JPS62291643A - Color photographic recording material developable by heat treatment - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 3. Detailed Description of the Invention The present invention relates to a color photographic recording material which can be developed by heat treatment, which material is applied to a layer support and comprises a photosensitive silver halide and a non-photosensitive silver halide. Consisting of at least one binder layer containing a diffusible dye-providing compound, the recording material further contains compounds which improve the D□a/D@@K relationship and the photosensitivity.

It is known to produce colored images by heat treatment using suitable color photographic recording materials.

Particularly suitable dye-forming compounds are those dye-releasing agents which can be incorporated into the layers of the photographic recording material in non-diffusible form and which release diffusible dyes as a result of the phenomenon. The particular suitability of the imagewise released dye is that it can be transferred to the special image-receiving layer to form a brilliant dye image without any troublesome image silver or silver halide being superimposed thereon and hence after the transfer. This can be attributed to the fact that no processing is required. Therefore, the combination of thermal development and a dye diffusion process provides an advantageous rapid method for producing color images. Recording materials suitable for this method are described, for example, in DE-A-3215485.

According to this publication, silver halide, silver pencitriacylate, dye release agents and guanidine trichloroacetate (
A recording material comprising a combination of base-donating agents) is exposed to light to form an image and then subjected to heat treatment while in contact with an image-receiving sheet to transfer the imagewise released dye to the image-receiving sheet.

Several such combinations are required to produce a multicolor image, and the silver halide in each of these combinations is sensitive to a different spectral region, and a joint name is assigned corresponding to its spectral sensitivity. containing a dye-releasing agent which releases a dye of another color, generally a color complementary to the color of light to which the particular silver halide is primarily sensitive. . Such associations can be arranged on top of each other in various layers.

The dye images obtained using the known thermally developable color photographic recording materials exhibit a rather low maximum color density and a high degree of fog; in order to overcome this disadvantage, DE 33 45 023 discloses fog-reducing agents. describes the use of mercapto compounds of the following types. However, the dye images obtained with these mercapto compounds are also unsatisfactory in terms of D□h/D II a M and in terms of photosensitivity.6 Therefore, it is an object of the present invention to obtain dye images that can be developed by heat treatment. It is a color photographic recording material.../D... It is an object of the present invention to provide materials which are further improved in this regard and with respect to photosensitivity.

The present invention can be developed by heat treatment and is disposed on a layer support and contains photosensitive silver halide but is essentially free of other inorganic silver salts and is diffusive as a result of development by heat treatment. at least one binder layer containing at least one non-diffusible dye-providing compound capable of releasing dye and a fog-reducing compound, wherein the fog-reducing compound has the following formula: represents a group necessary to complete a heterocyclic group containing a 5- or 6-membered heterocycle;
and X represents a carboxylic acid or sulfonic acid group or a group containing a carboxylic acid or sulfonic acid group, which carboxylic acid or sulfonic acid group is present in the anionic form, for example in the form of an alkali, alkaline earth or ammonium salt, or in the form of a tri- or tetra-alkyl The present invention relates to a photographic recording material characterized in that it corresponds to (which can also be present in the form of a salt of an organic base such as an ammonium salt).

Particularly advantageous fog-reducing compounds according to the invention have the following general formula:
R1 and R2 are the same or different, hydrogen, alkyl, preferably containing up to 6 carbon atoms, such as methyl, ethyl, alkenyl such as allyl, cycloalkyl such as cyclohexyl, aryl such as phenyl, aralkyl such as benzyl, halogen for example represents Ct or Br, or R1 and R2 together form a fused benzene ring; R3 is hydrogen, alkyl, preferably containing up to 6 carbon atoms such as methyl, ethyl, alkenyl such as allyl, cyclo Alkyl such as cyclohexyl, aralkyl such as benzyl, aryl such as phenyl,
These groups can optionally be further substituted, for example by hydroxy, alkoxy or halogen.

The heterocyclic mercaptoazole carboxylic acids or sulfonic acids used according to the invention are known compounds and their preparation is described in the relevant literature.

For example, the following compounds are suitable fog-reducing compounds: The fog-reducing compounds used in accordance with the present invention are added to the casting solution for the photosensitive layer. The amount used can vary within a wide range, and it can be easily determined by the expert by some simple routine tests. The fog-reducing compound preferably contains 0 per mole of silver halide.
．． Used in cliffs of 0.001 to 10.0 g. They can be added in aqueous acid or organic medium. However, it can also be added in other dispersed forms.

The color photographic recording material according to the invention contains a light-sensitive silver halide, a non-diffusible dye-providing compound capable of releasing a diffusible dye as a result of thermal development, and a fog-reducing compound according to the invention. on a dimensionally stable layer support.

Therefore, the essential constituents of the heat-developable recording material according to the invention are silver halides, which include silver chloride, silver bromide,
They can consist of silver iodide or mixtures thereof, and these can have a grain size of 0.02 to 2.0 μm. Silver halide crystals can have a regular crystal structure, for example cubic or octahedral crystal shapes. However, they can also have a disordered crystal structure or be present in plate-like form. In the case of mixed crystals, the silver halide can be uniformly distributed over the entire cross section of the crystal. However, the composition of the silver halide can also differ in the different zones.

It is thus also possible to use silver halide emulsions with a layered grain structure in which there are at least two layers of silver halide of different composition. Although negatively acting silver halide emulsions are generally used,
In another aspect, German Patent Application No. 23328
No. 02, No. 2308239 and No. 2211728
It is also possible to use the direct-positive silver halide emulsions described in No. The light-sensitive emulsions can be present in the unsensitized silver halide form, or they can be chemically and/or spectrally sensitized by suitable additives, with spectral sensitizers being chemically and/or spectrally sensitized. Before or during ripening, : is added after.

The amount of photosensitive silver halide in a particular layer is between 0.01 and 3.
The actual amount of silver halide used will be determined by the particular requirements of the reactants used and the desired effect.

As is already known, in photographic recording materials which can be developed by heat treatment, in addition to the light-sensitive silver halides, other substantially light-insensitive or in any case much less light-sensitive silver salts are also often used. .

These additionally used silver salts are also silver halides or other silver salts, such as silver cyanide, silver thiocyanate, silver sulfite or silver sulfate, which are sensitive to light by a factor of at least about 10. is low and also has a distinctly high solubility.

Although these additional silver salts generally do not contribute to photosensitivity, they are often advantageous because they increase color density. However, this effect is often accompanied by a significant increase in fog, especially when the silver halide emulsion used in the present invention contains no more than 4 mol %, preferably more than 2 mol %, of the total amount of silver salts. Only recording materials that are not available are used. The recording materials according to the invention which, apart from the photosensitive silver halide of the desired photosensitivity, do not contain inorganic silver salts in the photosensitive layer are used with particularly good results.

On the other hand, the addition of organic silver salts of approximately the same or less solubility as the photosensitive silver halide is advantageous. Silver salts of compounds containing imino groups are suitable. In a preferred example, such silver salts include silver salts of benzotriazole and its derivatives, such as alkyl-, hydroxy-
, sulfo- and/or halogen-substituted benzotriazole silver salts.

Another essential constituent of the recording material according to the invention is a non-diffusible dye-providing compound. This compound is one that can release a diffusible dye as a result of a redox reaction that occurs during development. This is hereinafter referred to as dye f) release agent.

The dye-releasing agents used according to the invention can be several different types of compounds, all of which are redox-dependent in their binding strength and link dye residues to carrier residues containing ballast residues. Characterized by Bond.

Regarding this, Angewante Hemoi International Edition English (^ngew,
Chew, Int, Ed, Engl.), 22
(1983), 191-209, in which the most important known systems are described.

A particular advantage in this regard is the redox equivalent to the first-order equation.
Provided by active dye release agent: BALLAST
-REDOX-DYE where BALLAST is a ballast residue and REDO
X is a redox-iodine group, i.e. a group that is oxidizable or reducible under alkaline development conditions and, depending on whether it is present in the oxidized or reduced form, can undergo an elimination reaction, a nucleophilic rearrangement. reaction, hydrolysis or other cleavage reactions to different extents, resulting in the elimination of DYE residues, and DYE contains residues of diffusible dyes, such as yellow, agenta or cyan dyes or residues of dye precursors. It is the basis.

Ballast residues can be regarded as residues that make it possible to incorporate the dye-releasing agents according to the invention in diffusion-resistant form into the hydrophilic colloids commonly used in photographic materials.

Particularly suitable residues of this type are organic residues containing linear or branched aliphatic groups of 8 to 20 carbon atoms and optionally carbocyclic or heterocyclic aromatic groups. These residues may be attached directly or indirectly to the rest of the molecule, such as one of the following groups -NHCO-1-NH3O2-1-NR-(
where R is hydrogen or alkyl), -〇- or -S-
1. In addition, the ballast residues can also contain water solubilizing groups, such as sulfo groups or carboxyl groups, which groups can also be present in anionic form. Since the diffusivity depends on the molecular size of the compound used, for example, if the entire molecule used is sufficiently large, it is sufficient to use a relatively short residue as a ballast residue.

Redox-active carrier residues with the BALLAST-REDOX-m structure and corresponding dye-releasing agents are known in different forms. For a detailed description, please refer to Angewante Hemy 92 (1983) 191-209.
Considering this, there is probably no need to provide it here.

Some examples of redox-active carrier residues from which dye residues are detached as a function of imagewise oxidation or reduction are listed below for illustrative purposes only: The group in parentheses is the functional group of the dye residue and Together with this residue it is separated from the rest of the carrier residues. The functional groups can be substituents which can have a direct influence on the absorption and optionally complexing properties of the released dye. On the other hand, however, the functional group can also be separated from the chromophore of the dye via an intermediate or a linker. Finally, the functional groups, optionally together with intermediates, can be important for the diffusion and mordanting behavior of the released dye. Suitable intermediates are, for example, alkylene or aryl groups.

Suitable dye residues are essentially any type of dye residue as long as it is sufficiently diffusive to be able to diffuse from the photosensitive layer of the photosensitive material into the image-receiving layer. . For this purpose, the dye residue can have one or more alkali-solubilizing groups. Suitable alkali-solubilizing groups are in particular carboxyl groups, sulfo groups, sulfonamido groups and aromatic hydroxyl groups. Alkali-solubilizing groups of the type in question may be preformed in the dye-releasing agent used in the invention or may be generated from removal of dye residues from carrier residues bearing pallast groups. There may be. Dyes particularly suitable for the method of the invention are azo dyes,
Includes azomethine dyes 1, anthraquinone dyes, phthalocyanine dyes, indigoid dyes and triphenylmethane dyes which are or can be complexed with metal ions.

Residues of dye precursors are converted into dyes during photographic processing, in particular under thermal development conditions, by oxidation, by coupling, by complexation or by liberation of auxochromes in the chromophoric system, e.g. saponification. is to be understood as the residue of a compound. In this sense, dye precursors can also be leucodyes, couplers or dyes which are converted into other dyes during processing. Provided that the distinction between dye residues and dye precursor residues is not critical, dye precursor residues shall also be understood as dye residues in the following.

Suitable dye release agents are described, for example, in the following publications: U.S. Pat. No. 3,277,550;
No. 3443940, German Patent Application Publication No. 19
No. 30215, No. 2242762, No. 24029
No. 00, No. 2406664, No. 2505248, No. 2543902, No. 2613005, No. 2645656, No. 2809716, No. 282
3159, Belgian Patent No. 861241, European Patent No. 0004399, German Patent Application No. 0004400, German Patent Application No. 3008588, German Patent Application No. 3014669 and European Patent No. 0038092.

In some embodiments of thermal development according to the present invention, the dye release agent is present as an oxidizable or coupled dye release agent, and in other embodiments it can be present as a reducible dye release agent. Depending on whether the dye is released from the oxidized or reduced form of the dye-releasing agent, negative or positive original copies are obtained when using standard negative-working silver halide emulsions. Therefore, appropriate f door - Chise 1 + JFL oral sentence I + 77L5/) - wL
l-el-Al/W-JJ,)↓Tshi\hahe images are generated as desired.

Particularly suitable oxidizable dye release agents for the heat-developable recording material according to the invention are, for example,
No. 645656.

If the dye release agent is oxidizable, it represents itself a reducing agent which is oxidized by the imagewise exposed silver halide directly or indirectly with the aid of an electron transfer agent (ETA). In this regard,
Image differentiation is done in relation to the ability to release diffusible dyes. On the other hand, if the dye-releasing agent is reducible, it is best used in combination with reducing agents present in limited amounts, so-called electron-donating compounds or electron-donating precursor compounds; The compound is in this case co-existed with the dye-releasing agent and the photosensitive silver halide in the same binder layer. The assistance of electron transfer agents is also advantageous when reducible dyes are used in combination with electron donating compounds.

A recording material according to the invention suitable for producing a dye image of 1 generation of color (if 蔚稍 1 of 100% of the dye image) is, for example, a carrier corresponding to the following formula: 20 containing a reducible dye-releasing agent having a group (wherein R1 represents alkyl or aryl; R2 represents alkyl, aryl, or a group that together with R3 completes a fused ring) R3 is hydrogen, alkyl, aryl, hydroxyl, halogen such as chlorine or bromine, amino, alkylamino, dialkylamino including also cyclic amino groups (e.g. piperidino, morpholino), acylamino, alkylthio, alkoxy, aroxy, sulfo, or R2 R4 represents alkyl; R5 represents alkyl or preferably hydrogen; and at least one of R1-R4 contains a ballast residue.

The electron donating compound used in combination with the reducing dye donor also serves as a reducing agent for the silver halide and the dye releasing agent. Since the silver halide and the dye-releasing agent compete with each other for the oxidation of the electron donor compound, and the former is superior to the latter in this respect, the silver halide present is As a function of the exposure - determines the area within which the dye-releasing agent is converted to the reduced form by the electron donor compound.

Under development conditions, for example when an imagewise exposed color photographic recording material is heated, the electrodonor compounds present in the limited indigo are oxidized according to the degree of exposure and are therefore no longer available for reaction with the dye release agent. is not used. This results, as it were, in an imagewise distribution of unused electron donor compounds.

Conventionally described electron donor compounds include, for example:
Non-diffusible or only slightly diffusible hydroquinone, benzisoxacilone, p-aminophenol or derivatives of ascorbic acid (eg ascorbyl palmitate) (DE-OS 28 09 716).

Examples of other electron donating compounds are DE 2947425, DE 3006268, DE 3130842, DE 3144037, DE 32
No. 17877 and European Patent No. 0124915 and Research Disclosure No. 24305 (Resear
ch Disclosure) 24305 (198
It has been known since July 1994). It has been found that the electron donor compounds described fulfill the requirements for them also under thermal development conditions and are therefore also suitable as electron donor compounds for the purposes of the present invention. Particularly appropriate? Erec), Roni 廿 Louis P compound suhiro [
fflφ is formed from the corresponding electron donor precursor compound in the layer, ie, the electron donor compound is present only in a masked form so that it is virtually inactive before development. Initially inactive electron donor compounds are converted to their active form by removing the protecting group under thermal conditions, for example by hydrolysis. For the purposes of the present invention, such electron donating precursor compounds are also considered to be electron donor compounds.

In other embodiments, dye release agents that can release a diffusible dye as a result of a coupling reaction can also be used. There are two possibilities regarding this. In the first case, the dye is formed by chromogenic coupling only by dislodging the diffusion-inhibiting ballast group from the coupling position. In other cases, a non-diffusible coupler is present, containing as a residual group a dye residue already preformed at the coupling position, which is detached upon coupling and thus becomes diffusive. Such systems are described, for example, in US Pat. No. 3,227,555.
It is stated in No. 0. In addition, dye release agents can also be
For example, dye-releasing polymeric couplers as described in German Patent Application No. 3,422,455 can also be used.

The essential constituents of the recording material of the invention described above, namely the photosensitive silver halide, the dye-releasing agent (optionally used in combination with an electron donor compound) and the flash-reducing compound used according to the invention, are mutually exclusive. They are present together dispersed in a binder. The binder can be either hydrophobic or hydrophilic, preferably a hydrophilic binder. Gelatin is preferably used as a binder for the photosensitive layer. However, it can be replaced in whole or in part by other natural or synthetic binders. Natural binders are, for example, alginic acid or its derivatives such as salts, esters or amides, cellulose derivatives such as carboxymethylcellulose, alkylcelluloses such as hydroxyethylcellulose, starches and their derivatives and capranates.

Synthetic bindu is polyvinyl alcohol, especially partially saponified polyvinyl acetate and polyvinylpyrrolidone.

Examples of hydrophobic binders are polymerizable ethylenically unsaturated monomers, such as polymers of alkyl acrylates, alkyl methacrylates, styrene, vinyl chloride, vinyl acetate, acrylonitrile and acrylamide. Polyesters, polyurethane compounds and waxes are also used. These polymers can be used, for example, in latex form.

To produce a monochromatic dye image, the photosensitive layer contains one or more dye-releasing agents from which, in association with the photosensitive silver halide, the dye of the corresponding color is released. The resulting overall color is produced by mixing several dyes.

In this way, it is also possible to produce black and white images by mixing several dye-donors of different colors in precise register with each other. In order to produce multicolor dye images, the color photographic recording material according to the invention contains several, generally three, combinations of dye-releasing agents and spectrally differently sensitized silver halide. , Ko/7-I Ifi weight 1 force medium chi 4 h kudzu and tke 11 to fishing 11 ~ heavy”L y 111
l(wa no ^)7N! +5 ■ Substantially corresponds to the spectral sensitivity range of the combined silver halide. Various associations of silver halide in association with dye release agents can be accommodated in various layers of the color photographic recording material, preferably between these various binder layers for the trapping of eg development oxidation products. There is a separating layer of a water-permeable binder, such as gelatin, containing an agent, which has the main purpose of separating the various associations from each other and thus counteracting color alterations. In such a case,
The color photographic recording material of the invention can be prepared, for example, by one light-sensitive binder layer in which the silver halide present is primarily red-sensitive due to spectral sensitization and in which a cyan dye-releasing ring is present; Another light-sensitive binder layer which is predominantly green-sensitive due to sensitization and in which the magenta dye-releasing agent is present, and the silver halide present which is predominantly blue-sensitive due to its own photosensitivity or due to spectral sensitization. a third photosensitive binder layer, which is photosensitive and in which a yellow dye is present.

Others of this invention! ! ! In this case, each combination of photosensitive silver halide and dye releasing agent described above is used in the form of a so-called complexed coacervate.

Complexed coacervates are to be understood as dispersed forms in which a mixture of essential constituents is surrounded by a common grain of hardened binder. Such dispersions are also known as packet emulsions. They are obtained by complex coacervation.

“Complexed coacervation” refers to the generation of two phases during the mixing process of an aqueous solution of a polycationic colloid and a polyanionic colloid: a concentrated colloidal phase (hereinafter referred to as complexed coacervate) and a dilute colloidal phase. (hereinafter referred to as equilibrium solution) is understood to be formed by electrical interaction.

The complexed coacervate is separated from the equilibrium solution in the form of drops and in the form of a cloudy cloud. If the complexed coacervation is carried out in the presence of a solid such as a silver halide or fine oil droplets, it is generally assumed that the complexed nia7acervate encapsulates the solid or droplet inside the colloidal particles. The result is a dispersion of coacervate particles encapsulated by oily droplets of a solution of solid (in the present case the photosensitive silver halide) and organic components (in the present case the dye release agent and optionally other auxiliaries). It will be done. This is then hardened with a hardening agent so that the original shape of the particles is not destroyed during subsequent manufacturing steps of the photographic recording material, such as casting solution preparation and coating steps. The dispersion is best cooled to a temperature of 25° C. or less before hardening, which results in a good quality packet emulsion.

Methods for preparing packet emulsions in which dye-forming substances are incorporated by complex coacervation are described, for example, in US Pat.
No. 869 and No. 3396026.

Examples of hardeners used for the preparation of packet emulsions according to the invention are chromium salts (e.g. chromium closure, chromium acetate),
aldehydes (e.g. formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (e.g. thumethylolurea, methyloltumethylhydantoin), dioxane derivatization methods (e.g. 2,3-dihydroxydioxane), activated vinyl compounds (e.g. 1,3,5- )
Liacryloylhexahydro-5-triazine, 1,3
-vinylsulfonyl-2-propatur), active halogen compounds (e.g. 2,4-dichloro-6-hydroxy-S-)ryanone) and mucohaloacids (e.g. mucochloric acid,
mucophenoxychloric acid).

Curing agents can be used alone or in combination.

According to the present invention, the use of a packet emulsion allows the combination in a single binder layer of several emulsion components with different spectral sensitivities, including each dye-releasing agent, to be spectral uncoupled. This ensures that no color alterations occur. This is possible because the exposure of the silver halide grains that it consists of almost exclusively determines the extent to which dye is released from the dye-donor present in the same coacervate grains (packets) as the silver halide. (1-) Spectrum of blue-sensitive silver halide emulsions, green-sensitive silver halide emulsions, and red-sensitive silver halide emulsions without the risk of major color alterations. This makes it possible to accommodate them in the same binder layer with a dye-releasing agent that is symmetrically associated with the dye-releasing agent.

In addition to the constituents already mentioned, the color photographic recording materials according to the invention can contain other components and auxiliaries useful, for example, for heat treatment and associated dye transfer. These other ingredients and adjuvants can be included in the photosensitive NJ or non-photosensitive layer.

Auxiliary agents of the type in question are, for example, auxiliary development layers.

These auxiliary developers generally have a developing performance for the exposed silver halide; in the case of the present invention, they primarily act as accelerators for the reaction that occurs between the exposed silver halide and the reducing agent. When an oxidizable dye-donor is used, the reducing agent is the same as the dye-donor, whereas when a reducible dye-donor is used, the reducing agent reacts with the dye-donor instead. Since the reaction consists primarily of electron transfer, auxiliary developers are also known as electron transfer agents (ETA).

Examples of suitable auxiliary developers are hydroquinone, pyrocatechol, pyrogallol, hydroxyamines, ascorbic acid, 1-phenyl-3-pyrazolidone and its derivatives such as 4-methyl-1-7enyl-3-pyrazolidone, 4
, 4-methyl-1-phenyl-3-pyrazolidone, 4
-Hydroxymethyl-4-methyl-1-phenyl-3-
Pyrazolidone, 4-hydroxymethyl-4-methyl-1
-tolyl-3-pyrazolidone and 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone. In such cases, it is advantageous to mask the auxiliary developer with a protecting group which can be removed by reaction with an alkaline reagent. Since the auxiliary developers serve a catalytic function, so to speak, they do not need to be present in stoichiometric amounts. Generally, they only need to be present in the layer in an amount up to 0.5 mole per mole of dye release agent. They can be incorporated into the layer, for example, from solutions in aqueous cutting or in the form of aqueous dispersions obtained using oil-forming agents.

In the case of coupled color systems, color developers are required. Reference is made here to the common 722 diamine developer and the ami/7 el/-. For reasons of stability, it is advantageous to use a developer which is added in masked form and then the protecting group is removed under the process conditions.

Other adjuvants may be compounds that activate development; suitable compounds of this type are bases or base precursors, ie compounds with a pka value of 8 and above. Suitable inorganic bases are, for example, hydroxides, tertiary phosphates, borates, alkali or alkaline earth metal carbonates or ammonium hydroxide. Suitable organic bases are, for example, aliphatic amines, heterocyclic amines, amines, cyclic amines, guanidine or cyclic guanidine.

A base precursor is to be understood as a compound that can release a base component when heated. Suitable base precursors are salts of the bases mentioned above with thermally decomposable organic acids, such as trichloroacetic acid, acetoacetic acid, cyanoacetic acid, sulfonylacetic acid or acetylenecarboxylic acid. Also advantageous are base precursors with covalent bonds of the base, which release the base when heated, for example by fractionation reactions. In this regard, hydrooxamic acid carbamate (European Patent No. 012040)
No. 2) or aldoximimine carbamate (No. 0118078).

Other aids are, for example, compounds capable of releasing water under the action of heat. Such compounds are in particular inorganic salts containing water of crystallization, such as (tNIL2sO4.10H20°N H4
Fe(SO-)2 .12H20. The water released by heating facilitates the development and diffusion steps necessary for image formation.

Other auxiliaries are, for example, so-called thermal solvents, which are generally non-hydrolyzable organic compounds which are solid under normal conditions but melt when heated to heat treatment temperatures and in which the development process is carried out. Compounds which release liquid media during the process are understood to be more rapid. Such thermal solvents can serve, for example, as diffusion enhancers.

Preferred examples of thermal solvents include, for example, US Pat. No. 33,476.
75, such as polyethylene glycols with an average molecular weight of 1500 to 20,000, polyethylene oxide derivatives such as their oleic acid esters, beeswax, monostearin. Suitable compounds are, for example, those with high dielectric constants and -802-
or contains a -〇〇- group.

In this regard, the thermal solvents cited in EP 11961.5 are also mentioned, namely urea, pyridine, pyridine-N-oxide, carboxylic acid 7amides, imides, sulfonamides, polyalcohols, oximes, pyrazoles and imidazoles. is referenced.

Other suitable auxiliaries are development accelerators, for example EP 0 160 313 and German Patent Application No. 15! ! ! $3
339810.

In addition, certain pH-lowering agents can be added which, among other things, contribute to the stabilization of the minimum density.

Suitable compounds are disclosed, for example, in German Patent Application No. 3442
No. 018 and f: J&351517 (acid precursor compounds of the type described in No. 5).

Development of the imagewise exposed color photographic recording material of the invention is initiated by subjecting it to a heat treatment, in which the light-sensitive binder layer is heated to an elevated temperature, e.g.
°C for approximately 0.5-300 seconds. Suitable conditions for the development process, including diffusion of the dye, are thus established in the recording material. This can occur under completely dry conditions, ie in the presence of only moisture present in the waste arrangement, or optionally, for example in the presence of added water. Upon development, the diffusible dye is imagewise released from the dye-releasing agent and transferred to the image-receiving layer which is an integral part of the color photographic recording material of the invention or is at least contacted during development. Ru.

Thus, the image-receiving layer may be disposed on the same layer support as the photosensitive element (single sheet material), or it may be disposed on a separate layer support (separate sheet material). or consisting essentially of a mordant-containing binder for fixing the diffusible dye released from the non-diffusible dye release agent. Preferred mordants for anionic dyes are long chain quaternary ammonium or phosphonium compounds, such as those of the type described in US Pat. Nos. 3,271,147 and 3,271,148.

Furthermore, it is also possible to use metal salts and hydroxides which form poorly soluble compounds with acid dyes. Here also polymeric mordants, e.g. )
Reference may also be made to those of the type described in 'I'7 Patent Application Publication No. 1jlifj S2315304, S2631521 or S2941818. Other preferred mordants are polyvinylimigsol mordants, which are partially quaternized with e.g. benzyl, hydroxyethyl, alkyl, epoxyprobyl, propyl, methyl and ethyl halides, with the degree of quaternization ranging from 1 to 50 6% of
The dye mordant is dispersed in the binder layer in one of the customary hydrophilic binders such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, fully or partially hydrolyzed cellulose esters. Some binders of course also function as mordants, such as nitrogen-containing, optionally quaternized, basic polymers such as those described in US Pat. No. 2,484,430.
-Methyl-4-vinylpyridine, 4-vinylbilinone,
It is a polymer of 1-vinylimigsol. Suitable mordant binders for ponds are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers as described in US Pat. No. 2,882,156, or as described in German Patent Application No. 200
9498, a guanylhydrazone derivative of an acylstyrene polymer. However, other binders, such as gelatin, are generally added to the last-mentioned mordant binder.

If the image-receiving layer remains in layer contact with the photosensitive element after development is complete, there is typically an alkali-permeable, pigment-containing, light-reflecting layer between them that provides optical separation between the dark and the light. Placed for and as an aesthetically appealing image background for transferred positive dye images.

If the image-receiving layer is disposed between the layer support and the photosensitive element and is separated by a preformed light-reflecting layer, the layer support is transparent and the dye transfer image formed therethrough is transparent. must be visible or the photosensitive element along with the light-reflecting layer must be removed from the image-receiving layer to expose the image-receiving layer. However, the image-receiving layer can also be present as the top layer in an integrated color photographic recording material, in which case the recording material is best exposed through a transparent layer support.

In the case of an integrated layer unit of photosensitive element and image-receiving element, a stripping layer can also be included to separate the two layer elements.

for the photosensitive element and optionally for the image-receiving element;
The layer support must be dimensionally stable at the processing temperature. 6 polyester materials are preferably used, of which standard film or paper supports are suitable. Conventional hardeners commonly used in photographic materials and also rapid and immediate hardeners can be used as hardeners for both light-sensitive elements and image-receiving elements.

Example 1 A photosensitive element of a photographic recording material for the diffusion transfer method was made by applying the layers described below to a transparent layer support of polyethylene Tele 7 grade. All amounts stated are based on 1 m2.

On the layer 0, 5 gA gN O) (4 mol% AgCl; 8
8.7 mol% AgBr, 7.3 mol% AgI; average particle size 0. green sensitized silver halide emulsion of 0.3 μm);
3 g of dye-releasing agent A ＼〜---- Dye-releasing agent A: N(CH))2 (emulsified in diethyl laurylamide 0.15.); 0.05 g of potassium bromide; 1 g having the following composition: Polyester Turethane: 84.1% polyester of 7-dipic acid, 1,6-hexaneol and neopentyl glycol, 13.1% hexamethylene diisocyanate, and 2.7% N-7 minoethyl taurine; and 1. Layer containing 5g gelatin.

Counterfeit 1.5g of guanidine trichloroacetate; 0°03
5 g of a7tylated product of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone; 0.3 g of compound B Compound B (emulsified in tricresyl phosphate); 0.03 g
Compound C Compound C: and layer containing 1.5 g of gelatin.

Layer - Protective layer containing 0.5g gelatin. A hardening agent is also applied to this protective layer.

The photosensitive element thus prepared is referred to as Sample 1 and serves as a comparative sample.

Further Samples 2-23 were prepared in a similar manner in which compounds according to the invention and comparative compounds were added to the silver halide emulsion in layer 1 in the amounts indicated, as shown in Table 1 below. The comparative compounds used were as follows: 2CM.

■ (Compound 43 of German Patent Application No. 3345023)
) Image-receiving elements for photographic recording materials are prepared by sequentially applying the following scraps to a polyethylene-coated paper layer support: !
! It was done. All amounts are based on 1 m2.

1. 2 g of polyurethane mordant of N-ethylgetanol and 4,4'-nophenylmethanoisocyanate quaternized with epichlorohydrin according to Example 1 of German Patent Application No. 2 631 521; 0.035 g of compound C
and 2 g of gelatin.

2. Preserves 0.8g of gelatin! 1! layer. This retains the hardening agent.
l! Apply to scraps.

First 1 Samples of photosensitive elements (Samples 1-23) were exposed through a staged wafer. The samples were developed in two steps; in the first step, the photosensitive element was heated to 120° C. for 60 seconds using a hot plate. To do this, the sample was placed with its layer side on a hot plate and then covered with another plate. In a second step, the sample was brought into contact with an image-receiving element that had been previously soaked with water on its layer side. The set thus produced was then treated at 70° C. for 2 minutes as in the first stage. During this period, dye was transferred from the photosensitive element to the image receiving element. A magenta color original negative image was then obtained on the zero image receiving element with the two layer elements separated from each other.

Table 1 shows the development results obtained for samples 1 to 23.

(7--, from Table 1 it can be seen that the minimum density is very clearly modified by the compounds according to the invention. In addition, an activation effect can also be observed. Despite the reduction, both the maximum density and the photosensitivity are improved. In contrast, the comparison materials show little or no effect of reducing heat loss, or lack of e.g. the absence of solubilizing groups. Only in the compound 5t-6 according to the invention even a strong fog-increasing effect is shown, as when using the different compound C-2.

A photographic recording material was prepared in the same manner as in Example 1 using the following scraps: L Same as Ml in Example 1, but with an additional 0.5 g
Contains silver pensitriacylate of AgNOs.

1ζ N containing the following substance: 1.5g guanidine trichloroacetate, On
Convex 9ζ, A-noto-no-shi-A-)-1 Lorreno 1,000 Ru-1-
Phenyl-3-pyrazolidone, 0.008g Sodium sulfite, 0.5g Compound B, o, oag Compound C1 and 0.5g Gelatin.

``One'' Same as M3 in Example 1.

The photosensitive element thus produced is called sample 24 and is used as a comparison sample.

Another sample 25 was prepared in a similar manner, in which 5 t of the compound according to the invention was added at 1.7 g per mole of silver halide.
-6 was added to the silver halide emulsion in layer 1.

The two samples above were processed as in Example 1. The results are shown in Table 2.

Table 2 24” 2.07/2.221
) Comparative sample 2) Compound according to the invention This example again shows the very clearly strong fog-reducing effect of the compound according to the invention.

0.5g AgN0z (95.5 mol% AgBr14
Contains a blue-sensitized silver halide emulsion of 5 mol % AgI, average grain size 0.4 microns), containing 0.3 g of dye release agent and dye release agent D = (0,15, in diethyl laurylamide). emulsified into); 0
．． A layer containing 0.05 g of potassium bromide, 1 g of the polyester urethane of Example 1; and 1.58 g of gelatin.

Layers 2 and V3 are the same as layers and 3 of Example 2.

The photosensitive element made in this way is called sample 2G.
This will be used as a comparison sample.

Another sample 27 was made in the same manner, here A
1.7 g of the compound according to the invention 5t-f3 per mole of g N O3 were added to the silver halide emulsion in N1.

The two samples above were processed as in Example 1. A yellow original negative image was obtained. The results are shown in Table 3.

Inu 11 Takumi” - L 0.5g AgN0sC4mol%AgC1,8867
Mol%AgBr, 7.3mol%AgI, average particle size 0.3
Containing 6μl11) of red sensitized silver halide emulsion,
Dye release agent E at 0.168 Dye release agent E: υn (emulsified in diethyl lauryl 7-amide at 0, Oag), O
, OSg of potassium bromide, 1 g of the polyester urethane of Example 1, and 1.5 g of gelatin. N2 and 3 are the same as layered V3 of Example 2.

The photosensitive element thus produced is referred to as sample 28.
This will be used as a comparison sample.

Another sample 29 was made in the same manner, here Ag
l, 7 g of the compound according to the invention 5t- per 0.1 mole of N
6 was added to the silver halide emulsion in Nl.

Two samples were processed as described in Example 1.

A cyan original #image was obtained. The results are shown in Table 3.

As can be seen from Table 3, sample 27 of Example 3 shows both an improvement in Rrl and an improvement in photosensitivity, possibly due to the addition of the compound according to the invention, while sample 2 of Example 4
9 showed a significant improvement in fog, among other things.

Large MJIL The following layers were applied to the same support as in Example 1 as an image-receiving element.

L Mordant layer containing 3 g of compound F and 3 g of gelatin Compound F'': L Coating layer containing 0.5 g of gelatin and 0.35 tr of tumethylol urea, which also serves as a hardening layer.

Photosensitive samples 1.3.5 and 6 of Example 1 (Sample 1 being a comparative sample) were processed in the same manner as described in Example 1 with the image receiving element of Example 5. A magenta colored original copy was obtained. The results are shown in Table 4.

1-0.79/1,6
53 5t-61,70,18/2,275
5t-71,70,20/2.22L) Comparative sample 2) Compound according to the invention As can be seen from Table 4, the compound according to the invention was 0.5g
AgN0* (95 mol% AgBr, 5 mol% AgI
; a green-sensitized laminar silver halide agent with an average I11 aspect ratio of about 10 and an average grain size of 0.61 μm (specifying spheres of equivalent volume); 0.005 g of a metal compound according to the invention St 6;
0.3 g dye release agent A, 0.02. of potassium bromide:
A layer containing 1 g of the polyester urethane of Example 1 and 1.0 g of gelatin.

1.5g guanidine trichloroacetate; 0°03
51? of 4-methyl-4-hydroxymethyl-1-phenyl-3-biracisotone; o,oo 8 g of sodium sulfite; 0.3 g of compound B; 0.03 g of compound C and 1.8 g of gelatin.

1. Layer 3 is the same as layer 3 of Example 1.

This sample was treated as described in Example 1')i.

However, for the material in which the compound according to the invention was not added in layer 1, the relationship /D was 0.31/2. OII@In
IIaX 4 showed a significantly higher fog.

After storage of two untreated materials at room temperature, the increase in fog in the sample containing the compound 5t-26 according to the invention was less than half that in the sample without the addition of said compound.

or R+) reducing compound (in each case A g
Samples 3 with different amounts of NO (1.7 g per mole of Os)
Further samples 0-37 were made and processed in the same manner as described in Example 1. The results are shown in Table 5. When using the compounds according to the invention, a clear improvement in the white part of the image and, in some cases, an increase in the maximum color density was obtained.

show.

Person-”-305t-141,580,30/2.1231
5t-152,110,26/2.2432 5t
-162,010,1472,23335L-171,
600,17/1.9234 5t-180,80
0,21/1.3435 5t-191,830,
32/1.9136 5t-121,320,2
1/1.8237 5L-131,220,25
1,71) Relative photographic speed and (K1) Photosensitive elements of photographic recording materials for the diffusion transfer method were prepared by applying the following scraps to a transparent polyethylene terephthalate layer support. Based on.

L O, 5g AgN0* (4 mol% AgC1, 88 mol% AgBr, 7.3 mol% Agl; average particle size 0.3 μm
] containing a green sensitized silver halide emulsion, containing 0.3 g of dye release agent G Dye release agent G: N(CH)2
Item 1: M containing 0.05 g of potassium bromide v1 g of the polyester urethane of Example 1 and 1.5 g of gelatin.

2.0g guanidine trichloroacetate, 0°03
5g monomethyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, 0.5g compound B, 0.03g
of Compound C and 1.5 g of gelatin.

The same layer as layer 3 in Example 1.

The photosensitive element thus prepared is referred to as Sample 38 and serves as a comparative sample. Another sample 39 was prepared in a similar manner in which 6.8.
As shown in Table 6, sample 39 showed clearly lower fog values than sample 38 after processing, as shown in Table 6.

Person-”shi38 1.12
/1.9639 5t-80,25/1
．． 89 Tue 11'' - A transparent layer of polyethylene terephthalate A photosensitive element of a photographic recording material for the diffusion transfer method by applying the following layers to the support? Made by f4. All quantities are based on per square meter.

L 1 , OgA gN O3 (4 mol% AgC+,
Green-sensitized silver halide emulsion with 88.7 mol% AgBr, 7.3 mol% Agr; average grain size 0.3 μm),
0.3 g of dye release: fqH Dye release agent H: N(C)lco)2 0.05 g of odorous potassium w1 g of the polyester urethane of Example 1 and a layer containing 1.8 g of gelatin.

"Counterfeit" - 1.5g Guanidine trichloroacetate, 0.2
Contains 4g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, o, 06g sodium sulfite, 0.03g compound C1 and 1.5g gelatin.

Same scrap as layer 3 of Example 1.

The photosensitive element thus prepared is referred to as Sample 40 and serves as a comparative sample. Another sample 41 was prepared in a similar manner in which 6.8 g of compound 5t-6 according to the invention per 0.1 mole of AgN was added to the silver halide emulsion in layer 1. These samples were processed as described in Example 1. In this example, the empty process used is a positive process. In areas where silver is exposed and developed, no dye is released; in areas where silver is not developed, dye is released. In this case, therefore, the reducing effect of the compounds according to the invention on J') is reflected above all in an increase in the maximum density. Therefore, the density of the comparative sample was 1.58, whereas the maximum density when using the compound according to the present invention was 0.07.

Patent applicant Age7Adevert Akchendeserscha7),, -T-.

+1

Claims (1)

Claims: 1. At least one layer applied to the support and containing photosensitive silver halide, but essentially free of other inorganic silver salts and capable of releasing a diffusible dye as a result of development. one non-diffusible dye-providing compound and at least one binder layer containing a fog-reducing compound, the fog-reducing compound having the following formula ▲ mathematical formula, chemical formula, table, etc. ▼ I (where Q is represents the group necessary to complete the heterocyclic group containing at least one 5- or 6-membered heterocycle and, optionally, a ring fused thereto; X is a carboxylic or sulfonic acid group or in anionic form; A photographic recording material which can be developed by heat treatment, characterized in that it corresponds to a residue containing carboxylic acid or sulfonic acid groups (which may also be present in the molecule). 2. The fog-reducing compound has the following general formula II ▲Mathematical formulas, chemical formulas, tables, etc. ▼II (In the formula, Y is -O-, -S-, -Se- or -NR^
3-; R^1 and R^2 are the same or different and represent hydrogen, alkyl, alkenyl, cycloalkyl, aryl, phenyl, aralkyl, halogen, or R^1 and R^2 together A recording material according to claim 1, which represents a fused benzene ring; R^3 represents hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl. 3. The binder layer containing silver halide contains a fog-reducing compound of 0.001 to 10% per mole of silver halide.
．． Claim 1 or 2 containing in an amount of 0g
Recording materials listed in Section. 4. Claim No. 4, wherein the binder layer containing photosensitive silver halide contains a substantially non-photosensitive inorganic silver salt in an amount of at most 4 mol % based on the total amount of silver salt. Recording material according to item 1 or 2. 5. Claim 4 in which the binder layer containing a photosensitive silver salt does not substantially contain a non-photosensitive inorganic silver salt
Recording materials listed in section. 6. The recording material according to claim 1, wherein the binder layer containing photosensitive silver halide additionally contains a silver salt of an organic imino compound. 7. The recording material according to claim 6, wherein the organic imino compound is benzotriazole or a benzotriazole derivative. 8. Recording material according to claim 1 or 2, which contains as dye-supplying compound an oxidizable dye-supplying compound capable of releasing a diffusible dye as a result of oxidation. 9. Recording material according to claim 1 or 2, which contains as dye-supplying compound a reducible dye compound capable of releasing diffusivity as a result of reduction in combination with an electron-emitting compound. 10. consisting of three combinations of a photosensitive silver halide and a non-diffusible dye-providing compound capable of releasing a diffusible dye, the silver halide in each of the three combinations having a different spectral photosensitivity; and the dye-providing compound associated with the silver halide releases a dye whose absorption range corresponds in large part to the spectral sensitivity range of the associated silver halide. Recording materials listed in section.