DE3510685A1 - COLOR PHOTOGRAPHIC RECORDING MATERIAL DEVELOPABLE BY HEAT TREATMENT - Google Patents

Description

AGFA-GEVAERT

Aktiengesellschaft D 5090 Leverkusen

Patent Department Hs / Div-c

Color photographic recording material developable by heat treatment \

The invention relates to a color photographic recording material which can be developed by heat treatment with a photosensitive binder layer, which in the form of separate complex coacervates several different spectrally sensitive assignments from each

a) a photosensitive silver halide of

relevant spectral sensitivity, if applicable in combination with a substantially non-photosensitive silver salt and

b) a non-diffusing coloring compound, which, as a result of the development, release a diffusible dye by heat treatment able to

contains, the silver halide being predominantly blue-sensitive in at least one of the assignments mentioned is.

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It is known to produce colored images by heat treatment using suitable color photographic recording materials to manufacture. Suitable as coloring compounds in particular those that are in non-diffusing form in the layer of a photographic Recording material can be stored and as a result of the development a diffusible Able to release dye (dye releasers). The particular suitability of such color releasers is based on the fact that the image-wise released dyes are transferred to special image-receiving layers can produce a brilliant color image that is not overlaid by interfering silver or silver halide and therefore does not require any follow-up treatment. By combining the heat generation process with the color diffusion process there is thus a advantageous rapid process for producing colored images. A suitable recording material for this is for example described in DE-A-32 15 485.

According to this publication, a recording material with a layer comprising a combination of silver halide, Contains silver benzotriazole, a dye releaser and guanidine trichloroacetate (base donor), imagewise exposed and then subjected to a heat treatment in contact with an image-receiving sheet, wherein the image-wise released dye is transferred to the image-receiving sheet. For making multicolored There must be several such combinations, with the silver halide in each of the

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these combinations for a different spectral range of the Light is sensitive and according to its spectral sensitivity contains a dye releasing agent that releases a dye of a different color, usually a color that is complementary to the color of light for which the silver halide in question is a has predominant sensitivity. Such assignments can be in different layers one above the other be arranged; however, it is often observed with such an arrangement that the heat build-up a sufficient transfer of color from the light-sensitive layer furthest away from the image-receiving layer Layer is difficult to reach.

The use of so-called packet emulsions, several of which are each with a different one, offers a remedy here Spectral sensitivity as a so-called "mixed grain emulsion" contained in a single photosensitive layer. Any of these package emulsions consists of particles ("packets") distributed in a binder phase containing light-sensitive silver halide a special spectral sensitivity and a spectrally assigned coloring compound, E.g. a color coupler or a color releaser are combined (ÜS-A-2 698 794, DE-A-26 45 656). This on Long-known technology has also been applied to the heat generation process (DE-A-32 32 674), but is known to have the problem that the red or green-sensitive Emulsion fractions in addition to their sensitized sensitivity (for red or green light) due to their Self-sensitivity to a considerable extent also for

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are sensitive to blue light and therefore only provide inadequate color rendering. With conventional multilayer color photographic recording materials this problem can be solved by arranging a yellow filter layer between the blue-sensitive ones Layer (self-sensitivity) on the one hand and the red- or green-sensitive layers (sensitized Sensitivity) on the other hand. However, this measure is not necessary in the case of single-layer multicolor recording materials. The color rendering can, however, be improved by adding a yellow dye to the red or green-sensitive emulsion fractions is introduced (GB-A-475 191, US-A-2 168 182). With a layer thickness as required to achieve sufficient color densities is, but then occurs through the yellow filter effect of the red or green sensitized emulsion components, namely in the lower area of the layer considerable decrease in blue sensitivity. In addition, the desired yellow filter effect is also on the red- or green-sensitive packages mainly limited to the lower layer areas. The same finding Of course, this also results if the yellow filter dye is not in the particles of the red- or green-sensitive emulsion components, but in the common seed binder phase is included. As a compromise, US Pat. No. 2,168,182 also describes a recording material, in which the mixed grain emulsion layer contains only red-sensitive and green-sensitive packages and is overcoated with a blue-sensitive silver halide emulsion layer with between the two photosensitive layers a yellow filter layer is located.

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Such a layer arrangement, although with the application chromogenic process could achieve good color rendering without loss of sensitivity to blue but, as already mentioned, not in favor of the heat generation process.

Attempts have also been made with single-layer, multicolor materials based on mixed grain emulsions to avoid a reduction in blue sensitivity completely without filter dyes while improving the color rendering (ÜS-A-2 618 553), A silver halide with the highest possible intrinsic sensitivity is used for the blue-sensitive emulsion components, e.g. silver bromide, and for the red or green sensitive, sensitized emulsion components Silver halide with the lowest possible sensitivity, e.g. silver chloride, is used. This method used in conventional silver halide emulsions in the

-1-2 2

range of approx. 10 to 10 erg / cm is well applicable, but is also not suitable for the Heat development process because the emulsion systems used there, e.g. silver behenate / behenic acid or Silver benzotriazolate, each partially converted to

-1 3 2 silver halide, with 10 to 10 erg / cm a very have much lower sensitivity. The use of chloride for the conversion is prohibited here instead of bromide or a mixture of bromide and Iodide, so as not to lose basic sensitivity again. In addition, for the hydrophilic emulsion systems in question here, e.g. silver benzotriazolate in gelatin as a binder, a conversion to AgCl for reasons of solubility product ratios in usually no longer possible.

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The invention is based on the object, a through heat treatment indicate developable color photographic recording material, the multicolored images with provides improved color rendering, in particular, improved color separation.

The object is achieved with a recording material the one covered or underlaid with a yellow filter layer (depending on the direction of exposure) mixed grain emulsion layer in which several different spectrally sensitive emulsion fractions each with spectral assigned dye releasers are included, at least one of the emulsion components mentioned is sensitive to blue and has a higher sensitivity than the green or red sensitive emulsion components.

The invention relates to a color photographic recording material which can be developed by heat treatment with a photosensitive binder layer, which in the form of separate complex coacervates several different spectrally sensitive assignments from each

a) a light-sensitive silver halide of the relevant Spectral sensitivity, optionally in combination with an essentially non-photosensitive silver salt,

b) a non-diffusing coloring compound, which is able to release a diffusible dye as a result of development through heat treatment, and

c) if necessary, further auxiliary materials A-G 502 4

contains, the silver halide being blue-sensitive in at least one of the assignments mentioned,

characterized in that a yellow filter layer over or is arranged under the photosensitive binder layer so that upon imagewise exposure the Light through the yellow filter layer into the photosensitive Binder layer arrives, and that the silver halide of the blue-sensitive assignment by at least 0.5 log I * t units is more sensitive than the silver halide in the other assignments.

With the recording material according to the invention can in a simple manner multicolored images with good color rendering, in particular merely by heat treatment improved color separation, can be produced according to your wishes and according to the color-imparting compounds used either in a negative-positive or in a positive-positive relationship to the photographed one Original (if the pictures are positive), the pictures are particularly distinguished by their uniformity low minimum color densities (veils) in the various colors.

The recording material contains as photosensitive Layer on a dimensionally stable support a binder layer in which all light-sensitive substances and all coloring compounds are contained in the form of the complex coacervates mentioned. The recording material further includes a yellow filter layer adjacent to the photosensitive layer. Latter is arranged so that the exposure light passes through

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the yellow filter layer into the photosensitive layer got. Usually the yellow filter layer overlies the photosensitive layer; however, it can if the support is transparent, even beneath the photosensitive one Be arranged layer. The yellow filter layer has an optical density (for blue light) between 0.5 and 1.2, preferably between 0.7 and 0.9. It can be yellow colloidal silver in the usual way or contain suitable yellow organic dyes.

If the yellow filter layer is above the photosensitive Layer is arranged, it can with additional Functions by incorporating suitable additives. The yellow filter layer can do the function take over a hardening layer when hardening agents are added to their casting solution, for example Formaldehyde, succinaldehyde, glutaraldehyde, N, N ', N "-Trisacryloylhexahydro-l, 3,5-triazine, Mucochloric acid, halogen-substituted aldehydes. The yellow filter layer can be formed by suitable additives as an adhesive and contact layer by using suitable polymers or Polymer mixtures are added and they can finally also be hard inorganic or organic particles Contains nature as a matting agent or spacer.

The photosensitive layer of the recording material according to the invention contains several of the complex coacervates mentioned, each of these complex coacervates is assigned to a different spectral range of light and as essential components at least one photosensitive silver halide and at least one Contains non-diffusing coloring compound which

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Al

capable of releasing a diffusible dye as a result of development by heat treatment. In the As a rule, the light-sensitive silver halide is essentially not in combination with another photosensitive silver salt.

A complex coacervate is understood to mean a dispersion form in which a mixture of the essential Components is enclosed in a common coating of a hardened binder. Such dispersions are also known as packet emulsions. They are obtained through complex coacervation.

Understood by the term "complex coacervation" the occurrence of two phases when mixing an aqueous solution of a polycationic colloid and a polyanionic colloid, one being concentrated Colloid phase (hereinafter referred to as complex coacervate) and a dilute colloid phase (hereinafter referred to as equilibrium solution) due to an electrical interaction. That complex coacervate is deposited from the equilibrium solution in the form of droplets and appears as white haze. When the complex coacervation in the presence of a solid such as silver halide or fine oil droplets is carried out, one generally takes indicate that the complex coacervate entraps the solid or droplets inside colloidal particles. As a result, a dispersion of coacervate particles is obtained in which the solid (in the present case In the case of the light-sensitive silver halide and optionally the essentially non-light-sensitive Silver salt) and oily droplets of a solution of the organic

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see constituents (in the present case the dye releasing agent and possibly other auxiliaries) are included. It is then hardened with a hardening agent so that the original shape of the particles is not destroyed in the following steps for the production of the photographic recording material, such as production of the casting solution and coating. Conveniently, the dispersion prior to curing at a temperature of 25 ⁰ C or less, cooled preferably from 10 ⁰ C or less, whereby a packet * emulsion of good quality is obtained.

A method of making a packet emulsion, in which a color-forming substance is incorporated by complex coacervation is described, for example in US-A-3,276,869 and US-A-3,396,026.

The hydrophilic colloids involved in complex coacervation can be used can be divided into two groups. A first group includes compounds containing a nitrogen atom; an aqueous solution thereof has a negative charge at pH higher than its isoelectric point, and a positive charge at a pH lower than that is as its isoelectric point (i.e. a cationic compound or polymer). Examples of this Compounds include gelatin, casein, albumin, hemoglobin, polyvinylpyrrolidone. A second group includes Compounds of which an aqueous solution always has a negative charge regardless of pH (i.e. an anionic compound). Examples of these compounds include a natural colloid, such as sodium

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alginate, gum arabic, agar agar, pectin, konjac, a synthetic polymer having an acidic group or an alkaline salt thereof, such as a copolymer of Vinyl methyl ether or ethylene and maleic anhydride, carboxymethyl cellulose, polyvinyl sulfonic acid, a condensation product of naphthalenesulfonic acid and Formalin or a gelatin derivative in which a part that would be capable of carrying a positive charge, blocked by esterification. Preferred examples of the anionic polymer used in the present invention can be, include compounds with repeating units, the carboxylate and / or Contain sulfonate groups and have a molecular weight of not less than 1,000, preferably not less than 3000. Of the compounds belonging to these two groups, gelatin, agar agar, Sodium alginate can be gelled by cooling. Gelatine is particularly suitable for the production of the package emulsion, since it can be gelled by cooling and easily hardened with a hardening agent.

To carry out the complex coacervation is preferred a combination of gelatin and an anionic polymer is used. The amount of colloidal Substances that are used vary depending on the charge density of the substances at the time of Coacervate formation. However, in general, the colloid of one group will be in an amount in the range from 1/20 to 20 times the amount by weight of the colloid of the other group is used. It is preferred to have a Weight ratio, from 0.5: 1 to 4: 1 in one combination of gelatine and gum arabic and a

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3 "5 ΙΌ 6 8

Weight ratio from 10: 1 to 40: 1 in one combination of gelatin and a condensation product of naphthalenesulfonic acid and formalin.

To effect the complex coacervation are as follows four conditions are required.

First, the concentration of the hydrophilic colloid must be both in the first group and in the second group in the range from 0.5 to 6%, preferably from 1 to 4%.

Second, the pH must not exceed 5.5. the The size of the package emulsion particles varies widely depending on the pH value, but also fundamentally on the degree of mixing. The optimal pH varies depending on the the type of colloid used, but in most cases is in the range of 5.2 to 4.0, preferably from 5.0 to 4.5. The size of the package emulsion particles used is usually in the range of 1 to 100 μπι, preferably from 2 to 60 pm and particularly preferred from 5 to 30 μm.

Third, the temperature of the system must be higher than the solidification temperature of the aqueous colloid solution. In the case of gelatin, the temperature must not be below 35 ^° C. and is preferably in the range from 40 to 55 ^° C.

Fourth, the amount of coexisting inorganic salt must not exceed a certain critical value which is characteristic of the type of salt. _Λ

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The manufacture of the package emulsion through complex coacervation is generally carried out by one of the following two methods.

According to the first method, hydrophilic colloids each selected from the first group and the second group are mixed in an appropriate ratio, and an aqueous solution thereof is prepared in a concentration of 1 to 4% by weight. The temperature of the solution is kept in a range from 35 to 60 ^° C., and the pH value is kept above 5.5. The pH value is reduced by adding an acid to cause coacervation.

According to the second method, a temperature (not less than 35 ⁰ C) and a pH (not more than 5.5) is maintained under conditions under which the coacervation can be performed, and an aqueous hydrophilic colloid solution having a concentration of initially at least 6 wt .-% is diluted by adding warm water until the concentration suitable for coacervate formation is reached.

However, if a packet emulsion is prepared by the first or second method or by both, then is the amount of the package emulsion compared to the volume of the dilute continuous phase of the hydrophilic Colloids very little. Therefore, a large amount of binder such as gelatin must be added afterwards so that the emulsion can be used directly for coating. Different methods can be used to concentrate and dry the package emulsion. According to a well-known

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In the method, the dilute colloid solution, which contains a packet emulsion in dispersed form, is filtered. According to Another method is to leave the colloid solution to precipitate the packet emulsion. The protruding Liquid is then removed by decanting. For accelerated precipitation can also a centrifuge separator can be used. In addition, for complete water removal, the Package emulsion can be atomized using spray drying methods such as those used for the Manufacture of microcapsules are known.

Examples of hardening agents that can be used to produce the package emulsion according to the invention, include chromium salts (e.g. chrome alum, chrome acetate), aldehydes (e.g. formaldehyde, Glyoxal, glutaraldehyde), N-methylol compounds (e.g. dimethylol urea, methyl oil dimethyl hydantoin), Dioxane derivatives (e.g. 2,3-dihydroxydioxane), active vinyl compounds (e.g. 1,3,5-triacryloylhexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g. 2,4-dichloro-6-hydroxy-s-triazine), and Mucohalic acids (e.g. mucochloric acid, mucophenoxychloric acid). These hardeners can can be used individually or as a mixture.

According to the invention, the use of package emulsions enables several emulsion fractions of different spectral sensitivity to be combined, including the relevant dye releasers in a single layer of binder without affecting the spectral Assignment is lost and this causes a color change

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ff - ■ ■■ -.- ■■■■ '■ ■■

schung occurs. This is possible because of the exposure level of a particular silver halide particle Almost exclusively determining the extent of the dye release from the dye releasing agent which is in the same coacervate particle (package) as the silver halide. The use of packet emulsions thus enables a blue-sensitive, a green-sensitive and a red-sensitive silver halide emulsion to be accommodated, optionally with additionally present, essentially non-light-sensitive silver salt and each spectrally assigned Color splitting off in the same binder layer without fear of serious color falsification got to.

The light-sensitive silver halide can consist of silver chloride, silver bromide, silver iodide or mixtures thereof and have a particle size between 0.02 and 2.0 μm, preferably between 0.1 and 1.0 μm. It can be in the form of an unsensitized silver halide or it can be chemically and / or spectrally sensitized by suitable additives. The amount of light-sensitive silver halide in the respective layer can be between 0.01 and 5.0 g per m ² , or even more Embodiments mainly in the lower part of the specified range. For emulsion systems, which consist of a mixture of silver halide and organic silver salt, the amount of the used

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Silver halide mainly in the upper range: Preferably for each emulsion fraction at 0.25-1.0 g / m ² .

In the case of the essentially non-photosensitive silver salt For example, it can be a silver salt that is comparatively stable to light, e.g. an organic one Act silver salt. Suitable examples include the silver salts of aliphatic or aromatic carboxylic acids and the silver salts of nitrogen-containing heterocycles; also silver salts organic mercapto compounds.

Preferred examples of silver salts of aliphatic carboxylic acids are silver behenate, silver stearate, silver oleate, Silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, Silver furoate, silver linolate, silver adipate, silver sebacate, silver succinate, silver acetate or Silver butyrate. The underlying silver salts Carboxylic acids can be substituted, for example, by halogen atoms, hydroxyl groups or thioether groups be.

Examples of silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include Silver benzoate, silver 3,5-dihydroxybenzoate, SiI-ber-o-methylbenzoate, Silver m-methylbenzoate, silver p-methylbenzoate, Silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver gallate, silver tannate, silver phthalate, Silver terephthalate, silver salicylate, silver phenyl acetate, silver pyromellitate, silver salts of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione or similar heterocyclic

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see connections. Silver salts of are also suitable organic mercaptans, e.g. the silver salts of 3-mercapto-4-phenyl-l, 2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptooxadiazole, mercaptotriazine, Thioglycolic acid, and also the silver salts of dithiocarboxylic acids, such as the silver salt of dithioacetate.

The silver salts of compounds are also suitable with an imino group. Preferred examples of this include the silver salts of benzotriazole and its derivatives, e.g. silver salts of alkyl and / or halogen substituted Benzotriazoles ^ such as the silver salts of methylbenzotriazole, 5-chlorobenzotriazole, as well as the silver salts of 1,2,4-triazole, 1-H-tetrazole, carbazole, Saccharin and silver salts of imidazole and its derivatives.

The amount of essentially non-photosensitive silver salt according to the present invention applied in the respective layer is between 0.05 and 5 g per m ² .

The substantially non-photosensitive silver salt and the photosensitive silver salt can further be used in the coacervate particles side by side as separate Particles are present or else in a combined form, which can be produced, for example, that an essentially non-photosensitive silver salt is treated in the presence of halide ions, wherein on the surface of the particles of the substantially non-photosensitive silver salt through double conversion (conversion) to form light-sensitive centers from light-sensitive silver halide. Reference is made to US Pat. No. 3,457,075.

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The essentially non-photosensitive silver salt serves as a reservoir for metal ions that are generated during heat generation in the presence of a reducing agent under the catalytic influence of the imagewise exposed Silver halide can be reduced to elemental silver and thereby act as an oxidizing agent (for the existing Reducing agents).

Another essential component in the coacervate particles of the recording material according to the invention is a non-diffusing coloring compound that occurs as a result of a development Redox reaction is able to release a diffusible dye and is used below as a dye releasing agent referred to as.

The dye releasers used according to the invention can be a variety of compound types, all of which are characterized by a redox-dependent link in its bond strength, which one Dye residue linked to a carrier residue containing a ballast residue.

In this context, a summary of the subject area in Angew. Chem. Int. Ed. Engl. £ 2 (1983), 191-209, in which the most important of the known systems are described.

Redox-active ones prove to be particularly advantageous here Color releaser of the formula

BALLAST - REDOX - COLORANT,

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in which mean

BALLAST a remainder of ballast

REDOX a redox-active group, i.e. a group that under the conditions of alkaline Development is oxidizable or reducible and depending on whether it is in the oxidized or in the reduced state is present, to varying degrees of an elimination reaction, a nucleophilic displacement reaction, hydrolysis or other cleavage

reaction is subject to the consequence that the rest of the DYE is split off, and

DYE the remainder of a diffusible dye, e.g. of a yellow, magenta or cyan dye, or the remainder of a dye precursor

fers.

Those residues are to be regarded as ballast residues which make it possible to use the paint releasers according to the invention in to store the hydrophilic colloids usually used in photographic materials in a diffusion-proof manner. Organic radicals, which are generally straight-chain or branched, are preferably suitable for this purpose aliphatic groups with generally 8 to 20 carbon atoms and optionally also carbocyclic or optionally contain heterocyclic aromatic groups. With the rest of the molecule, these are Residues either directly or indirectly, e.g. linked via one of the following groups: -NHCO-, -NHSO_-, -NR-, where R is hydrogen or alkyl, -0-

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or S-. In addition, the ballast residue can also be water-solubilizing Contain groups, such as SuI-fogruppen or carboxyl groups, which are also in anionic Form can be present. Because the diffusion properties depend on the molecular size of the total compound used depend, it is sufficient in certain cases, e.g. if the entire molecule used is large enough, to use short-chain residues as ballast residues.

Redox-active carrier residues with the structure BALLAST-REDOX- and corresponding paint releasers are known in the most varied of embodiments. On a detailed Presentation can be dispensed with at this point in view of the overview article mentioned in the Angew. Chem. Int. Ed. Engl. 22 (1983) 191-209.

A few examples of redox-active carrier residues are listed below, by where a dye residue is split off in accordance with an image-wise oxidation or reduction that has taken place will:

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Ik

OH

CO-NH-BALLAST

(NH-SO ₂ -)

OH (NH-SO ₂ -)

0 BALLAST

—Jj— (NH-SO ₂ -)

\ CO-NH-BALLAST

BALLAST

NH

NH- (SO ₂ -)

ballast

- SO ₀ - ·)

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is

ballast

ballast

ballast

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BALLAST

CO - (O CH ₂ -N-CH ₃

BALLAST-SO ₂ -

SO ₂ -BALLAST O EALLAST

CH- (SO ₂ -)

BALLAST-SO

CH- (SO ₂ -) SO ₂ BALLAST

NO-

-ίΐΗ-ν ^χ > - S- (J ₁ -SO--)

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The groups enclosed in brackets are functional groups of the dye residue and are taken together with this separated from the remaining part of the carrier residue. The functional group can be be a substituent that has a direct influence on the absorption and, where appropriate Complex formation properties (e.g. a post-complexable Chromophore) of the released dye can exercise. On the other hand, the functional group can also separated from the chromophore of the dye by an intermediate or linking member. The functional one Finally, the group, together with the intermediate member, can be of importance for the diffusion and Pickling behavior of the released dye. Suitable intermediate members are, for example, alkylene or Arylene groups.

In principle, the residues of dyes of all dye classes are suitable as dye residues, insofar as they are suitable They are diffusible enough to be sensitive to light Layer of light-sensitive material to be able to diffuse into an image-receiving layer. to For this purpose, the dye residues can be provided with one or more alkali-solubilizing groups. Suitable alkali-solubilizing groups include carboxyl groups, sulfo groups and sulfonamide groups as well as aromatic hydroxyl groups. Such alkali-solubilizing groups can be used according to the invention dye releasers used already be preformed or only from the elimination of the dye residue result from the carrier residue afflicted with ballast groups. Of dyes that are used for the invention

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u '-' · ■ ' ■■ - ■ --- ■■ -.

according to methods are particularly suitable are to be mentioned: azo dyes, azomethine dyes, anthraquinone dyes, Phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, including those dyes that are complexed or complexable with metal ions.

among the residues of dye precursors are the residues such compounds to be understood in the course of photographic processing, in particular under the conditions of heat generation, be it through Oxidation, be it by coupling, by complex formation or by exposing an auxochromic group in one chromophoric system, for example by saponification, are converted into dyes. Dye precursors in this sense can be leuco dyes, couplers or also dyes that are used in the course of processing converted into other dyes. Unless there is a distinction between dye residues and the Residues of dye precursors are essential is, the latter are to be understood in the following also under the term dye residues.

Suitable color releasers are described, for example, in:

US-A- 3 227 550, US-A- 3 443 939, USA-A- 3 443 940,

DE-A- 19 30 215, DE-A- 22 42 762, DE-A- 24 02 900,

DE-A- 24 06 664, DE-A- 25 05 248, DE-A- 25 43 902,

DE-A-26 13 005, DE-A-26 45 656, DE-A-28 09 716,

DE-A-28 23 159, BE-A-861 241, EP-A-0 004 399,

EP-A-0 004 400, DE-A-30 08 588, DE-A-30 14 669,

GB-A-80 12 242.

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The paint releasers can in some embodiments of the invention as oxidizable or couplable paint releasers, in others as reducible color releasers. Depending on whether the dye from the oxidized or the color releasing agent is released from the reduced form, one obtains when using the usual negative working silver halide emulsions from the original a negative or positive illumination. One can therefore, if required, by selecting suitable paint release systems create positive or negative images.

If the dye releaser can be oxidized, then it is itself a reducing agent that is directly or indirectly with the participation of electron transfer agents (ETA) through the pictorial exposed silver halide or through the essentially non-light-sensitive silver salt under the catalytic action of the imagewise exposed SiI berhalogenids is oxidized. This creates a visual differentiation with regard to the ability to release the diffusible dye. if on the other hand, the color releasing agent can be reduced, then it is expediently used in combination with a A reducing agent present in a limited amount, a so-called electron donor compound or one Electron donor precursor compound, which in this case is the light-sensitive silver halide in addition to the dye releaser and possibly essentially not photosensitive silver salt is contained in the same coacervate particles. Also in the case of using Reducible dye-releasing agents in combination with electron donor compounds are found to involve electron transfer agents usually as cheap.

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For generating positive color images from positive ones
Originals (original) when using negative-working silver halide emulsions, for example, a recording material according to the invention which contains reducible dye releasers of the following formula I is suitable:

in which mean

R alkyl or aryl?

2
R is alkyl, aryl or a grouping together

with R completes a fused ring;

R is hydrogen, alkyl, aryl, hydroxyl, halogen such as
Chlorine or bromine, amino, alkylamino, dialkylamino including cyclic amino groups (such as piperidino, morpholino), acylamino, alkylthio, alkoxy, aroxy, sulfo, or a grouping together

2
with R completes a fused ring;

R ⁴ alkyl;

R is alkyl or preferably hydrogen;

A the remainder of a diffusible dye or Dye precursor;

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X is a bivalent link of the formula -R- (L) - (R) -, wherein R is an alkylene radical having 1-6 carbon atoms or an optionally substituted arylene or Aralkylene radical and where the two radicals R have the same meaning or different from one another Can have meanings;

L -0-, -CO-, -CONR ⁶ -, -SO-NR ⁶ -, -0-CO-NR ⁶ -, -S-,

6th
-SO- or -SO ₃ - (R = hydrogen or alkyl);

ρ 0 or 1;
10q 0 or 1;

m 0 or 1,

12 3 4 and where at least one of the radicals R, R, R and R contains a ballast residue.

12 3 5 Those represented by R, R, R and R in formula I Alkyl radicals can be straight-chain or branched and generally contain up to 18 carbon atoms. Examples are methyl, n-propyl, tert-butyl, tetradecyl, octa-

12 3 decyl. The radicals R, R and R mentioned aryl radicals shown are, for example, phenyl groups which may be substituted, for example by long chain alkoxy groups.

In an acylamino radical represented by R, the acyl group is derived from aliphatic or aromatic

table carboxylic or sulfonic acids. In the case of the R

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and R completed fused rings are preferably carbocyclic rings, e.g. fused-on benzene or bicyclo / 2,2, 17 ~ heptene rings.

An alkyl radical represented by R can be straight-chain or branched, substituted or unsubstituted and contain up to 21 carbon atoms. Examples are methyl, nitromethyl, phenylmethyl (benzyl), heptyl, tridecyl; Pentadecyl, heptadecyl, "C ₃₁ H ₄₃ .

Preferred embodiments of the inventively

1 are those in which R, R and R in a quinoid carrier residue are not used together more than 8, in particular not more than 5, carbon atoms

4th
included, and R e

Represents carbon atoms.

4th
contain, and R is an alkyl radical with at least 11

Preferred embodiments are also those in which R is an alkoxyphenyl radical with at least

2 3

12 carbon atoms in the alkoxy group and R, R,

4th
R together do not contain more than 8 carbon atoms.

These dye releasers contain, bound to the dye residue, a releasable quinoid which makes it diffusion-proof Carrier residue of the formula

'Carquin'

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worxn

R, R, R, R and R are those given for formula I.

Have meaning.

Examples of such dye releasers which are preferably used in the context of the present invention, are listed below.

T)

H ₂ C-SO ₂ - <ξΖ *> -

NH-SO ₂ -

-N = N-HC C-

0 = C _v N

OCH _x ^N 7

2)

CH ₂ -NO ₂ HC-Σ

-NH-CO-CH. -OH

N = N-

Cl

3)

SO _n NH-

SO ₂ CH ₃

_r ^ ZS> -NH-SO ₂ '

A-G 5024

3t

CH ₃ -

-CH >"" € - ^ -NH- ^S0 2 "^ Hy

SO ₅ -NH- -2 ^ - N = N-

I.

CN

-CH-SO ₂ - ^ 3.

N = N-

-NHCOC ₆ H ₅

OCH.

^H 31 ^C 15 ^CO

N = H-HC C-CONHC ₁₁ H ₉

A-G 5024

Jf

8) O ^ S-NH-

) CH.

-CH-SO ₂ -, ^ 3

NHSO ₂ -

-NHCOCH, -Ot

N = N-,

-OH °

CH.

OCH

-C-SO ₀ CH,

H ₃ C-SO ₂

CH -

^< f-i3 ^H 2?
SO

-CH-SO ₂ - ^> -N-SO ₂ - ^

A-G 5024

11)

? 13 ^Η 27 CH ^ - ^ - CH-SO ₂ -

⁵ P ΓΗ

.-OCH;

CH

'3 "7

12) CHj

CC

. S ~%> - ^ = N- ^ Ζ> -QH CHj

CH SO ₀

ι β

N (CH ₃ ) ₂

13)

NH-SOp -. ^^ - ^{N = N} - ^HC C-CONHCH,

A-G 5024

J?

CH, -

-CH-SO-- JZ ^ - NH-SO ₂ -

Il

0. CHj

CH-SO,

SO - NH- <_

O = C

AG 5024

$ 3

17)

HO-XS-CH-SO, -4U> -N = N- ^ Z υ, H ₇ j

^y ' so _D

²

18)

CH, -

. * ^H J1 '"J _

-CH-SO ₃ - ^ Z $> -N-SO ₂ - ^ 2

SOpNH N = N

CH, SO ₂ -

19)

CH ₃ O-

-CH-SO ₂ - UC ₃ H ₇

-N = N-

HN-

SO-

ι «

NO ₂

SO ₂ N (C ₂ H ₅ ) -

-OH

AG 5024

33

3510635

H, C-O ₂ S-NH

-NH-O ₂ S-

-NHSO ₂ -

O = C 'I

-N = N-HC-

N U

C-CH,

Examples of such dye releasers and methods for their production are described in EP-A-0 004 399.

A-G 5024

The electron donor compound used in combination with the reducible dye releaser also serves as a reducing agent for the silver halide, the essentially non-photosensitive silver salt and the parbo-splitter. The fact that the essentially non-photosensitive silver salt and the dye releaser are also present the oxidation of the electron donor compound to a certain extent compete with one another, the former with the latter but is in any case superior in the presence of exposed silver halide, the silver halide present becomes according to a previous image-wise exposure determining the image areas within which the dye releaser is converted into its reduced form by the electron donor compound. the Electron donor compound present in a limited amount is produced under the conditions of development, in the present case when the imagewise exposed color photographic recording material is heated According to the extent of exposure under the catalytic effect of exposure in the silver halide generated latent image nuclei by the essentially non-photosensitive silver salt and the light-sensitive silver halide oxidizes and consequently no longer reacts with the Paint splitter available. This creates, as it were, a pictorial distribution of the unused Electron donor compound.

The one responsible for the release of the diffusible dyes The necessary reaction between the electron donor compound and the dye releasing agent can naturally only take place there-

A-G 5024

find where the electron-donating compound failed previously by other reactions, e.g. in the present case by the image-wise oxidation by the im essential non-photosensitive silver salt consumed has been. An important requirement for the image forming mechanism according to this embodiment of the present invention is accordingly a suitably graded reactivity of those components those for reaction with that present in the layer Reducing agents, namely the electron donor compound, potentially come into question. With the ones in question Components are

1. - the essentially non-photosensitive

Silver salt or silver halide in the absence of latent image nuclei,

2. - the essentially non-photosensitive

Silver salt or silver halide in the presence of latent image nuclei,

3. - the paint releaser.

It turns out to be extraordinarily favorable that under the conditions of heat generation, the components mentioned have the desired graded reactivity in view of on the reaction with the electron-donating compound and that the reducing power of the latter is so dimensioned that through it the substantially non-photosensitive silver salt is absent practically none of latent image nuclei, in the presence of

A-G 5024

ti

Sheit of latent image nuclei is reduced comparatively quickly and that the color releasers through they are comparatively slow, but faster than the essentially non-photosensitive metal salt (in Absence of latent image nuclei) is reduced.

Electron donor compounds are, for example, little or no diffusing derivatives of hydroquinone, of benzisoxazolone, p-aminophenol or of ascorbic acid (e.g. ascorbyl palmitate) has been described (DE-A-28 09 716).

Further examples of electron donor compounds are from DE-A- 29 47 425, DE-A- 30 06 268, DE-A- 31 30 842, DE-A-31 44 037, DE-A-32 17 877, EP-A-0 124 915 and Research Disclosure No. 24 305 (July 1984) are known.

It has been shown that the electron donor compounds mentioned even under the conditions of heat generation, the demands placed on them are sufficient and therefore also as electron donor compounds for the recording material of the present invention are suitable. Those electron donor compounds are particularly suitable, only under the conditions of heat development in the layer of corresponding electron donor precursor compounds are formed, i.e., electron donating compounds contained in the recording material before development only in a disguised form in which they are practically ineffective. Under the conditions of heat generation, the initially ineffective electron donor compounds are then in their effective form is converted, for example, by hydrolytically splitting off certain protective groups.

A-G 5024

iß ■ · - ■ - ■ ■■■■■■■:

For the purposes of the present invention, the electron donor precursor compounds mentioned are accordingly also used as Understood electron donor compound. Particularly suitable electron donor compounds are, for example those of the following general formulas II, III and IV.

II

in which mean

R is a carbocyclic or heterocyclic aromatic ring;

2 3 4

R, R, R identical or different substituents, namely hydrogen, alkyl, alkenyl, aryl, alkoxy, Alkylthio, amino or

3 4

R and R together complete a condensed, especially carbocyclic ring

1 2 and where at least one of the substituents R, R,

O A

R and R a ballast residue that makes diffusion difficult contains;

R - NHCO - CH - CONH - R III

¹ 2

Q-CO-R

A-G 5024

where mean:

R is a carbocyclic or heterocyclic aromatic group, and

R is hydrogen, alkyl, alkenyl or acyl

1 2 where at least one of the substituents R and R contains a ballast radical;

IV

OH

in which mean

R is a hydrocarbon group

2 3 4 5
R, R, R, R identical or different substituents, namely hydrocarbon groups, halogen or alkoxy, or R and R together complete a fused, in particular carbocyclic ring,

12 3 4 where at least one of the substituents R, R, R, R and R · contains a ballast residue.

A-G 5024

Examples of suitable electron donor compounds which can be used in the context of the present invention are listed below.

6 ^H 33

^H0 \ OH CH,

- NO,

A-G 5024

351068S

While the silver salt is in the various emulsion proportions with regard to the spectral sensitivity and the color releasing agents in the various emulsion fractions with regard to the color of the released dye differs, this does not necessarily also apply to the electron donor compound that may be present. The electron donor compound can therefore be the same for all three assignments. she can may also be wholly or partially contained in the common binder phase, if it is also preferred, to include them together with the silver salt and the dye releaser in the coacervate particles.

The silver halide in the different emulsion fractions (assignments) is differently spectrally sensitized, according to the respective assignment to a color releasing agent or the color of the released color Dye. According to the invention, the blue-sensitive emulsion portion has a higher sensitivity on than the other emulsion fractions, the sensitivity being derived from the totality of the individual Coacervate particles of the emulsion portion in question containing constituents, thus also taking into account the filter effect of the colored compounds contained in the coacervate particles, essentially but results from the silver halide. According to the invention, the blue-sensitive emulsion portion is for blue Light at least 0.5 log I * t units more sensitive than the green-sensitive emulsion component for green Light or the red-sensitive emulsion component for red light. The sensitivity advantage of the blue-sensitive emulsion portion is preferably in the range from 0.7 to 0.9 log I * t units.

A-G 5024

nt

Methods of determining the sensitivity of each Emulsion fractions are known to the person skilled in the art. The person skilled in the art is also familiar with measures that can be used in a targeted manner a difference in sensitivity between the blue-sensitive part of the emulsion on the one hand and the green- or red-sensitive emulsion fractions, on the other hand, can be adjusted to the desired level, such as off can be seen in the following overview:

Measure green or red-blue

sensitive sensitive

mean grain size e.g. 0.04 - 0.06 \ m 0.10 - 0.15 \ m

Halide - e.g. AgBr or AgBrCl AgBrI

composition (without I)

chemical ripening e.g. not or slightly stronger

matured matured

Proportion of the organic silver salt
on the total silver salt, for example,> 50% by weight <. 50% by weight

Order to

Silver halide e.g. 0.5 g / m2 - q - ^, 2

In addition, there is still the possibility of targeting the sensitivity of the green- or red-sensitive emulsion components to press, e.g. by adding stabilizers, this measure with one or more of the already The measures outlined can also be used in combination.

Finally, one can also look at the optical filter effect of the particles contained in the coacervate Make use of color releasers by removing color from the green or red-sensitive emulsion components

A-G 5024

Mt - '

used, which absorb a considerable proportion of the light effective in these emulsion fractions, while dye releasers for the blue-sensitive part of the emulsion be used with little absorption for blue light; the one from the latter Image dye released from dye-releasing agents suffers the development a shift in the absorption maximum ("shifted dye" -US-A-3 854 945).

In addition to the components already mentioned, the photosensitive binder layer of the invention color photographic recording material contain other components and auxiliaries that for example, for carrying out the heat treatment and the color transfer that takes place here are. These further constituents or auxiliaries are preferably in the common binder phase light-sensitive layer or in one of the other layers.

Such auxiliaries are, for example, auxiliary developers. These auxiliary developers generally have developing properties for exposed silver halide; in the present case they have a beneficial effect primarily on those between the exposed silver salt (= Silver salt in the presence of exposed silver halide) and the reducing agent occurring reactions off, whereby the reducing agent is identical to the latter if oxidizable paint releasers are used, or in the case of the use of reducible paint releasers in turn reacts with the color releasers. This one Reactions mainly in a transfer of elec-

A-G 5024

trons exist, the auxiliary developers are also called electron transfer agents (electron transfer agents; ETA).

Examples of suitable auxiliary developers are hydroquinone, pyrocatechol, pyrogallol, hydroxylamine, Ascorbic acid, l-phenyl-3-pyrazolinone and their Derivatives. Since the auxiliary developers exercise a catalytic function, it is not necessary that they are present in stoichiometric amounts. In general, it is sufficient if they are in quantities there are up to 1/2 mole per mole of parabolic splitter in the layer. Incorporation into the shift can for example from solutions in water-soluble solvents or in the form of aqueous dispersions which obtained using oil formers.

Other auxiliaries are, for example, basic substances or compounds which, under the influence of heat treatment, are able to provide basic substances. Examples to be mentioned here are sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, Sodium acetate and organic bases, especially amines such as trialkylamines, hydroxyalkylamines, Piperidine, morpholine, dialkylaniline, p-toluidine, 2-picoline, guanidine and their salts, in particular Salts with aliphatic carboxylic acids. By making the basic substances available, the Heat treatment in the photosensitive layer and the adjacent layers a suitable medium created to release the diffusible To ensure dyes from the dye releasing agents and their diffusion into the image receiving layer. A-G 5024

so "■■■ ·

Further auxiliaries are, for example, compounds that are capable of releasing water under the action of heat. Inorganic salts containing water of crystallization are particularly suitable for this purpose, for example Na ₂ SO ₄ .10H ₂ O, NH ₄ Fe (SO ₄ ) ₂ .12H ₂ O.

The water released during heating favors the development and imaging required for image formation Diffusion processes.

Further auxiliaries are, for example, the so-called thermal solvents, which generally include understands non-hydrolyzable organic compounds that are solid under normal conditions, but when heated melt up to the temperature of the heat treatment and thereby provide a liquid medium in which the Development processes can run faster. Such thermal solvents can, for example, as Diffusion accelerators act. Preferred examples for the thermal solvents include polyglycols as described, for example, in US-A-3,347,675, e.g.

Polyethylene glycol with an average molecular weight of 1500 to 20,000, derivatives of polyethylene oxide, such as, for example, its oleic acid esters, beeswax, monostearin, compounds with a high dielectric constant which have a -SO ₃ or -CO group, such as acetamide, succinamide, ethyl carbamate , Urea, methylsulfonamide, ethylene carbonate, and also polar substances, as described in US Pat. No. 3,667,959, the lactone of 4-hydroxybutanoic acid or 4-hydroxybutyric acid, dimethyl sulfoxide, tetrahydrothiophene-1,1-dioxide and 1,10-decanediol , Methyl anisate, biphenyl suberate, etc. as described

A-G 5024

in Research Disclosure, pages 26-28 (December 1976), etc.

The development of the imagewise exposed color photographic recording material according to the invention comprises the sub-steps of silver halide development, production of an imagewise distribution of diffusible dyes and diffusion transfer of this imagewise distribution into the image receiving layer. It is initiated by subjecting the exposed recording material to a heat treatment in which the photosensitive binder layer is brought to an elevated temperature, for example in the range from 80 to 250 ^° C., for a time of about 0.5 to 300 s. This creates suitable conditions in the recording material for the development processes, including dye diffusion, without the need to supply a liquid medium, for example in the form of a developer bath. During development, image-wise diffusible dyes are released from the color releasers and transferred to an image-receiving layer which is either an integral part of the color photographic recording material according to the invention or is in contact with it at least during the development time.

Here, in a one-step development process, image-wise silver development, dye release and Color transfer takes place synchronously.

In addition, the color image formation with the inventive color photographic recording material also in a two-step development process

A-G 5024

effected, wherein in a first step, the silver halide development and dye release takes place, whereupon in a second step, the color image transfer from the photosensitive member to a contacted therewith image receiving member, for example by heating to a temperature zwichen 50 and 15O ⁰ C, preferably at 70 to 90 ^° C., in which case diffusion aids (solvents) can be applied externally before the photosensitive part and image receiving part are laminated.

The image-receiving layer can accordingly be arranged on the same support as the light-sensitive layer Element (single sheet material) or on a separate substrate (two sheet material).

It essentially consists of a binding agent, the mordant for fixing the non-diffusing ones Contains diffusible dyes released by dye releasing agents. As a pickling agent for anionic dyes preferably serve long-chain quaternary ammonium or phosphonium compounds, e.g. those as described in US-A-3,271,147 and US-A-3,271,148.

Certain metal salts and their hydroxides, which are sparingly soluble with the acidic dyes, can also be used Form connections, are used. Polymeric mordants should also be mentioned here, such as those which are described in DE-A-23 15 304, DE-A-26 31 521 or DE-A-29 41 818. The dye mordants are dispersed in the mordant layer in one of the usual hydrophilic binders. e.g. in gelatine, Polyvinylpyrrolidone, wholly or partially hydrolyzed

A-G 5024

S3

ten cellulose esters. Of course, some binders can also act as mordants, e.g. Polymers of nitrogen-containing, optionally quaternary bases, such as N-methyl-4-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, such as described in US-A-2,484,430. Other useful pickling binders are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers, as described, for example, in US Pat. No. 2,882,156, or guanylhydrazone derivatives of acylstyrene polymers, as described, for example, in DE-A-20 09 498. In general, however, other binders, e.g. gelatine, to add.

If the image-receiving layer is in contact with the light-sensitive layer even after development has been completed Element remains, there is usually an alkali-permeable pigment-containing one between them light reflective binder layer which the optisehen Separation between negative and positive and as an aesthetically pleasing image background for the transferred serves positive color image. The yellow filter sheet used according to the present invention is located in this case on the side of the light-sensitive layer, that of the pigment-containing light-reflecting layer Binder layer is opposite. If the image-receiving layer is between the support and the light-sensitive Element is arranged and from the latter by a pre-formed light reflective Layer is separated, either the support must be transparent, so that the color transfer image produced can be viewed through it, or that

A-G 5024

The light sensitive element must be together with the light reflective Layer can be removed from the image-receiving layer to reveal the latter. The image receiving layer but can also be used as the top layer in an integral color photographic recording material be present, in which latter case the exposure expediently through a transparent support is made.

A-G 5024

si

example 1

Production of the silver salt emulsions

Emulsion 1

17.0 g AgNO, dissolved in 200 ml of 45 ⁰ C warm water, were within 2 minutes to a 45 ⁰ C. solution of 20.0 g of gelatin in 1000 ml of water which contained 13.0 g of benzotriazole (BTA) , metered in with stirring. The mixture was then stirred for a further 5 minutes. The pH was adjusted to 5.0 with 5% Na ₂ CO _{3 solution.} By adding 20 ml of a 10% Polystyrolsulf onsäurelösung, cooling to 25 ⁰ C and addition of 10% sulfuric acid (up to pH 3.0 to 3.5) was flocculated and then washed three times with 1000 ml of water. The flocculate was heated to 45 ⁰ C, with 5% Na ₂ CO ₃ solution to pH 6.0 provided, mixed with 5 ml of 1% aqueous phenol solution and brought g by addition of water to a final weight of 435th

Emulsion 2

34.0 g of AgNO dissolved in 200 ml of water were added within 10 minutes to a 50 ° C. solution of 40.0 g of gelatin, 23.7 g of KBr and 1.66 g of KI. Then, 20 minutes at 50 ⁰ C was stirred and then cooled to 35 ° C. 40 ml of a 10% strength polystyrene sulfonic acid solution were added dropwise and the mixture was then cooled ^{to 20 ° C.} By adding 10% sulfuric acid (up to pH 3.0 to 3.5) it was flocculated and mixed three times

A-G 5024

washed 700 ml of water each time. Then C was heated to 4O ⁰ and made basic with 10% sodium hydroxide solution to pH 6.0. Final weight 11.71 g.

Example 2
Manufacture of the Dispergate

Dispersion 1 (color releaser cyan)

50 g of dye releaser 3 (cyan) were in a mixture of 40 g of tricresyl phosphate and 35 g of palmitic acid diethylamide dissolved and in the presence of 2.6 g of sodium dodecylbenzenesulfonate in 1260 g of 6% strength aqueous gelatin solution dispersed.

Dispersion 2 (color releaser magenta)

50 g of paint releaser 12 (magenta) were in a mixture dissolved from 64 g of tricresyl phosphate and 21 g of diethyllaurylamide and in the presence of 1.7 g of sodium dodecylbenzenesulfonate dispersed in 833 g of 6% aqueous gelatin solution.

Dispersion 3 (color releaser yellow)

50 g of color releasing agent 4 (yellow) were in a mixture of 47 g of tricresyl phosphate and 46 g of palmitic acid diethylamide dissolved and in the presence of 3.0 g of sodium dodecylbenzenesulfonate in 1280 g of 6% strength aqueous gelatin solution dispersed.

A-G 5024

Disperse 4 (electron donor compound)

50g of compound ED-I (electron donor compound) dissolved in 50 g of palmitic acid diethylamide and in the presence of 0.1 g of sodium dodecylbenzenesulfonate in 540 g 10% aqueous gelatin solution dispersed.

Dispergat 5 (auxiliary developer)

50 g of the compound of the following formula CH ₃ O-COCH ₃

were dissolved in 100 g of diethyl lauramide and in the presence of 0.2 g of sodium dodecylbenzenesol sulfonate dispersed in 1000 g of 10% strength aqueous gelatin solution.

Disperse 6 (filter yellow)

In 84 ml of water there was added 0.3 g of sodium dodecylbenzenesulfonate dissolved and 16.3 g of a 40% strength dispersion of Cholanylgelb (from Höchst) dispersed.

From the yellow filter dispersion thus obtained (dispersion 6) a casting solution was prepared as follows:

83.7 g of dispersion 6 were dissolved in 136 g of 15% strength aqueous gelatin solution dispersed and diluted with 100 ml of water.

A-G 5024

Example 3

Production of the package emulsions

PE-I (cyan)

34.4 g of Emulsion 2 were melted at 4O ⁰ C and neutralized by addition of a 0.1% methanolic solution

-4 a red sensitizer spectrally sensitized in an amount of 4x10 mole per mole of silver halide and 70 digested min at 4O ⁰ C. Then, 25.6 g of Emulsion 1 and 35 ml of 4O ⁰ C water was added. Then 44.8 g of dispersion 1 (cyan) and 11.2 g of dispersion 4 were added. 55 out of a 10% solution were abicum ml aqueous rubber Ar and stirred 15 min, after which were added dropwise over 4 min 140 ml 4O ⁰ C hot water. The pH is adjusted to 4.8 by slowly metering in 1% acetic acid and stirring is continued for 15 min. With continued stirring, the mixture is then rapidly ^{cooled to about 8 °} C. and a solution of 0.55 g of chrome alum in 160 ml of water is metered in over the course of 4 minutes. Stirring is continued at 8 ° C for 1 to 1 1/2 hours. By centrifuging and separating off the supernatant liquid, 49 g of PE-I (cyan) with an average particle size of approx. 7 μm were obtained.

PE-2 (magenta)

in a manner analogous to that described for PE-I, was also PE-2 manufactured, but with the following special features:

A-G 5024

-4

Green sensitizer (4x10 moles per mole of silver halide) instead of red sensitizer,

24.3 g of Dispersion 2 (magenta) instead of Dispersion

After centrifugal separation, there was obtained 41 g of PE-2 (magenta) having an average particle size obtained from about 10 pm.

PE-3 (yellow)

In a manner analogous to that described for PE-I, was also PE-3 manufactured, but with the following special features:

—4

Blue sensitizer (8x10 moles per mole of silver halide) instead of red sensitizer,

34.2 g of Disperse 3 (yellow) instead of Disperse

After separation by centrifugation, 55 g of PE-3 (yellow) with an average particle size of approx. 5 μm were obtained.

PE-4 (cyan)

In a manner analogous to that described for PE-I, was also PE-4 manufactured, but with the following special features:

An additional 16.4 g of dispersion 6 were added to the mixture of emulsion and dispersion 1.

Yield: 45 g

A-G 5024

(O

yt -

PE-5 (magenta)

In a manner analogous to that described for PE-2, PE-5 was also produced, but with the following special feature

An additional 16.4 g of dispersion 6 were added to the mixture of emulsion and dispersion 2.

Yield: 39 g.

The following spectral sensitizers were used.

Red sensitizer:

^C 2 ^H 5 = C CH =

10 green sensitizer:

^C 2 ^H 5

= C

CH =

A-G 5024

Blue sensitizer:

CH =

A partial casting solution was prepared from each of the above package emulsions PE-I , PE-2, PE-3, PE-4, PE-5 as follows:

Each of the package emulsions was homogenized with 100 ml of water for 10 minutes and with 40 ml of a 10% aqueous guanidine trichloroacetate solution, 4 ml of wetting agent Triton X 100 (4%), 18.4 g of Dispersion 5 (auxiliary developer) and one A solution of 19 g of gelatin in 170 ml of water was added.

Example 4

The image receiving part of a photographic recording material for the color diffusion transfer process was produced by applying the following layers successively to a transparent support made of polyethylene terephthalate. The quantities given relate to 1 m ² ,

1. A pickling layer with 2 g of polyurethane pickling made of 4,4'-diphenylmethane diisocyanate and N-ethyldiethanolamine, quaternized with epichlorohydrin according to DE-A-26 31 521, Example 1, and 2 g Gelatin.

A-G 5024

a "· ■ '- ■

2. A light-reflecting layer contains 20 g of Ti ₂ and 2 g of gelatin.

3. A protective layer with 1 g gelatin.

The image receiving material thus obtained is used in the following Examples as a coating base for the production of integral recording materials. It is also suitable as a separate image receiving sheet.

Example 5
Material 1 (according to the invention)

Using the coating base described in Example 4 (Image receiving part) having layers 1, 2 and 3 became a photographic recording material produced according to the invention by coating with the following layers:

4. Mixing of partial pouring solutions of the package emulsions PE-I, PE-2 and PE-3 (see Example 3) in a ratio of 1: 1: 1.3;

Wet application 300 pm.

5. Casting solution made from yellow filter dispersion (cf. Example 2);
Wet application 40 μπι.

6. Hardening layer.

A-G 5024

(3

Example 6

Material 2 (comparison)

A photographic recording material was used for comparison using the coating base (image receiving part) described in Example 4 Coating made with the following additional layers

4. Mixing of partial pouring solutions of the package emulsions PE-4, PE-5 and PE-3 (cf. Example 3) in the ratio 1: 1: 1.3;

Wet application 300 μm.

5. Hardening layer.
Example 7

The photographs described in Examples 5 and 6 are seen Recording materials were passed through a combination extract filter (with gray wedge) exposed to red, green and blue light, whereby to determine the

D. - and D values of the mixed grain emulsion with light mm max

normal exposure was carried out on the relevant third of the spectrum and total exposure was carried out with light from the other two thirds of the spectrum. Then, the recording materials were heated for 60 sec by means of a heating drum to 137 ⁰ C, then 30 s in water allowed to swell and finally heated s 60 on a hot stage at 75 ⁰ C. With help

A-G 5024

of a computer densitometer were the D. ~ D values of the transferred into the image receiving layer

max * ■ ^J

colored wedges were determined (Table 1). Table 1

^D max ^D min

Φ EE ^ 2 Sb EE bg

(invention 1.10 1.13 1.25 0.21 0.17 0.23

according to)

(Comparison) 1.08 1.08 1.21 0.98 0.18 0.24

The absolute yellow filter densities in the two recording materials (Material 1 and Material 2) were identical. From Table 1 it can be seen; that in the inventive Recording material both the D. ~ The values as well as the D values of the ink transfer were comparable. In the comparison material without the separate yellow filter layer according to the invention met this

probably for the D values, but not also for the max

D. Values too. The comparison material had a non-mm

high yellow haze to be tolerated.

A-G 5024

Claims (5)

Claims 1. Color photographic developable by heat treatment Recording material with a photosensitive Binder layer, which in the form of separate complex coacervates several different spectrally sensitive assignments from each a) a photosensitive silver halide of relevant spectral sensitivity, optionally in combination with an essentially non-photosensitive silver salt, b) a non-diffusing coloring compound, which is a diffusible dye as a result of development by heat treatment able to release and / ** c) where appropriate, other auxiliaries contains, the silver halide being sensitive to blue in at least one of the assignments mentioned is, characterized in that a yellow filter layer above or below the photosensitive binder layer is arranged so that during the imagewise exposure the light passes through the yellow filter layer gets into the photosensitive binder layer, and that the silver halide in the blue-sensitive Assignment is at least 0.5 log I't units more sensitive than the silver halide in the other assignments. A-G 5024 2. Recording material according to claim 1, characterized in that the photosensitive binder layer contains a blue-sensitive, a green-sensitive and a red-sensitive assignment, where each of these assignments a) a photosensitive silver halide of relevant spectral sensitivity, optionally in combination with an essentially non-photosensitive silver salt, b) a non-diffusing coloring compound, which as a result of development through Heat treatment is able to release a diffusible dye, and c) where appropriate, further auxiliaries and the silver halide in the blue-sensitive assignment by at least 0.5 log I * t units is more sensitive than the silver halide in the green-sensitive and in the red-sensitive assignment. 3. Recording material according to claim 1 or 2, characterized characterized in that the non-diffusing color-giving compound is a reducible color releaser, is used in combination with a non-diffusing electron donating compound. A-G 5024 - ** - 3510635 4. Recording material according to claim 1, characterized in that that the silver halide in the blue-sensitive assignment by 0.7-0.9 log I't units is more sensitive than the silver halide in the other assignments. 5. Recording material according to claim 4, characterized in that that the yellow filter layer creates a "te from 0.7 - 0.9 has. A-G 5024