DE2533137A1 - Colour photograph prodn. by high temp. development - using material contg. (co) poly-vinyl-pyrrolidone, giving improved graininess - Google Patents

Abstract

In the prodn. of a colour photograph by colour development of a photographic material with a base and Ag halide emulsion(s) at a temp. above 30 degrees C, a photographic material is used which contains a polymer (I) with recurring vinyl-pyrrolidone units in the Ag halide emulsion or an adjacent hydrophilic colloid layer. (I) can be a homopolymer or a copolymer with an addn.-polymerisable monomer. The graininess of the photograph is improved and the colour fogging reduced without redn. in the speed.

Description

Method of forming a color photographic image The invention relates to an image forming method, particularly to a method of forming a Color image with improved graininess; it relates in particular to a method to form a color photographic image by color not a photographic one Material having a support and at least one silver halide emulsion layer applied thereon at a temperature above about 30 ° C.

It is known that by color developing a photographic material a color image from dyes such as indoplenols, indamines, azomthines, phenoxazipene and the like, by coupling color couplers to the oxidation product one primary aromatic amine developing agent can be generated.

One of the important factors in evaluating the quality of color photographs is the graininess of a color image based on the conventional one described above Way has been generated. The graininess becomes serious especially then Problem when viewing an enlarged color image. There are therefore already various methods of improving graininess have been proposed. Included it was found that by using silver halide particles with a low Diameter necessary for the formation of dye particles of a correspondingly smaller one Lead diameter, the graininess can be significantly improved. This method however, it has the serious disadvantage that the sensitivity also decreases. According to the known method described in British Patent 923,045 was found to be through a double layer of two silver halide emulsion layers with different sensitivities, the graininess is significantly improved can be. However, this method is because of the increase in the number of to be applied Shifts very time consuming and labor intensive. In addition, this method has the Disadvantage that the amount of silver to be applied is significantly increased and that the thickness of the emulsion layers also increases. So one has been up for a long time the search for a new method to improve the graininess of color images, in which the undesirable side effects described above do not occur.

The aim of the present invention is to provide a method for improvement the graininess of color images, in particular to specify a method with which Help the graininess of color images can be improved without affecting the Sensitivity decreases. The aim of the invention is also to provide a method which allows the rapid generation of color images with improved graininess, without doing the Sensitivity decreases, and with the help of it the color haze can be reduced or suppressed.

It has now surprisingly been found that the graininess of color images can be improved by performing the color development treatment in a high temperature above about 3000 performs. This is particularly surprising because because it was previously assumed that the graininess of the color images was much more pronounced when the development is carried out at high temperature. In color development however, at a temperature above 3000, a color haze often occurs. It Many connections have already been proposed to prevent the occurrence of the Advertised to keep these links to a minimum, however not found satisfactory because they lead to the occurrence of other undesirable Side effects, such as reducing sensitivity, lead to development time extend the shelf life (shelf life) of the color images through binding on the finished dye images, and the like.

It has now been found that a sufficient reduction or prevention the appearance of the color haze without the aforementioned undesirable Side effects occur, can be achieved by being sensitive to light at least one polymer incorporated into photographic materials, vinylpyrrolidone contains as a recurring unit (repeating unit). This is particular surprising because it was previously assumed that home or copolymers of Vinyl pyrrolidone reduce the development effects and, consequently, the sensitivity reduce.

The invention relates to a method for producing a color photographic Image by color developing a photographic material with a support and at least one silver halide emulsion layer coated thereon in one temperature above about 3000, which is characterized in that it is a photographic Material used in or in the silver halide emulsion layer adjoining (neighboring) hydrophilic colloid layer at least one polymer with vinylpyrrolidone as a recurring unit.

For polymers which can be used according to the invention, the vinylpyrrolidone included as a recurring unit, include e.g. B.

Vinylpyrrolidone homopolymers and copolymers made from recurring Vinyl pyrrolidone units and other repeating units from other monomers, which are addition-polymerizable therewith, or hydrolyzed products thereof.

Addition polymerizable monomers that form the repeating Units in the copolymers containing recurring vinylpyrrolidone units can be used from the usual addition polymerizable vinyl monomers to be selected. Typical examples of suitable monomers include acrylic acid, Methacrylic acid, acrylic acid and methacrylic acid amides (e.g. acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, N-tert. -Butyl acrylamide, N-cyclohexyl acrylamide, diacetone acrylamide, N- (1,1-dimethyl-3-hydroxybutyl) acrylamide, N- (f-Morpholino) ethylacrylamide, N-benzylacrylamide, N-acryloylmorpholine, N-methacryloylmorpholine, N-methyl-N'-acryloylpiperazine, N-acryloylpiperidine, N-acryloylpyrrolidine, N -acryloylhexamethyleneimine and the like), acrylic acid and methacrylic acid alkyl esters (e.g. methyl methacrylate, Ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, cyclohexyl acrylate, 2-0thylhexyl acrylate, Decyl acrylate, ß-cyanoethyl acrylate, chloroethyl acrylate, 2-ethoxyethyl acrylate, sulfopropyl methacrylate and the like), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl lactate and the like), vinyl ethers (e.g. 3. methyl vinyl ether, butyl vinyl ether, Oleyl vinyl ether and the like), vinyl ketones (e.g. methyl vinyl ketone, ethyl vinyl ketone and the like), Styrenes (e.g.

Styrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, ethylstyrene, laurylstyrene, chlorostyrene, dichlorostyrene, methoxy styrene, cyanostyrene, dimethylaminostyrene, chloromethylstyrene, vinylbenzoic acid, styrenesulfonic acid, α-methylstyrene and the like), heterocyclic vinyl compounds (e.g. vinylpyridine) , Vinylpyrrolidone, vinylisoxazolidone, vinylimidazole and the like), acrylonitrile, vinyl chloride, ethylene, propylene, butadiene, isoprene, chloroprene, maleic anhydride, itaconic anhydride, citraconic anhydride, vinylsulfonic acid and the like. Suitable repeating units which may be contained in these copolymers include units of the following formulas: where: R1 denotes a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g. a methyl, ethyl, PTOSY1, isopropyl, n-butyl, sec.-butyl, t-butyl, pentyl group and the like), a hydroxyalkyl group with 1 to 5 carbon atoms in its alkyl radical (e.g. a hydroxyethyl, hydroxypropyl, hydroxybutyl, ffydroxypentyl group and the like) or an alkoxyalkyl group with 1 to 5 carbon atoms in its alkyl radical and 1 to 2 carbon atoms in its alkoxy radical (e.g. ethoxyethyl, ethoxypropyl, methoxybutyl and the like); R2 is a hydrogen atom, an alkyl group with 1 to 8 carbon atoms (e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, Hexyl <, heptyl, octyl group and the like), a hydroxyalkyl group with 1 to 8 carbon atoms in its alkyl radical (e.g.

B. a hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl group and the like) or an alkoxyalkyl group having 1 to 8 carbon atoms in their Alkyl radical and 1 to 2 carbon atoms in its alkoxy radical (e.g. a methoxyethyl, Xthoxypropyl, methoxybutyl group and the like); and R3 is a hydrogen atom or a methyl group.

Particularly preferred copolymers are those used as recurring Unit each one of the repeating units specified above (A), (B), (C) and (D) included. That contained in the copolymers given above Vinyl pyrrolidone is effective when it is in an amount greater than about 20 moles is preferably present in an amount within the range of 50 to 100 mole percent. Specific examples of copolymers containing vinylpyrrolidone units are the following: (1) polyvinylpyrrolidone, (2) vinylpyrolidone / acrylic acid (monomer ratio 1: 1) copolymer, (3) vinyl pyyrolidone / methacrylic acid (1: 1) copolymer, (4) vinylpyrrolidone / acrylamide (7: 3) copolymer, (5) vinylpyrrolidone / N-thylacrylamide (3/2) copolymer, (6) vinylpyrrolidone / N-acryloylmorpholine (2/3) -1 copolymer, (7) vinylpyrrolidone / N-acryloylpiperidine (2/3) copolymer, (8) vinyl pyrrolidone / N, N-diethylacrylamide (1/1) copolymer, (9) vinyl pyrrolidone / diacetone acrylamide (1/1) copolymer, (10) vinylpyrrolidone / methgacrylaX7 / 3; copolymer, (11) Vinylpyrrolidone / butyl acrylate (7/3) mixture;, polymer, (12) yinylpyrrolidone / 2-ethylhexyl acrylate (7/3) copolymer, (13) vinylpyrrolidone / 2- (N-acetyl) aminoethyl acrylate (3/2) copolymer, (14) vinylpyrrolidone / vinyl acetate (4/1) copolymer, (15) vinyl pyrrolidone / vinyl acetate (1/1) copolymer, (16) vinyl pyrrolidone / vinyl alcohol (7/3) copolymer, (17) vinylpyrrolidone / styrene (7/3) copolymer, (18) vinylpyrrolidone / N-vinylmethylimidazole (3/2) copolymer, (19) vinylpyrrolidone / maleic acid (3/2) copolymer, (20) vinylpyrrolidone / acrylamide / hydroxyethyl acrylate (5/5/2) copolymer.

The polymers containing vinylpyrrolidone units are preferred hydrophilic. Suitable polymers have a molecular weight within the range from about 10,000 to about 500,000, preferably from 20,000 to 200,000 because Polymers with a molecular weight that is too low cause the color haze to appear to a lesser extent, while polymers with too high a molecular weight are difficult to mix with gelatine.

Although the amount of the polymer containing vinylpyrrolidone units, which can be used effectively is not subject to any special restrictions, in most cases the polymer containing vinylpyrrolidone units preferably in an amount within the range from about 0.5 to about 40% by weight, based on the total weight of the layer in which the polymer is used incorporated binder. A particularly preferred amount is within of the range from 0.1 to 30 total%.

The polymer used according to the invention can be produced by processes as described, for example, in U.S. Patents 2,335,454; 3,052,544,3 479 186, 3,655,389, 3,730,726, and the like. The vinyl pyrrolidone units containing polymers which can be used according to the invention can be one Silver halide emulsion layer or one to the silver halide emulsion layer adjoining (neighboring) hydrophilic colloid layer, for example an intermediate layer, a filter layer, a protective layer and the like can be added.

The photographic materials used in the practice of the invention can be selected from various commonly used Materials prepared in a conventional manner The silver halide emulsions, which can be used according to the invention can usually by mixing a Solution of a water-soluble silver salt (e.g. silver nitrate) and a solution of a water-soluble halide in the presence of a solution of a water-soluble one macromolecular material such as gelatin. To silver halides, which can be prepared in the manner described above include e.g. B.

Silver chloride, silver bromide and mixed silver halides such as silver chloride bromide, Silver iodide bromide, silver chloride iodide bromide and the like. The crystal form of the Silver halide grains are preferably cubic, octahedral, one mixture thereof or the like. The silver halide grains can be prepared using known, conventional processes. On suitable methods of manufacture of the silver halide grains include the so-called single jet method, the double jet method and the controlled double jet process. In addition, if desired two or more silver halide photographic emulsions prepared separately have been mixed together. The crystal structure of the silver halide grains can be homogeneous, they can have a structure in which the inner and the outer layer are different from one another, in particular a layer-like structure have, or it can be the so-called silver halide grains from Conversion type act as described in British Patent 635 841 and in US Pat U.S. Patent 3,622,318. You can also use it as a photographic Emulsions those which have latent images on the surface of the silver halide grains form, or those which form latent images inside the silver halide grains, be used. These photographic emulsions are described, for example, by C. B. K. Mees and T. H. James in "The Theory of the Photographie Process", Macrnillan Co., New York (1966), and by P. Glafkides in "Chimie Photographique", Paul Mantel, Paris (195?), And they can be produced by a wide variety of processes are, for example, according to the known ammonia process, the neutral process, the acid method and the like.

After preparing the above-described silver halide particles the reaction system can be washed with water to produce water-soluble salts that formed as a by-product (such as potassium nitrate, which is formed when Silver bromide made from silver nitrate and potassium bromide), remove and it can then be counteracted by chemical sensitizers, such as sodium thiosulphate, N, N, N'-trimethylthiourea, a thiocyanate complex of inenovalent gold, one Thiosulfate complex of monovalent gold, tin (II) chloride, hexamethylenetetramine and the like are heated to increase sensitivity without the silver halide grains to coarsen. These general procedures are also used by Mees and James, ibid. and Glafkides, ibid. bez written.

The silver halide photographic emulsions can be based on conventional ones Way to be chemically sensitized. On suitable examples of chemical sensitizers include gold compounds such as chloraurate, gold (III) trichloride and the like, such as described in U.S. Patents 2,399,083, 2,540,085, 2,597,856, and 2,597,915; Salts of precious metals such as platinum, palladium, iridium, rhodium and ruthenium such as in U.S. Petitions 2,448,060, 2,540,086, 2,566,245, 2,566,263 and 2,598,097 described, sulfur compounds that react with A-silver salts to form of silver sulfide, as in U.S. Patents 1,574,944, 2,410,6898 3,189,458, 3,501,313 and the like, stannous salts as in U.S. Patents 2 487 850, 2 518 698, 2 521 925, 2 521 926, 2 694 637, 2,983 610 and 3 201 254 described, and amines and other reducing materials. The photographic emulsions. can with cyanine dyes, such as cyanine, merocyanine, carbocyanine and the like either individually or in combination or in combination with styryl dyes spectrally sensitized or supersensitized These dye sensitization methods are known and described, for example, in US Patents 2,493,748, 2 519 001, 2 977 229, 3 480 434, 3 672 897, 3 703 377, 2 688 545, 2 912 329, 3 397 060, 3,615,635 and 3,628,964, in British patents 1,195,302, 1,242 588 and -1 293 862, in German Offenlegungsschriften 2 030 326 and 2 121 780, in Japanese Patent Publication No.

4,936/68, 14 030/69 and 10 773/68, in U.S. Patent No. 3,511 664, 3 522 052, 3 527 641, 3 615 613, 3 615 632, 3 617 295, 3 635 721 and 3 694 217, in British Patents 1 137 580 and 1 216 203 and the same. A sensitization method useful in the present invention can be appropriately selected from those described above depending on of the wavelength range to be sensitized, the desired sensitivity and the purpose and end use of the sensitive materials.

To prevent a decrease in sensitivity and occurrence fogging during production, storage or treatment (development) the materials according to the invention can contain various compounds according to the invention useful photographic emulsions can be added. They are very different Compounds known that are suitable as such additives. Examples of typical Compounds are 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole and many other heteroeyelic compounds, mercury containing compounds, metal salts and the like. Suitable compounds that can be used are described, for example, by 0. E. K. Mees and T. H. James in "i'he Theory of the Photographie Process", ibid., 3rd edition, 1966, times 344-349, and in the original literature cited therein and in US patent documents 1 758 576, 2 110 178, 2 131 038, 2 173 628, 2 697 040, 2 304 962, 2 324 123, 2 394 198, 2 444 605, 2 444 606, 2 444 607, 2 444 608, 2 566 245, 2 694 716, 2 697 099, 2 708 162, 2 728 663, 2 728 664, 2 728 665, 2 476 536, 2 824 001, 2 843 491, 2 886 437, 3 052 544, 3 137 577, 3 220 839, 3 226 231, 3 236 652, 3 251 691, 3 252 799, 3,287,135, 3,326,681, 3,420,668 and 3,622,339, in British Patents 893,428, 403,789, 1,173,609 and 1,200,188 and the like.

Appropriate hydrophilic colloids that are effective in the silver halide emulsion layers or hydrophilic colloid layers of the present invention Can be incorporated include cellulose derivatives such as gelatin, colloidal Albumin, Casein, carboxymethyl cellulose, hydroxyethyl cellulose and the like, saccharides such as agar, sodium alginate, starch derivatives and the like, synthetic hydrophilic colloids, such as polyvinyl alcohol, poly-N-vinylpyrrolidone, Acrylic acid copolymers, polyacrylamide, the derivatives and partially hydrolyzed Products thereof and the like. If desired, a combination of two or more of these colloids which are compatible with one another can be used. The most commonly used hydrophilic colloid is gelatin, however, some or all of the gelatin can be obtained by synthetic polymeric compounds be replaced. In addition, the so-called gelatin derivatives can namely Gelatin derivatives in which the functional groups of gelatin, such as. B. the Amino, imino, hydroxyl and carboxyl groups, with compounds that are at least contain a functional group associated with any of the above functional Groups of gelatin can react, be reacted, and grafted gelatins, in which the above-mentioned functional groups of gelatin through the polymer chains other polymeric compounds are substituted. To suitable Compounds for the preparation of the derivatives described above include e.g. B. Isocyanates, acid chlorides and acid anhydrides, as in U.S. Patent 2,614 928, acid anhydrides as described in U.S. Patent 3,118,766, Bromoacetic acids as described in Japanese Patent Publication No. 5,514/64, Phenyl glycidyl ether as described in Japanese Patent Publication No. 26845/67, Vinyl sulfone compounds as described in US Pat. No. 3,132,945, N-aryl vinyl sulfonamides, as described in British patent specification 861 414, maleimide compounds, as described in US Pat. No. 3,186,846, aeryl nitriles as in US Pat 2,594,293, polyalkylene oxides as described in U.S. Patent 3,312,553, Epoxy compounds as described in Japanese Patent Publication No. 26 845/67, Esters of acids as described in U.S. Patent 2,763,639 Alkane Sultones 1 as described in British Patent 1,033,189 and the like. Polymers Compounds that can be graft polymerized with gelatin are, for example in U.S. Patents 2,763,625, 2,831,767 and 2,956,884 and in Polymer Leiters ", , 595 (1967), Phot. May be. Eng. ", 9, 148 (1965) and" J. Polymer Sci. ", A-1, 9, 3199 (1971) written. As grafted polymeric compounds as indicated above A wide variety of vinyl polymers or copolymers can be used with advantage of acrylic acid, methacrylic acid, derivatives thereof such as ester. Amide and nitrile derivatives thereof, and other common vinyl monomers such as styrene can be used. As grafted polymer compounds are particularly suitable are hydrophilic vinyl polymers, the are compatible with gelatin to a certain extent, e.g. B. Home or Copolymers of acrylamide, methacrylamide, hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates.

The binders used in the layers of photographic materials can be included, can be hardened by adding hardeners. Typical Examples of hardeners that can be used are ßlaehydverbindungen such as formaldehyde, glutaraldehyde and the like, ketone compounds such as diacetyl1 cyclopentanedione and the like, Bis- (2-chloroethefiurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, reactive Halogen containing compounds as in U.S. Patents 3,288,775 and 2,732 303 and in British Patents 974 723 and 1,167,207, active Olefin-containing compounds such as divinol sulfone. 5-acetyl-1,3-diacrylovlhexahydro-1,3,5-triazine, and such as disclosed in U.S. Patents 3,635,718 and 3,232,763 and in US Pat British patent specification 994 869 are described, N-hydroxymethylphthalimide, N-methylol compounds, as described in U.S. Patents 2,732,316 and 2,586,168, isocyanates such as in US Pat. No. 3,103,437, aziridine as in US Patents 3,017,280 and 2,983,611, acid derivatives as described in U.S. Patents 2 725 294 and 2 725 295 described, Carbodiimide compounds such as in U.S. Patent 3,100,70 '+, epoxy compounds as in U.S. Patent 3,091,537, isoxazole compounds as described in U.S. Patents 3,321 313 and 3 543 292 described, halocarboxyaldehydes, such as mucochloric acid, dioxane derivatives, such as dihydroxydioxane and diehlordioxane; inorganic hardeners such as ear alum and zirconium sulfate and the like Instead of the hardeners mentioned above, precursors of the materials mentioned above, for example the addition compounds from a Alkali metal bisulfite and an aldehyde, the methylol derivatives of hydantoin and primary aliphatic nitro alcohols can be used.

The layers of the photographic materials used according to the invention surfactants can be added singly or in the form of a mixture thereof will. These surfactants are not only used as coating aids, but in some cases also as an emulsifier, dispersing aid, for sensitization, to improve the photographic properties, to achieve antistatic Effects and used to prevent adhesion. Suitable examples of surfactants include natural surfactants, such as saponin, nonionic surfactants such as alkylene oxide surfactants, surface-active glycerin compounds or surface-active glycidol compounds, cationic surfactants, such as higher alkylamines, tertiary ammonium salts, Pyridine and other heterocyclic compounds as well as phosphonium or sulfonium compounds, anionic surfactants containing acidic groups, e.g. B. a carboxylic acid group, contain a sulfonic acid ester group, a phosphoric acid ester group and the like, and ampholytic surfactants such as amino acids, aminosulfonic acids, the sulfate esters or phosphate esters of amino alcohols and the like. Suitable Examples of surface-active agents that can be used according to the invention, are for example in the U.S. Patents 2,271,623; 2,240 472, 2 288 226, 2 739 891, 3 068 101, 3 158 484, 3 201 253, 3 210 191, 3 294 540, 3415649, 3441 413, 3442654, 3475174 and 3 545 974, in the German Offenlegungsschrift 1,942,665 in British Patents 1,077,317 and 1,198,450 to Ryohei Oda et al.

in "Synthesis and Applications of Surface Active Agents", Maki Shoten (1964) by A. M. Schwartz et al. In "Surface Active Agents", Interscience Publications Incorporated, (1958) by J. P. Sisley et al. in "Encyclopedia of Surface active Agents't, Volume 2, Chemical Publishing Company, (1964), and the like.

The silver halide emulsion layers or those adjacent to them (adjacent) hydrophilic collective layers in the photographic images used according to the invention Materials can contain color couplers. These color couplers are to compounds produced when coupling with the oxidation products of primary aromatic Amine developing agents form dyes, and there is already a large number known of compounds which are suitable as color couplers. It can be tetravalent and divalent color couplers can be used. For suitable compounds that are listed in The photographic materials that can be incorporated include couplers, the contain a so-called ballast group, each containing more than about 8 carbon atoms included in the ballast group so that the coupler during manufacture or Treatment or development does not diffuse into other layers or the couplers do not diffuse even during manufacture or processing. A suitable one The amount of color coupler that can be incorporated into the emulsion layer is within of the range from about 5 x 10 5 to about 5 x 10 3, preferably from 2 x 10-4 to 2 x 10 3 mol / m2.

Examples of suitable, a yellow color-forming couplers (yellow color couplers) are open-chain ketomethylene compounds, such as. B. the Benzoylaeetoanilide and Pivaloylacetoanilide. Specific examples of suitable yellow driving couplers are for example in US Patents 3,341,331, 2,875,057 and 3,551,155, in German Offenlegungsschrift 1,547,868, in US Patents 3,265,506, 3,582,322 and 3,725,072, in German Offenlegungsschrift 2,162,899, U.S. Patents 3,369,895 and 3,408,194 and German Offenlegungsschriften 2,057,941, 2,213,461, 2,219,917, 2,261,361 and 1,263,875. Typical examples of suitable yellow couplers that can be used include the following couplers: 5-pyrazolone compounds are mainly used as magenta color couplers, but indazolone and cyanoacetyl compounds can also be used. Specific examples of such couplers are for example in U.S. Patents 2,439,098, 2,600,88, 3,062,653 and 3,558,319, British Patent 956,261, U.S. Patents 3,582,322, 3,615,506 , 3,519,429, 3,311,476, and 3,419,391, in Japanese Patent Application Nos. 21 454/73 and 56 050/73, in German Offenlegungsschrift 1,810,464, in Japanese Patent Publication No. 2,016/69, in US Pat Japanese Patent Application No. 45,971/73 and U.S. Patent No. 2,983,608. Typical examples of suitable magenta couplers that can be used include the following couplers: Phenols and naphthols are mainly used as cyan color couplers. Specific examples of suitable cyan couplers that can be used are, for example, in U.S. Patents 2,369,929, 2,474,293, 2,698,794, 2,815,826, 3,311,476, 3,458,315, 3,560,212, 3,582,322, 3,591,383, 3,386,301, 2,434,272, 2,706,684, 3,034,892 and 3,583,971, in German Offenlegungsschrift No. 2 163 811, in Japanese Patent Publication No. 28836/70, in Japanese Patent Application No. 33 238/73 and the like. Typical examples include the following compounds: When carrying out the coupling reaction, development inhibitor-releasing couplers (so-called DIR couplers) and compounds capable of releasing compounds having a development-inhibiting effect can also be added to the photographic materials according to the invention. Specific examples of the above-mentioned development inhibitor releasing compounds can be found, for example, in US Pat. in U.S. Patents 3,297,445, 3,379,529, and 3,639,417, and the like. One or more of the above-mentioned color couplers and the like can be added to the same layer, or the same coupler as described above can also be added to two or more different layers. The color couplers can be incorporated into the photographic materials in a conventional manner. A typical method is to dissolve the couplers in an organic solvent and disperse the resulting solution in an aqueous hydrophilic colloid solution (which may contain silver halide grains). Three classes of organic solvents can be used to dissolve the couplers: those solvents which are difficult to mix with water and have high boiling points (greater than about 20,000), those solvents which are difficult to mix with water and have low boiling points, and those Solvents that are miscible with water. These solvents can be used singly or in combination thereof. Examples of organic solvents which are difficult to mix with water and which have high boiling points are di-n-butyl phthalate, dibenzyl phthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl mono-p-tert. butylphenyl phosphate, mono-phenyl-di-o-chlorophenyl phosphate, monobutyl dioctyl phosphate, 2,4-di-tert-amylphenol, 2,4-di-n-amylphenol, 4-n-nonylphenol, 2-methyl-4-n-octylphenol , N, N-diethylcaprylamide, N, N-diethyllaurylamide, and the like. Examples of organic solvents which are difficult to mix with water and have low boiling points are methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, butyl formate, nitromethane, chloroform, cyclohexane and the like. Examples of organic solvents which are miscible with water are methyl isobutyl ketone, ß-ethoxyethyl acetate, diethylene glycol monoacetate, diethylene glycol monomethyl ether, ethylene glycol, acetone, methanol, ethanol, acetonitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, isocyanate: -.

Specific examples of methods for incorporating the couplers into Photographic materials are described, for example, in U.S. Patents 2,304 939, 2,322,027, 2,801,170, 2,801,171, and 2,949,360, and the like. In the silver halide emulsion layers or in other layers, latex-like, water-dispersible vinyl polymers, in particular compounds which the Improve dimensional stability (.Mabhaltif, ^ keit) of photographic materials can, individually or in the form of a combination of different vinyl polymers or in the form of a combination of the above-mentioned compounds and one hydrophilic, water-permeable colloid can be incorporated. examples for suitable polymers for incorporation into silver halide emulsion layers or in other layers are for example in US Patents 2,376,005, 2 739 1578, 2 853 475, 3 062 674, 3 411 911, 3 488 708, 3 525 620, 3 635 715, 3 607 290 and 3,645,740, in British Patent Nos. 186,699 and 1,307,373. Suitable poly merisate, as described in the above-mentioned patents: 3 are generally homopolymers or copolymers of monomers, such as alkyl acrylates, Alkyl methacrylates, acrylic acid, methacrylic acid, sulfoalkyl acrylates, sulfoalkyl methacrylates, Glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, Alkoxyalkylacryla th, alkoxyalkyl methacrylates, styrene, butadiene, vinyl chloride.

Vinylidene chloride, maleic anhydride and itaconic anhydride depending on Depending on the circumstances, a so-called emulsion-polymerized latex of the graft type, that by polymerizing the aforementioned vinyl monomer emulsion in the presence made of hydrophilic protective colloid materials with a high molecular weight has been used. In the silver halide emulsion layers or in others Layers of the photographic materials which can be used according to the invention can also be used so-called matting agents are incorporated Examples of suitable matting agents are finely divided particles of water-soluble organic or inorganic compounds with an average diameter of 0.2 to 10, preferably 0.5 to 5 / u. Specific Examples of organic compounds that are used with advantage as matting agents are water-dispersible vinyl polymers, such as polymethyl methacrylate, Polymethyl acrylate, polyacrylonitrile, acrylonitrile / W - '. Ethyl styrene copolymers, Polystyrene, styrene / divinylbenzene copolymers, polyvinyl acetate, polytetrafluoroethylene and the like, cellulose derivatives, such as methyl cellulose, ethyl cellulose, cellulose acetate, Cellulose acetate propionate and the like, starch and starch derivatives such as carboxy starch, Carboxynitrophenyl starch, the reaction products of urea, formaldehyde and starch and the like, gelatin hardened by known hardeners and hardened types of gelatin, by. Hardening woacervates have been made from hollow gelatin capsules are. Examples of inorganic compounds suitable as matting agents are Silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, marijuana sulfate, calcium carbonate, desensitized silver chloride, desensitized silver bromide, glass and the like. The aforementioned matting agents can be used individually or in the form of a mixture be used.

The photographic layers, for example the silver halide emulsion layers, the hydrophilic collol roof sealers and the like, are in the form of a layer on an im essentially flat material (carrier) applied, which (the) no significant noticeable change in size during treatment or development subject. Examples of suitable supports include rigid supports such as these made of glass, metal or ceramic, or flexible supports, depending on the end use. Typical examples of flexible supports are cellulose nitrate films, cellulose acetate films, Cellulose acetate butyrate, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, Polycarbonate films, laminates of these pilms, thin sheets of glass, paper and the like. Examples of other suitable supports are barite-coated papers, papers, on the polymers of α-olefins, in particular those with 2 to 10 carbon atoms, such as polyethylene, Pclye propylene, ethylene / butene-Mis <hpolymerisate and the like> have been applied or laminated in the form of a layer, or synthetic resin films, the surfaces of which have been matted to ensure adhesion to other polymeric materials and to improve printability as disclosed in Japanese Patent Publication No. 19 068/72 described, with which good results are also obtained. One suitable silver halide coating amount can be within the range of about 5 x 10 5 to about 10 1 mol / n2 carrier.

The type of carrier used, whether it is transparent or opaque (opaque) depends on the use of the photographic material. Furthermore can not only colorless transparent carriers, but also colored transparent ones Supports colored by adding dyes or pigments are used will. The dyeing of the support is used, for example, for X-ray films and is described in "J. Si4PTE",, 296, (1958). Too opaque (opaque) Carriers that can be used effectively are inherently opaque Carriers, such as paper, transparent films, which by adding dyes or pigments, such as titanium oxide, have been made opaque, synthetic resin films, their surfaces according to a procedure have been treated like it for example in Japanese Patent Publication No. 19 068/72, papers and Synthetic resin films completely block out the light by adding carbon black, dyes and the like shield, and the like.

In the case of insufficient adhesion of a support to a photographic Emulsion layer can have an adhesive layer (Substriero layer), which both on the carrier as well as adhering to the photographic layer or the surface of the carrier can be caused by a corona discharge, by irradiation with UV light flame treatment and the like.

In the production of the light-sensitive ones which can be used according to the invention Photographic materials can employ any photographic layer the most varied of coating processes, for example by dip coating, Buft knife coating, curtain coating, spray coating, extrusion coating using a funnel as described in U.S. Patent 2,681,294 and the like can be applied, if desired, two or more layers can be applied simultaneously using methods such as in U.S. Patents 2,761,791, 3,508,947 and 837,095.

The photographic light-sensitive materials used in the present invention can be used have one or more silver halide emulsion layers on a support on.

Color photographic light-sensitive materials usually contain a blue-sensitive silver halide emulsion layer; a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. The silver halide emulsion layer can be in two or more layers facing practically the same spectral range are sensitive to be split. The photosensitive ones used in the present invention Photographic materials can be used in addition to the silver halide emulsion layers opposite light im contain essential insensitive layers, such as B.

conventional layers, such as a surface protective layer, a Filter layer, an intermediate layer, an antihalation layer, a barrier layer, an anti-curling layer, a backing layer and the like the imagewise exposure become the photographic ones used in the present invention Materials at a temperature of about 3000 or higher color development subjected to forming a color image. Suitable temperatures for color development can generally be within the range of up to about 6500; it can but temperatures below 6500 can also be used. When developing can known color developer solutions and other treatment solutions can be used.

Suitable color developer solutions are alkaline solutions, the color developer compounds contain. As the color developing agent, known aromatic primary amine developing agents can be used be used. Suitable aromatic primary amines to be incorporated in a color developer solution can be incorporated are p-phenylenediamine derivatives. Typical p-PheQylenediamine derivatives are z. B. N, N-diethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-Amino-5 (N-ethyl-N-laurylamino) toluene, 4 [N-ethyl-N (ß-hydroxyethyl) -aminoj anlin sulfate, 2-methyl-4- [N-ethyl-N- (ß-hydroxythf1) -amino] aniline sulfate, N-ethyl-N (ß-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sesquisulfate monohydrate, as described in US Pat. No. 2,193,015, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide sulfate, as described in VS Patent 2,592,364, N, N-dimethyl-p-phenylenediamine hydrochloride and the same. These color developing compounds are in "Kagaku Shashin Binran (Manual of Scientific Photography ", Volume 2, Page 72, Maruzen Publisher, Tokyo (1959), and in L. F. A. Mason, Photographic Processing Chemistry, "pp. 22b-229, Focal Press, London (1966). Autver the above aromatic primary Amine compounds the color developer solutions can still usual additives, such as. B. alkali metal sulfites, carbonates, bisulfites, bromides, iodides, alkaline buffering agents and the like. The color developer solutions If desired, color couplers that form a dye, competing couplers, Antifoggants, hardeners, anti-oxidants, agents for increasing viscosity and the like, may be added. Put an appropriate amount of the color coupler in the Developer solutions can be within the range of about 0.2 to about 50, preferably from 0.5 to 10 g per liter of developer.

To alkaline agents and buffers, which are suitable for treatment or treatment. Developer solutions suitable and can be used according to the invention include sodium hydroxide, Potassium hydroxide, sodium carbonate, potassium carbonate, sodium or potassium tert-phosphate, Potassium metaborate, borax and the like. These lWats can be used individually or can be used in the form of combinations. In addition, disodium or dipotassium hydrogen phosphate, Potassium or sodium dihydrogen phosphate, sodium or potassium bicarbonate, boric acid, Alkali metal nitrates, alkali metal sulfates and other salts for buffering the treatment or. Developer solutions are used. Specific examples of antifoggants, which can be used according to the invention are alkali metal bromides, ammonium bromide and the same. In addition, inorganic halides, such as potassium iodide or sodium iodide, and known organic antifoggants can be used to advantage. Specific Examples of organic antifoggants used in the present invention can are heterocyclic compounds, such as. B. 6-nitrobenzimidazole, as in in U.S. Patent 2,496,940, 5-nitrobenzimidazole as described in U.S. Patents 2,497,917 and 2,656,271, diaminophenazine and o-phenylenediamine, as described in "Nippon Shashin Gakkai Kaishi (Journal of the Japanese Photographic Society) 11, Volume 11, page 4.3 (1948), described, Mercaptobenzimidazol, Methylben30tlliazol, Mercaptobenzoxazole, Thiouracil, 5-t-ethylbenzotriazole, compounds as described in Japanese Patent Publication No.

41 675/71, and the like. Make these connections However, these are only examples and besides that, numerous compounds of which are known is that they are effective antifoggants used according to the invention will. Some of the antifoggants described above are also in "Kagaku Shashin Binran (Manual of Scieritific Photography) ", Volume 2, Page 119, Maruzen Publisher, Tokyo, (1959). To regulate surface development can also use development limiters as described in Japanese patent publications Nos. 19 030/71 and 6 149/70, described in U.S. Patent 3,295,976, and the like are to be used. In addition, if desired, the treatment or Developer solutions ammonium chloride, potassium chloride, sodium chloride and the like, be admitted.

To development accelerators that ZV-given the developer solutions can include various types of pyridinium compounds and others cationic compounds, ionic dyes such as phenosafranin, neutral salts, such as thallium nitrate and potassium nitrate, such as those described in U.S. Patent 2,648,604, Japanese Patent Publication No. 9 503/69 and U.S. Patent 3 671 247 are described, polyethylene glycol or derivatives thereof and directionally ionic Compounds such as polythioethers such as those described in Japanese Patent Publication No. 9,504/69 and in U.S. Patents 2,533,990, 2,531,832, 2,950 9/0 and 2 577 127 are described, organic solvents and organic amines, such as ethanolamine, Ethylenediamine, diethanolamine and the like, as described in Japanese Patent Publication No. 9 509/69 and in Belgian patent 682 862, and the like. In addition, suitable development accelerators also include those as described by L.

F. A. Mason in Photographic Processing 5hemistry ", pages 40 to 43, Focal Press, London (1966).

Other effective development accelerators are benzyl alcohol and phenylethyl alcohol, as described in US Pat. No. 2,515,147, and pyridine, ammonia, hydrazine, Amines and the like as described in "Nippon Shashin Gakkaishi (Journal of the Japanese Photographic Society) ", Volume 14, page 74, (1952). Furthermore, Hydroxylamine sulfate, hydroxylamine, hydrochloride, sodium sulfite, potassium sulfite, potassium bisulfite and sodium bisulfite are added to the processing and developer solutions, respectively.

In addition, polyphosphate compounds can be used as water softeners, such as B. sodium hexamet-aphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate or the potassium salts of any of the aforementioned polyphosphoric acids and aminopolycarboxylic acids uranium, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, Iminodiacetic acid, N-hydroxymethylethylenediamine triacetic acid, diethylenetriamine pentaacetic acid and the like can be used. The amount of the above water softener used depends on the hardness of the water, but an effective amount will be in most Cases within the range of about 0.5 to about 1 gram per liter of water. aside from that can the photographic processing or developer solutions also calcium and Magnesium sequestrant can be added. These funds are provided by J. Willens in Belgische Chemische Industrie ", 21, 325 (1956), and ibid., 23, 1105 (1958), in more detail described.

The photographic processing or developer solutions can, if desired Organic solvents can also be incorporated to increase the solubility of the components the developer solution, in particular the developer compounds, to increase.

Examples of suitable organic solvents that can be used for this purpose can be used are ethylene glycol, hexylene glycol, diethylene glycol, methyl cellosolve, Methanol, ethanol, acetone, triethylene glycol, dimethylformamide, dimethyl sulfoxide and those in Japanese Patent Publication No. 33378/72 and 9 509/69 described compounds. The Uienge used of the above organic solvent can vary widely depending on the present pn Components, but a sufficient amount is usually one concentration within the range up to about 50 wt.%, in most cases up to about 10% by weight. In some cases, treatment or development solutions can also be used that contain solvents that are almost free of water.

Examples of suitable competing couplers are citrazinic acid, J-acid, H-acid and those disclosed in Japanese Patent Publication No. 9 505/69, 9 506/69, 9 507/69, 14 036/70 and 9 508/69 and in U.S. Patents 2,742,832, 3,520,69D, 3,560,212, and 3,645,737 and the like. examples for suitable antifoggants are alkali metal borohydrides, aminoboranes, ethylers, diamine, those described in Japanese Patent Publication No. 38816/72, and the same. Examples of compensation developers are p-aminophenol, benzyl-p-aminophenol, 1-phenyl-3-pyrazolidone and those described in Japanese patent publications Nos. 41 475/70, 19 037/71 and 1943/71, and the like. The usual way The amount of these compensating developers used is within the range of about 0.01 to about 1.0 g / l. Typical examples of work development solutions that consist of The various components described above are in "Kagaku Shashin Binran (Manual of Scientific Photography) ", page 72, IvIaruzen, Tokyo (1959), described.

Among the so-called dispersible color couplers, those of a developer solution may be added include the cyan couplers such as those shown in, for example U.S. Patents 3,002,836 and 3,542,552, the Purpurrottu1ypleer, as described, for example, in Japanese Patent Publication No. 13111/69 are, and the YellowPupplers, like see them, for example, in US patent specification 3 51Q 306 are described. Before color development, one treatment can be carried out in one a hardener containing before bath can be carried out.

The various treatments after color development can be applied to be carried out in the usual way.

According to one embodiment of the invention, color images with a improved graininess. According to another embodiment of the invention wiser. the resulting color images are excellent photographic ones Own.

properties and obfuscation properties. In addition, will through the present invention shortens the development time.

The invention is illustrated in more detail by the following examples, but without being limited to it. The parts, percentages, Unless otherwise stated, ratios and the like refer to the weight.

Example 1 For 1000 g of a highly sensitive negative photographic emulsion, the 6.5 g of silver iodobromide (silver iodide content 6.0 mol%) and 10 g of gelatin Containing 100 g of emulsion, 200 ml of a 0.3% methanolic solution of the VerZ connection (1) as an optical sensitizer, 20 ml of a 1 own.

aqueous solution of 5-methyl-7-hydroxy-1,3,4-triazaindolizine 450 g a cyan coupler emulsion prepared according to that described below Emulsion (A), and 50 ml of a 2% strength aqueous solution of the sodium salt of 2-HydroxJr-4,6-dichloro-s-triazine added as a gelatin hardener.

Connection (1) Emulsion (A) 3 (1) gelatin (10% aqueous solution) 1000 ml (2) ethyl acetate 110 ml blue-green knockers (compound 2)) 80 g sodium p-dodecylbenzenesulfonate 5 g sorbitan monolaurate (20% methanolic solution) 30 ml tricresyl phosphate 65 ml compound (2) After the compounds listed in (2) above were mixed and dissolved at a temperature of 6,000, they were added to the above-mentioned solution (1) heated to 6,000 and stirred with a mixer for 2 minutes to form an emulsion.

By applying a solution for a red sensitive emulsion layer, which had been produced by the method described above, to one with an intermediate layer (adhesive layer) provided cellulose triacetate carrier in the form a layer in a coating amount of 20 mg of silver per 100 cm 2 became a Film (1) produced.

A film (11) was produced as follows: 40 μl of a 5% strength aqueous Solution of polyvinylpyrrolidone (molecular weight about 150,000) became the coating solution for the red-sensitive emulsion layer prepared beforehand after the above Process had been prepared, added and the resulting solution was in the form of a layer on top of one provided with an intermediate layer (adhesive layer) Cellulose triacetate carrier in a coating amount of 20 mg silver per 100 cm2 upset.

The films (1) and (11) were through a step part (gray wedge) with exposed to a density difference of 0.15 with red light and below the following Conditions color developed: (i) for 12 minutes at 24 ° C, (2) for 6 minutes at 30 ° C, (3) for 2 minutes at 40 ° C and (4) for 50 seconds at 50 ° C, the for the color development at each temperature depending on the time required the respective development temperature was changed to accommodate the changes in the photographic Correct properties due to the temperature difference. After that were performed the following stages of treatment: Treatment level Temperature (° C) Time (minutes) Stopping 24 4 Hardening 24 4 Washing 24 4 Bleaching 24 4 Fixing 24 8 Washing 24 8 Drying Below are the compositions each of the treatment solutions indicated.

Color developer solution Benzyl alcohol 5.0 ml anhydrous sodium sulfite 1.85 g sodium bromide 1.40 g potassium iodide 0.5 mg sodium hydroxide 12.5 g borax 44.9 g 4-amino-3-methyl-N-ethyl-N- (ß- methylsulfonamidoethyl) aniline 5.0 g water ad 1 l stopping solution glacial acetic acid 17.0 ml anhydrous sodium acetate 2s9Li g water ad 1 1 hardening solution 35% formalin 20.0 ml sodium carbonate 9.04 g sodium hydroxide 0.32 g water ad 1 l bleaching solution sodium ferrocyanide decahydrate 36 , 5 g potassium persulfate 7.4 g sodium bromide 12s8 g borax 7'3 6 boric acid 16.6 g sodium hydroxide o, 3 g water ad 1 1 fixing solution sodium sulfite 5.90 g sodium thiosulfate 320 g sodium bisulfite 1547 g water ad 1 1 The density of each of the samples obtained thereby were measured through a red filter and the haze, the sensitivity and the gamma were determined. The individual granularities of the samples obtained in this way are compared with one another at an image density of ° s5. The logarithmic value of the amount of exposure required to achieve a density of 0.2 above fog (Schleicr + 0.2) was used to determine the relative value of the sensitivity to be controlled. The higher the value in the positive direction, the higher the sensitivity. The gamma was determined according to the following equation: where (log E) D is the logarithine of the amount of exposure required to achieve a density D. The Selwin G value ("Phot.

J. ", Volume 79, page 513 (1939)) at an image density of 0.5. The graininess is the better, the more this value becomes smaller. The results obtained are shown in Table 1 below. Tabel I Development temperature and development time 24 ° Cx12 min. 30 ° Cx6 min. 40 ° Cx2 min. 50 ° Cx50 sec.

Film I II I II I II I II Polyvinylpyyrrolidone - +1) -2) + - + - + Veil 0.08 0.06 0.13 0.07 0.20 0.09 0.26 0.12 Sensitivity (relative value) 0 +0.01 -0.03 -0.01 +0.02 +0.04 -0.04 -0.03 Gamma 0.78 0.79 0.77 0.79 0.74 0.76 0.74 0.77 G value 0.55 0.53 0.47 0.45 0.39 0.38 0.35 0.35 1) + = available 2) - = missing the end From the results in Table 1 above, it can be seen that by increasing the developing temperature the graininess of the obtained color image was greatly improved and that at the same time the veil rose. This veil can be created by incorporating polyvinylpyrrolidone almost completely prevented (suppressed). That is, in the practical By carrying out the invention, color images can be generated which have a significantly improved Have graininess without undesirable effects in relation to the photographic Properties such as the grinder, the sensitivity, the gamma and the like. Occur.

Example 2 180 ml of a 0.3% strength methanolic solution of the compound (3) as a spectral sensitizer, 20 ml of a 1% aqueous solution of 5-methyl-7-hydroxy-1,34-triazaindolizine, 300 g of a magenta coupler emulsion, prepared according to the following described emulsion (B), and 50 ml of a 2% aqueous solution of the sodium salt of 2-hydroxy-4,6-dichloros-triazine became 1000 g of a highly sensitive silver iodobromide negative emulsion added, the per 100 g of emulsion 6.5 g of silver iodibromide (silver iodide content 6.0 Mol% ') and 10 g gelatin.

Connection 3 Emulsion (B) (1) gelatin (10% aqueous solution) 1000 ml (2) sodium p-doedecylbenzenesulfonate 5 g sorbitan monolaurate (20% methanolic solution) 30 ml tricresyl phosphate 65 ml purple coupler (compound 4)) 60 g ethyl acetate 110ml compound (4) After the compounds listed in (2) above were mixed with each other at a temperature of 6,000 and dissolved, the mixture was added to the gelatin aqueous solution (1) kept at a temperature of 6,000 and stirred with a mixer for 20 minutes forming an emulsion.

In the same manner as above, two kinds of coating solutions for a green-sensitive emulsion layer were prepared. 40 ml of a 5% aqueous solution of polyvinylpyrrolidone (molecular weight 150,000) were added to one of the solutions, while 10 ml of a 1% aqueous solution of a known antifoggant compound (5) were added to the other emulsion: Compound (5) as described in Japanese Patent Publication No. 15471/71. In this way, two kinds of coating solutions for green-sensitive emulsion layers were obtained.

By applying any of the three types of Coating solutions for green-sensitive emulsion layers on one with a Interlayer (adhesive layer) provided cellulose triacetate carrier in the form of a Layer in a coating amount of 20 mg of silver per 100 cm2 were films (III), (1V) and (V) produced. Films (III), (1V) and (V) were passed through a step part (GrauReil) exposed to green light with a density difference of 0.15 and on color developed in the same manner as in Example 1 under two different conditions : i.e. for 12 minutes at 24 ° C and for 2 minutes at 40 ° C. Dense everyone of them samples obtained were determined in the same manner as in Example 1, wherein this time, however, to determine the haze, the sensitivity and the gamma Green filter instead a red filter was used. The graininess of the samples were compared with each other in the same manner as in Example 1. The results obtained are given in Table II below.

Table II Development temperature and development time Film III IV V III IV V Antifoggants - polyvinyl compound - polyvinyl compound pyrrolidone (5) pyrrolidone (5) sensitivity (relative value) 0 +0.02 +0.24 +0.05 +0.05 +0.28 Veil 0.13 0.11 0.10 0.28 0.13 0.12 Gamma 0.81 0.80 0.81 0.76 0.79 0.70 G-value 0.51 0.51 0.50 0.35 0.34 0.37 From the results of the above It can be seen from Table II that the use of a known antifoggant, such as the compound (5) are effective from the standpoint of preventing fogging with compound (5) showing a marked decrease in sensitivity. On the other hand, by using polyvinylpyrrolidone, a satisfactory one could be obtained Control of fogging can be achieved without a decrease in sensitivity occurred.

Example 3 20 ml of a 1% strength aqueous solution of 5-methyl-7-hydros 1,3f4-triamaindolizine, 400 g of an emulsion containing a yellow coupler, the was prepared according to the emulsion (C) described below, and 50 ml of a 2% aqueous solution of sodium sal% es of 2-hydroxy-4,6-dichloro-s-triazine, used as a gelatin hardener became 1000 g of a high sensitivity Silberåod dbromid-Negativemulsien added, per 100 g of emulsion 5.6 g of silver iodobromide (Silver iodide content 6.0 mol%) and 10 g of gelatin.

Emulsion (c) (1) gelatin (10% aqueous solution) 1000 ml (2) ethyl acetate Yellow coupler (compound 6)) 100 g sodium p-dodecylbenzenesulfonate 5 g sorbitan monolaurate (20% methanolic solution) 30 ml tricresyl phosphate 65 ml After the above below (2) specified compounds mixed with one another at a temperature of 60 ° C and had been resolved the mixture became the aqueous one at 6000 Gelatin solution (1) was added and stirred with a mixer to form an emulsion.

Connection (6) Using a coating solution for a blue-sensitive emulsion layer prepared using the methods described above, and using another coating solution for a blue-sensitive emulsion layer containing 40 ml of a 5% aqueous solution of a vinylpyrrolidone / vinyl alcohol copolymer (monomer molar ratio 7 : 3, molecular weight about 100,000), which had been added in addition to the coating solution described above, films (VI) and (VII) were produced, each coating solution in the form of a layer on a cellulose triacetate support provided with an intermediate layer (adhesive layer) in a coating amount of 20 mg silver per 100 cm2 was applied.

Films (VI) and (VII) were replaced by a step part V gray wedge) exposed to blue light with a density difference of 0.15 and the color development was made in the same manner as in Example 1 under two different conditions performed: i.e. for 12 minutes at 24 ° C and for 2 minutes at 4000.

The density of the samples thus obtained was determined in the same way as determined in example, but this time to determine the veil that Sensitivity and gamma, a blue filter is used instead of a red filter became.

The grains of the samples were determined in the same manner as in Example 1 compared to each other. The results thereby obtained are as follows Table III given.

Table III Development Temp. and development time 24 ° Cx12 minutes 40 ° Cx2 minutes Film VI VII VI VTT PVP / PVA mixed polymer + + haze 0.21 0.15 °, 39 0.15 Sensitivity (relative value) Q +0.02 -0.02 0 Gamiiia 0.81 0.79 0.78 0.80 G value 0.68 0.66 0.56 °, 55 As from the results in Table III above As can be seen, the use of the PVP / PVA blend polymer was effective for the prevention of the occurrence of fog in high temperature development and excellent color images were obtained with improvement the graininess due to the high temperature development.

Example 4 Using the procedures described below A coating solution for a yellow filter layer was prepared: 10 ml of one 1% aqueous solution of sodium iodecylbenzenesulfonate and 50 ml of a 2% aqueous solution of the sodium salt of 2-hydroxy-4,6-dichloro-s-triazine were too 1000 g of a 6% aqueous gelatin solution were added, the 8 g of yellow Colloidal Contained silver of the Carev Lea type. Another coating solution was also used prepared, the coating solution described above being a vinyl pyrrolidone / vinyl alcohol (Monomeruol ratio 7: 3) -STi.schw polymerisat (molecular structure about 100,000) was admitted.

The two coating solutions for a yellow filter layer were each as described in Example 2 in a dry dense thickness of 2 / u on the Film (III) in the form of a layer applied under. Formation of the film (VIII) or of the film (IX).

The films (VIII) and (IX) were each separated by a step (gray wedge) exposed to green light with a density difference of 0.15 and on the same Color-developed in the same manner as in Example 1. The density of each of the samples thus obtained was determined in the same way as in Example 1, but this time for Determination of the Schleser, the sensitivity and the Gamila instead of the red filter a green filter was used and the G-value was determined at the same time. The results obtained are given in Table Iv below.

Table IV Development temperature and development time 24 ° Cx12 minutes 30 ° Cx6 minutes 40 ° Cx2 minutes 50 ° Cx50 seconds Film VIII IX VIII IX VIII IX VIII IX Antifoggant - + - + - + - + Veil 0.13 0.12 0.21 0.15 0.32 0.17 0.45 0.20 Sensitivity (relative value) 0 +0.01 +0.02 0 0.03 +0.03 +0.05 +0.07 Gamma 0.79 0.79 0.79 0.77 0.76 0.78 0.75 0.77 G-value 0.49 0.50 0.45 0.44 0.37 0.37 0.33 0.34 From the results of Table 1V above, it can be seen that that by adding polymers containing vinylpyrrolidone units to a a hydrophilic colloid layer adjacent to a silver halide emulsion layer the formation of fog in the high-temperature development can be significantly inhibited could.

Example 5 The films produced as described in Example 4 (VIII) and (IX) were exposed and applied in the same manner as in Example 4 Reversal development was performed at the following process stages: Treatment stage Temp. (° C) Time (min.) Hardening bath 30 1 washing 30 1 first development 30 3 washing 30 ° s5 reversal (uniform exposure at 8000 iiux per second on the Emulsion surface) Second development (for 12 minutes at 2400 or 2 minutes long at 40 ° C) washing 30 1 bleaching 30 1 washing 30 0.5 fixing 30 1 washing 30 1 The solutions used in the various stages had the following compositions: Hardening bath Sulfuric acid (mixed with water in a volume ratio of 1: 1) 5.4 ml of sodium sulfate 150 g of sodium acetate, 20 g of formaldehyde (40% strength aqueous solution), 10 ml of acetylformaldehyde (40% aqueous solution) 10 ml of water ad 1 l. First developing solution 4- (N-methylamino) phenol sulfate 2 g sodium sulfite 90 g hydroquinone 8 g sodium carbonate monohydrate 52.5 g potassium bromide 5g potassium thiocyanate Ig water ad 1 1 Second developing solution benzyl alcohol 6 ml anhydrous sodium sulfite 4g sodium tert-phosphate 40 g sodium hydroxide 1.5 g Potassium bromide 0.5 g ethylenediamine 5 g citrazinic acid Ig p-amino-N-ethyl-N-ß-methanesulfonamidoethylm-toluidine sulfate 11 g water ad 11 chlös Ferricyanid 100 g sodium acetate 40 g glacial acetic acid 20 ml potassium bromide 30 g water ad 1 1 Fixing solution sodium thiosulfate 150g sodium acetate 70 g sodium sulfite 10 g potassium al aun 20 g water ad 1 1 The maximum density that Sensitivity, the gamma and the G value of the samples obtained thereby were on determined in the same manner as in Example 1. The results obtained are given in Table V below.

Table V Temperature and duration of the second entry 24 ° C x 12 minutes 40 ° C x 2 minutes Film VIII IX VIII IX Antifoggant - + + + mux 2.55 2.38 2.10 2, @ 0 Dmax 2.95 2.96 2.78 2.90 Sensitive 0 +0.01 +0.05 +0.02 speed Gamma 1.86 1.85 1.84 1.87 G-value 0.42 ¼42 0.35 0.32 From the results of the above Table V shows that when the process of the invention is used the color reversal development of color images with excellent photographic properties and excellent granularity.

Although the invention has been described above with reference to specific, preferred embodiments explained in more detail, but it is self-evident to the person skilled in the art that it is by no means limited to this, but that it is in many ways could be changed and modified without departing from the scope of the present Invention is abandoned.

Claims (9)

Claims Process for producing a color photographic image by Color developing a photographic material comprising a support and at least a silver halide emulsion layer coated thereon at a temperature around 3000, characterized in that one uses a photographic material used that in the silver halide emulsion layer or in an adjacent (adjacent) hydrophilic colloid layer at least one polymer with vinylpyrrolidone as a recurring unit. 2. The method according to claim 1, characterized in that one is a Photographic material used which is a vinyl pyrrolidone homopolymer and / or a copolymer of vinylpyrrolidone and an addition polymerizable therewith Contains monomers. 3. The method according to claim 2, characterized in that the repeating unit of the monomers copolymerizable with Vin; srlpyrrolidone has one of the following formulas in which R1 is a hydrogen atom, an alkyl, hydroxyalkyl, or alkoxyalkyl group, R2 is a hydrogen atom, an alkyl, hydroxyalkyl or alkoxyalkyl group and R3 is a hydrogen atom or a methyl group. 4. The method according to at least one of claims 1 to 3, characterized characterized in that a photographic material is used as vinyl pyrrolidone polymer containing at least one of the following as a repeating unit Compounds contains: polyvinylpyrrolidone and / or a vinylpyrrolidone / acrylic acid Mixed polymer, a vinyl pyrrolidone / methacrylic acid mixed polymer, a vinyl pyrrolidone / acrylamide mixed polymer, a vinylpyrrolidone / N-ethyl acrylamide copolymer, a vinylpsyrrolidone / N-acryloylmorpholine copolymer, a vinylpyrrolidone / N-acryloylpiperidine copolymer, a vinylpyrrolidone / N, N-diethyl acrylamide copolymer, a vinyl pyrrolidone / diacetone acrylamide "mixed polymer, a vinyl pyrrolidone / methyl acrylate mixed polymer Vinyl pyrroidone / butyl acrylate copolymer, a vinylpyrrolidone-2-ethylhexyl acrylate mixed polymer, a vinylpyrrolidone / 2- (N-acetyl) aminoethyl acrylate mixed polymer, a vinylpyrrolidone / vinyl acetate mixed polymer, a vinyl pyrrolidone / styrene copolymer, a vinyl pyrrolidone / styrene copolymer a vinylpyrrolidone / N-vinylmethylimidazole copolymer, a vinylpyrrolidone / maleic acid copolymer and a vinylpyrrolion / acrylicide / hydroxyethyl acrylate copolymer. 5. The method according to at least one of claims 1 to 4, characterized characterized in that a photographic material is used which is vinyl pyrrolidone as a repeating unit containing polymer in an amount of about 0.5 to about 40 wt .-%, based on the total weight of the polymer containing Layer existing 3indmittel contains. 6. The method according to at least one of claims 1 to 5, characterized characterized in that one contains a vinylpyrrolidone as a repeating unit Polymer used that has a molecular weight within the range of about 10,000 to about 500,000. ?. Method according to at least one of Claims 1 to 6, characterized in that that one uses a photographic material contained in a silver halide emulsion layer contains at least one color coupler. 8. The method according to at least one of claims 1 to 7, characterized in that that one uses a photographic material with a support on which at least a blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive Silver halide emulsion layer are applied. 9. The method according to at least one of claims 1 to 8, characterized characterized in that the color development is carried out with a color developer, containing an aromatic primary amine developing agent and a color coupler.