receiving element (1) and the photosensitive element (2) is capable, and b) a frangible container capable of being released after breaking its contents between the photosensitive Element (2) and the water-impermeable sheet (3) capable of being the photosensitive element (2) contains a practically colorless and diffusible compound which develops silver halide and which for Formation of a paraffin in the implementation with the Oxidation product of an aromatic primary amine compound is suitable, wherein at least one of the frangible containers contains an alkaline treatment solution and where A) the pilm moiety is an aromatic primary amine compound and an oxidizing agent together or separately in one or more components of the image recording element (1), the light-sensitive element (2), the waterproof sheet (3) or at least one of the frangible containers (a) and (b), and 309884/113 /. B) this film unit has a shading agent, in i) at least one of the between the photosensitive silver halide emulsion layer of the photosensitive Element (2), which is closest to the image pickup element, and the pickling layer of the image pickup element and layer or attached to the frangible container (a) ii) in at least one of the materials of impermeable sheet (3) or breakable container (b),
contains. 2. Photographic film unit for diffusion transfer color process according to claim 1, characterized in that the practically colorless and diffusible ' Connection through the general. formula (Connection) - (coup) OH is represented in which (Coup) a coupler group, (compound) a group (Coup) and the hydroquinone nucleus connecting group and R ^, ILj and IU a hydrogen atom, represent a hydroxyl group, a halogen atom, an alkoxyl group or an alkyl group. 3. Photographic film unit for diffusion transfer color process according to claim 2, characterized in that the coupler group (Coup) consists of a phenol or a naphthol. 4. Photographic film unit for diffusion transfer color process according to claim 2, characterized in that the coupler group (Coup) consists of a benzylacetanilide or a 1-phenyl-5-pyrazolone. 309884/1 13 / * 5. Photographic film unit for diffusion transfer color process according to claim 2, characterized in that the coupler group (Coup) consists of a cyanoacetyl, a phenylacetonitrile, a pyrazole compound, a pyrazolobenzimidazole or an indazolin-3-one. 6. Photographic film unit for diffusion transfer color process according to claim 2 to 5, characterized in that the indicated by (connection) Group consisting of an alkylene group, an arylene group, an ether group, a thioether group, a carbonyl group, a sulfonylamino group, a sulfonylamino group or an amide group ". 3 0 9 8 B 4/1 13A Blank page