DE2744489A1 - High-speed photographic colour negative material - contg. development inhibitor releasing cpd. and having fast and slow red-sensitive emulsions - Google Patents

Abstract

High-speed multilayer photographic colour negative material consists of a base with a red and a green sensitive emulsion, yellow filter layer and a blue-sensitive emulsion. The emulsions contain immobile cyan, magenta and yellow couplers respectively and Ag halide (AgX) grains with a numerical average particle size >1.0 um. Improvement is that (i) >=1 AgX emulsion contains a DIR cpd.; and (ii) the red-sensitive layer consists of >=2 AgX emulsions, the farthest from the base having >1.0 mu grains and contg. not 1.8 g Ag/m2 and is not >40 x 10-5 mole cyan coupler/m2, whilst the grain size is not >1.0 mu m in the other(s). The graininess and definition are improved without causing an imbalance of the development properties, esp. of the red-sensitive layer.

Description

Multi-layer photosensitive color

materials This invention relates to silver halide color photosensitive materials. In particular, the invention relates to multilayer silver halide negative photosensitive materials.

Silver halide color negative multilayer photosensitive materials generally comprise a support and a red sensitive silver halide emulsion layer, containing a non-diffusible cyan-forming coupler, a green sensitive one Silver halide emulsion layer, the one indifferent magenta-forming coupler contains a yellow filter layer that is colorless throughout photographic processing, and a blue-sensitive silver halide emulsion layer, containing a non-diffusible yellow forming coupler on the support. she sometimes have an antihalation layer, intermediate layers, filter layers and protective layers other than the above-mentioned photographic layers.

In photographically sensitive silver halide materials a higher sensitivity not only in cases of monochromatically sensitive Material (black and white material) required, but also in cases of color sensitive Materials. Numerous have already been carried out to achieve greater sensitivity Efforts regarding the method of forming the silver halide particle, the composition of the silver halide, the chemical sensitization or Spectral sensitization and the like and these have been quite successful.

Even if, however, all of these known measures to increase The sensitivity applied is that in color-sensitive negative materials The sensitivity obtained is worse than that of those in black-and-white sensitive Materials.

Another effective way to increase sensitivity in sensitive silver halide materials consists in increasing the particle size of the silver halide particles. However, according to this method, the grain is deteriorated and the sharpness is lowered as the sensitivity is increased. The grain of the color images ultimately obtained in the delicate color negatite materials not only through the grain size of the silver images, but also through developing agents, Coupler and other materials present affected Als Process to improve the grain and the sharpness of the color-sensitive materials a method is known which involves the use of couplers of the one development inhibitor releasing type, commonly referred to as DiR couplers, or of a Non-coupler development inhibitor releasing compounds To increase the sensitivity of silver halide color-sensitive materials it is effective that an average particle size of the silver halide particles, the meaning of this term in the photographic field being clear, in at least one emulsion layer, which is the blue-sensitive layer and the green-sensitive layer Layer or build up the red sensitive layer, is more than 1>. In this In case it is effective for improving grain and / or sharpness, DIR coupler or use DiR connections. However, delicate color negative materials cause with a blue sensitive layer, a green sensitive layer and a red-sensitive layer comprising an emulsion layer containing silver halide particles with an average particle size greater than 1p include other new ones Problems that have not been observed with the previous color-sensitive materials could never be no comparably high sensitivity except for the problems of grain or sharpness. If namely the DIR couplers or DiR connections are used for these sensitive materials so as not to damage the Because graininess and sharpness is caused, it becomes very difficult to balance the color between To keep every color image, as there are great differences between the development process properties the red-sensitive layer and the full-sensitive layer and the blue-sensitive layer Layer caused. Namely, it becomes the area of development conditions, among which the densities and y-values in the area of low, the medium and high density in each layer under satisfactory conditions be kept extremely tight and as a result it becomes nearly impossible for that Practice appropriate color negative images due to the change in numerous factors such as e.g. the sensitive materials given before or after exposure to light Time of standing w the state of the development equipment, the degree of fatigue the developing solution or the temperature of the developing solution and the like.

It is an object of the invention to provide an improved balance the development progress properties of each color-sensitive layer in high-sensitivity multilayer color negative photosensitive materials, the blue-sensitive Layer, the green-sensitive layer and the red-sensitive layer at least a highly sensitive silver halide emulsion layer comprising silver halide particles with more than 1.0 average particle size and at least one of the Silver halide emulsion layers contain a DiR coupler or DiR compounds. Specifically, the object of the invention is to improve the development progress property the red-sensitive layer of the high-sensitivity multilayered ones discussed above color negative photosensitive materials.

Another object of the invention is to improve the Grain and sharpness of the high-sensitivity multilayer listed above color negative photosensitive materials without causing an intolerable imbalance the development progress properties of each color-sensitive layer will. -In particular, this task consists in improving the grain and the Sharpness of the cyan images without any Damage to the development progress property the red-sensitive layer.

The objects of the present invention are achieved by using highly sensitive multilayer color negative photosensitive materials comprising a support and the The following layers formed thereon can be produced: (1) A red-sensitive light-sensitive silver halide layer comprising at least one silver halide emulsion layer containing a nondiffusible cyan coupler wherein the silver halide particles have a numerical mean particle size greater than i, O'L, (2) a green-sensitive light-sensitive silver halide layer which comprises at least one silver halide emulsion layer containing a nondiffusible magenta coupler, wherein the silver halide particles have a numerical mean particle size greater than 1.0, (3) a yellow one Filter layer and (4) a blue-sensitive light-sensitive silver halide layer, the at least one silver halide emulsion layer containing a non-diffusible one yellow coupler, the silver halide particles having a numerical average particle size greater than 1, with at least one of the silver halide emulsion layers contains a development inhibitor releasing compound and the red sensitive light-sensitive silver halide layer comprising at least two silver halide emulsion layers is constructed in which is the numerical average particle size the contained in the red-sensitive emulsion layer furthest from the support Silver halide particles is more than 1.0μ and the red-sensitive emulsion layer at least 1.8 gIm2 silver and 40 X 10 5 mol / m2 or less of the cyan dye-forming agent Coupler contains and the average numerical particle size of the silver halide particles in the further red-sensitive emulsion layer is 1.0p or less.

In the drawings, FIG. 1 is a graphical representation of FIG photographic characteristic curves representing each development progress property the blue-sensitive layer (B), the green-insensitive layer (G) and the red-sensitive layer Layer (R) in a known light-sensitive color negative material shows, Fig. Fig. 2 is a graph showing the photographic characteristic curves showing each the development progress property of the blue-sensitive layer, the green-insensitive layer and the red-sensitive layer in the color-sensitive Show material according to the invention.

Included in the description of preferred embodiments the light-sensitive materials have a red-sensitive layer, a green-sensitive layer Layer and a blue-sensitive layer, at least one of which is two or more emulsion layers each having different silver halide particle sizes and a different sensitivity and the advantages thereof are known from GB-PS 923 045 and US-PS 3,643,369. The photosensitive Materials according to the invention, of course, have the advantages of such More sensitive Materials. However, the technical problems that arise due to the present Invention can be solved very difficult only by those in the above listed patents to solve listed measures.

In the color-sensitive materials according to the invention, it will it is preferred that the silver halide contained in the blue-sensitive layer be 1.0 up to 2.5 g per 1 m2, calculated as silver, and that in the green-sensitive layer contained silver halide is 2.0 to 4.5 g per 1 m2, calculated as silver. These amounts are opposite to that in the known color light-sensitive materials having an average particle size of silver halide of 1.0p or less used silver content does not differ greatly. In the color sensitive materials in accordance with the invention it is therefore preferred that the total sum of the silver halide contents in the blue-sensitive layer and the green-sensitive layer 3.0 to 7.0 g / m2, calculated as silver.

In the case of the color-sensitive materials according to the invention, the red sensitive silver halide layer made of at least two different silver halides emulsion layers built up. The red-sensitive layer can be composed of two silver halide emulsion layers be constructed as indicated in GB-PS 923 045, or can be composed of three silver halide emulsion layers may be constructed as disclosed in U.S. Patent 3,843,369 or four or more Silver halide emulsion layers exist.

In the photosensitive materials according to the invention, the Silver content in the top layer of the red-sensitive layer 1.8 gIm2 or amount more. One an amount of 2.2 g or more is further preferred.

Although not to achieve the objects of the present invention is necessary an upper limit of the silver content in the above To establish the layer, it is preferred that the silver content be 4.5 g / m 2 does not exceed so as not to have difficulty in bleaching during color photographic Development occur. The average particle size of the silver halide particle according to the invention, the numerical average value of the diameter is the Particle specified as it is according to the Particle Size Analysis, pages 45 to 55, British analytical chemistry Association, W. Heffer Co., 1967, method given, after determining the statistical distribution of the diameter of the particles assuming that each particle is a circle with an equal projection area for each particle approximates, based on the in The Theory of the Photographic Process, Pages 36 to 44, 3rd edition, C.E.K. News, Nacmillan Co., 1966, Specified Way, is determined.

Contains in the color-sensitive materials according to the invention at least one of the silver halide emulsion layers comprises a compound having a Releases development inhibitor. Such compounds are called DIR couplers or DIR connections known. Although the development inhibitor releasing compound can be contained in any silver halide emulsion layer, it is advantageous in the layer with an average particle size of the silver halide of i'OLL or less included. If the DIR coupler or the DiR connection in at least one Emmlsionsschicht in sufficient amount to improve the Grit or sharpness is included, if the silver content the topmost red sensitive emulsion layer with an average particle size of the silver halide of more than 1.0p in the one commonly used for this purpose Amount, i.e., less than 1.8 g / m2, is the development progressing property in terms of the cyan images on the red-sensitive layer, i.e., a change the photographic properties with an increase in the development time, such as R can be seen in Fig. 1, remarkably different from that of the green sensitive Layer and the blue-sensitive layer indicated as G and B in FIG. According to the invention, the silver content in the top layer is the red-sensitive Layer more than 1.8 g / m2, as that has not been used before, which reduces the development speed the red-sensitive layer closer to that of the green-sensitive layer blue-sensitive layer, as can be seen from FIG. Even if that's why the conditions itir the development and the conditions before the development in in the same manner as the known color negative photosensitive materials be controlled, it becomes possible to obtain sufficiently stabilized photographic properties and especially to get a good color balance.

In the sensitive materials according to the invention it is preferred that the sum total of the silver content of the emulsion layers, excluding the topmost Layer, which builds up the red-sensitive layer, in a range from 1.5 to 3.0 gIm2, however, it is preferred that the ratio of silver content be to that of the uppermost layer ranges from 0.7 to 1.2. When the relationship Exceeds 1.2, it is somewhat difficult to have the development progress characteristic shown in FIG to obtain, so that therefore ratios above 1.2 are not preferred to this extent will.

In the sensitive materials according to the invention, the green-sensitive Layer and the blue-sensitive layer of two or more different emulsion layers each with different sensitivity and / or different average Be the particle size of the silver halide. It is preferred that at least one the layers of red-sensitive layer, green-sensitive layer and blue-sensitive layer Layer made up of emulsion layers, each with a different sensitivity thereby achieving the advantages set forth in US Pat. No. 3,843,369. the Relationships between a plurality of emulsion layers in each color-sensitive Layer in terms of sensitivity, average particle size, amount or type of coupler and other various properties may be appropriate Wise and this selection can easily be made by any person skilled in the art will.

In the photosensitive materials according to the invention it is preferred that the red-sensitive layer, the green-sensitive layer, the yellow filter layer and the blue-sensitive layer are in that order on the support. However, at least one of the red sensitive emulsion layers can be applied to at least one of the green-sensitive emulsion layers, at least one the green-sensitive emulsion layers or blue-sensitive emulsion layers can be placed underneath at least one red sensitive emulsion layer (page closer to the carrier) or at least one of the red-sensitive emulsion layers or the green-sensitive emulsion layers can be on at least one of the blue-sensitive Emulsion layers be formed.

As in the low-sensitive, red-sensitive layer with a average particle size of the silver halide of 1.0p or less DIR couplers or DiR compounds, the known materials can be used. However, the amount of the DIR coupler or the DiR compounds must correspond to the Kinds of the same can be varied. The person skilled in the art can, however, determine the amount easily referring to publications or patents regarding each DIR connection or the DiR coupler.

The DiR compounds used in the context of the invention include DIR couplers, non-coloring DiR coupling compounds and DIR redox compounds. Examples of DIR couplers which can be used in the context of the invention include DIR couplers of the o-aminoazotype according to US Pat. No. 3,148,062, DIR couplers of the thioether type corresponding to US Pat. No. 3,227,554, 2-benzotriazolyl-type DiR couplers correspondingly U.S. Patent 3,617,291, DiR-Kuppier of the 1-benzotriazolyl type corresponding to the German OLS 2 414 006 and Japanese Patent Publications 159 263/75 and 34 615/76, DIR coupler of nitrogen-containing heterocycles substituted acetic acid ester s corresponding to Japanese Patent Application Nos. 30 591/75 and 159 255/75, DIR cyan couplers of the 2-equivalent type according to Japanese Patent Applications 7,770/76 and 70 592/75 and the German OLS 2 527 652 and DiR-Kuppier of the malonic acid diamond type corresponding to Japanese Patent Application 146 570/75.

Examples of non-coloring DiR coupling compounds in the frame of the invention include cyclic non-staining DIR compounds of the thioether type corresponding to GB-PS 1 423 588, the German OLS 2 405 442, 2 523 705, 2 529 350, 2,448,063 and U.S. Patent 3,938,996, non-staining DiR compounds of the thioether type corresponding to U.S. Patent 3,632,345 and 3,928,041, non-staining DiR compounds of the benzotriazolyl type according to Japanese patent applications 147 716/75, 31 480/75 and 143 538/75 and DIR coupling compounds of the picolinium type, respectively Japanese Patent Application 147 091/74. Examples of DiR redox compounds for use in the context of the invention, the DiR-hydroquinones comprise accordingly U.S. Patent 3,297,445, DT-OS 2,460,202, and U.S. Patent 3,639,417 and Coupler of U.S. Pat DIR redox type according to Japanese patent application 133 693/75.

The preferred DIR compounds according to the invention are made by the following general formulas (VII) to (x) are given.

General formula (VII) or wherein A1 denotes a yellow coupler group, a magenta coupler group, a cyan coupler group, a malondiimide coupler group, a hydrochloric acid diester coupler group or an indanone coupler group, and B1 denotes a bromine atom, an acylamino group, a benzothiazolinylidene amino group or an aralkyloxy group.

General formula (VIII) wherein A2 represents a cyari coupler radical and B2 represents a halogen atom, a nitro group, an alkoxy group, an alkyl group, an amino group or an acylamine group.

General formula (IX) wherein A2 has the same meaning as in the general formula (VIII) and Bi has the same meaning as in the general formula (VII).

General formula (x) where B2 has the same meaning as in the general formula (VIII) and A3 is a yellow coupler radical, a magenta coupler radical, a cyan coupler radical, a malondiimide coupler radical, a malonic acid diester coupler radical, an indanone coupler radical, a coupler radical of the «- (2-benzothia- (or benzidoxa-) acetanil ) type or a hydroquinone radical.

Examples of particularly preferred developer inhibitor releasing compounds (DIR advertisements) include the following compounds (DIR couplers) (DIR magnetic coupler) (DIR cyan coupler) (Non-coloring DIR coupler compound) (DIR-Pedox connections) The photographic emulsions used in the invention can be prepared by the methods described in Chimie et Physique Photographique, "P. Glafkides, Paul Montel Co., 1967, Photographic Emulsion Chemistry", GF Duffin, The Focal Press, 1966, and " Making and Coating Photographic Emulsion ", VL Zelikman et al., The Focal Press, 1964, and the like. Both acidic emulsions and neutral emulsions and ammoniacal emulsions can be used. Further, as the method for reacting water-soluble silver salts with soluble halides, any methods such as single jet method, double jet method and combinations thereof can be used.

Two or more silver halide emulsions prepared separately can be mixed.

Eadmium salts, zinc salts, lead salts, thallium salts, iridium salts or Complex salts thereof, rhodium salts or complex salts thereof and iron salts or Complex salts thereof can be used in the processes for forming the silver halide particles or in the physical aging process.

In the photographic emulsion layers of the invention The photographic light-sensitive materials used may be any silver halide such as silver bromide, silver iodobromide, silver iodobromochloride, silverbromochloride and Silver chloride as silver halides in addition to the super-sensitive ones described above Emulsion can be used. The preferred silver halides are silver iodobromide and silver iodobromochloride, each containing 2 moles or more silver iodide.

The soluble silver salts are generally made from the emulsions their formation by precipitation or after the physical ripening of the same, removed. As such a method, the known method of water washing of pasta, which is carried out after gelatinizing the gelatin, or a coagulating process (Extraction process), which involves the use of inorganic polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers, for example polystyrene sulfonic acid or gelatin derivatives, for example aliphatic acylated gelatin, aromatic acylated gelatin or aromatic carbamoylated Gelatin and the like. Can be used. The process of removing soluble Salts can also be omitted. The syllable halide emulsions are generally used chemically sensitized. To carry out chemical sensitization, it is possible to those in the books by Glafkides or Zelikmann and employees listed above or in the basics of photographic processes with silver halides, H. Frieser, Akademische Verlagsgesellschaft, 1968.

Namely, it is possible to use one or a combination of sulfur sensitization methods apply which the application of sulfur-containing compounds necessary to implement with silver ions or activated gelatin are capable of a reduction sensitization process, which includes the use of reducing materials; and a precious metal sensitization process, which requires the use of compounds of gold or other precious metals, apply. As sulfur sensitizers, thiosulfates, thioureas, Thiazole, rilodanine and others Connections are used for what Examples in U.S. Patents 1,574,944, 2,410,689, 2,278,947, 2,728,668, and 3,656,955 are specified. Tin (II) salts, amines, Sydrazine derivatives, formamidinesulfinic acid and silane compounds can be used and Examples of this are in US Pat. Nos. 2,487,850, 2419974, 2518698, 2983609, 2983610 and 2694637. Not only gold complex salts can be used to sensitize precious metals but also complex salts of metals of group VIII of the periodic table, such as Platinum, iridium or palladium and the like can be used and are examples thereof in U.S. Patents 2,399,083 and 2,448,060 and British Patent 618,061.

If necessary, the photographic emulsions can be one Spectral sensitization or supersensitization using one or more Dyes of cyanine type wje cyanine dyes, merocyanine dyes or carbocyanine dyes and the like, or using a combination of such cyanine type dyes with styryl dyes.

These methods are already well known. As dyes for the blue-sensitive layers are those described, for example, in US Pat. Nos. 2,493,748 and 2,519 001, 2 977 229, 3 480 434, 3 672 897 and 3 703 377 mentioned.

Dyes for the green-sensitive layer are, for example in U.S. Patents 2,688,545, 2,912,329, 3,397,060, 3,615,635 and 3,628,964, GB = PS 1 195 3 () 2, 1 242 588 and 1 293 862, the German OLS 3 030 326 and 2 121 780 and Japanese Patent Publications 4936/68 and 14 030/69. as Dyes for the red sensitive layer are those in Japanese, for example Patent Publication 10 773/68, U.S. Patents 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, GB-PS 1 137 580 and 1 216 202 described. The choice of the same can be made in a suitable manner accordingly the purpose or intended use of the sensitive materials, such as to be sensitized Wavelength range or sensitivity or the like can be carried out.

In the red-sensitive layer of the sensitizing materials according to of the invention, it is particularly advantageous to use combinations of the Japanese Patent Publication 6207/74 and Japanese Patent Application 76 163/75, 109 366/75, 122 012/75, 130 044/75, 17 575/76 and 27 941/76 apply.

Various types of compounds can be added to the photographic Emulsions are added to each layer to avoid damaging the sensitivity or the appearance of veils at the stage of making the delicate ones Materials, during storage of sensitive materials or during prevent their processing. Examples of compounds include 4-hydroxy-6-methyl-1 , 3,3a, 7-tetrazaiden, 3-allylbenzothiazolium compounds, 1-phenyl-5-mercaptotetrazole and benzotriazole compounds and the like.

In the photographically sensitive prepared according to the invention Materials can include the photographic emulsion layers and other hydrophilic ones Colloid layers contain inorganic or organic hardeners. It is for Example possible, chromium salts (chromium alum or chromium acetate and the like), aldehydes (formaldehyde, Glyoxal or glutaraldehyde and the like). N-methylol compounds (dimethylol urea or methyloldimethylhydantoin and the like), dioxane derivatives (2,3-dihydroxydioxane and Like.), active vinyl compounds (1,3,5-trlacryloylhexahydros-trlazine or bis (vinylsulfonyl) methyl ether and the like), active halogen compounds (2,4-chloro-6-hydroxy-striazine and the like), Mucohalogenic acids (mucochloric acid or Mucophenoxychloric acid and Like.), isoxazoles, dialdehyde starch and 2-chloro-6 "hydroxytriazinyl gelatin and the like.

which can be used individually or in combination.

typical examples of color image-forming couplers used in the For use in the present invention include the following materials.

The yellow-forming couplers known are the open-chain couplers from Ketomethylene type. Among them are benzoylacetanilide type and pivaloylacetanilide type compounds particularly advantageous. Examples of yellowing couplers which can be used are described in US Pat U.S. Patents 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 2,725,072, and 3,891 445, the DT-PS 1 547 868 and the German OLS 2 213 461, 2 219 917, 2 261 361, 2 263 875 and 2 414 006.

As the magenta-forming couplers, pyrazolone type compounds are compounds imidazolone type and cyanoacetyl compound and the like; and pyrazolone type compounds particularly advantageous. Usable examples of the magenta-forming coupler include those in U.S. Patents 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3 519 429, 3 558 319, 3 582 322, 3 615 506, 3 834 908 and 3 891 445, DT-PS 1 810,464, DT-OLS 2,408,665, 2,417,945, 2,418,959 and 2,424,467, of the JA patent publication 6031/65 described connections.

Phenol compounds and naphthol compounds are used as cyan-forming couplers preferred. Examples of these include those disclosed in U.S. Patents 2,369,929, 2,434,272, 2,474 293, 2 521 908, 2 895 826, 3 034 892, 3 311 476, 3 458 315, 3 476 563, 3 583 971, 3,591,383 and 3,767,411, the DT-OLS 2,414,830 and 2,454,329 and the JA patent application 59 838/73 described connections.

Colored couplers, for example, in U.S. Patents 3,476,560; 2,521,908 and 3 034 892, the JA patent publications 2016/69, 22 335/63, 11 304/67 and 32 461/69, the JA patent applications 98 469/74 and 118 029/75 and the DT-OLS 2 418 959 described.

Two or more of the above-listed couplers can be used in one Layer be included. Further, any of the above-listed couplers be contained in two or more layers.

In order to introduce the couplers into the emulsion layers, it is possible to to use known methods, for example that given in US Pat. No. 2,322,027 Procedure.

They are here in the hydrophilic colloids after dissolution in organic solvents with boiling points above 180 ° C, such as phthalic acid alkyl esters, e.g. dibutyl phthalate or dioctyl phthalate and the like, trimellitic acid esters, e.g. tri-tert.-octyl trimellitate, Benzoic acid esters, for example 2-ethylhexyl benzoate, phosphoric acid esters, for example Diphenyl phosphate, triphenyl phosphate, tricresyl phosphate or dioctyl butyl phosphate, Citric acid esters, for example tributyl acetyl citrate or alkylamides, for example N, N-diethyllaurylamide and the like, or organic solvents having a boiling point from 30 to 15, such as lower alkyl acetates such as ethyl acetate or butyl acetate and Like., ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, ß-ethoxyethyl acetate or methyl cellosolve acetate and the like. The organic ones listed above Solvents with higher boiling points and the organic solvents with lower ones Boiling points can also be used in the form of mixtures.

If the coupler has acidic groups such as carboxyl groups or sulfo groups they are introduced into the hydrophilic colloids as aqueous alkaline solutions.

Albeit gelatin with advantage as a binder or protective colloid Photographic emulsions can also contain other hydrophilic colloids can be used.

For example, it is possible to use proteins such as gelatin derivatives, graft polymers of gelatin and other high molecular weight materials, albumin or casein and the like, sucrose derivatives, such as cellulose derivatives, such as hydroxyethyl cellulose, carboxymethyl cellulose or cellulose sulfates and the like, sodium alginate or starch derivatives and the like, and synthetic hydrophilic ones high molecular weight materials, such as homo- or copolymers, such as polyvinyl alcohol, polyvinyl alcohol partial acetal, Poly-N-vinylpyrrolidone, polyacrylic acid, polynethacrylic acid, polyacrylamide, polyvinylimidazole or polyvinylpyrazole and the like.

Not only lime-treated gelatin but also acid-treated gelatine can be used.

Furthermore, hydrolyzed gelatin products or enzymatic Decomposition products of gelatin can be used. Materials are used as gelatin derivatives listed by the reaction of gelatin with compounds such as acid halides, Acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, Brassimides, polyalkylene oxides or epoxy compounds and the like. Examples of this are in U.S. Patents 2,614,928, 3,132,945, 3,186,846 and 3,312,553, GB-PS 861 414, 1 033 189 and 1005 784 and the JA patent publication 26 845/67 and the like.

As gelatin graft polymers, it is possible to use materials obtained by grafting gelatin with homopolymers or copolymers of vinyl monomers, such as acrylic acid, methacrylic acid, esters or amides of acrylic acid or methacrylic acid, Acrylonitrile or styrene and the like. In particular, it is preferred Use graft polymers made from gelatin and polymers with a certain Degree of compatibility with gelatin, such as polymers of acrylic acid, methacrylic acid, Acrylamide, methacrylamide or hydroxyalkyl methacrylate and the like. Are built up. Examples of these are shown in U.S. Patents 2,763,625, 2,831,767 and 2,956,884.

Typical synthetic hydrophilic high molecular materials are for example in DT-OLS 2,312,708, U.S. Patents 3,620,751 and 3,879,205, and US Pat JA patent publication 7561/68.

Polymer latexes can also be included. As polymer latexes vinyl polymers such as acrylic acid ester polymers, methacrylic acid ester polymers are listed, g-substituted acrylic acid ester polymers, acrylamide derivative polymers, methacrylamide derivative polymers, -Substituted acrylamide derivative polymers, vinyl ester polymers, vinyl halide polymers, Vinylidene halide polymers, styrene polymers, styrene derivative polymers, ethylene polymers, Propylene polymers, butylene polymers, butadiene polymers, vinyl ether polymers or acrylonitrile polymers. The polymers can be homopolymers or can be composed of copolymers with other vinyl compounds exist.

The photographic emulsion layers and other hydrophilic colloid layers in the sensitive materials produced according to the invention various Types of known surfactants for a variety Purposes, e.g. as a coating aid, to reduce the electrical charge, for Improvement of the sliding property, emulsification or dispersion, for prevention the adhesion or to improve the photographic properties, such as development acceleration, hard tone or sensitization and the like.

contain.

For example, it is possible to use non-ionic upper acetic agents, such as saponin (steroid type), alkylene oxide derivatives, for example polyethylene glycol, Polyethylene glycol polypropylene glycol condensate, polyethylene glycol alkyl or alkyl aryl ether, Polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone-ethylene oxide addition products and the like, glycide derivatives, for example Alkenyl succinic acid polyglyceride or alkylphenol polyglyceride, aliphatic acid ester of polyhydric alcohol, alkyl esters of saccharides, urethanes of saccharides or Ethers of saccharides and the like, anionic surfactants with an acidic one Group such as carboxyl group, sulfo group, phosphorus group, sulfuric acid ester group or phosphoric acid ester group and the like, such as saponin of the triterpenoid type, alkyl carboxylic acid salts, Alkyl sulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalene sulfonic acid salts, Alkylsulfuric acid esters, alkylphosphoric acid esters, N-acrylic-N-alkyltaurines, sulfosuccinic acid esters, Sulfoalkylpolyethylene alkylphenyl ether or polyoxyethylene alkyl phosphoric acid ester and the like, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, Aminoalkylsulfuric acid esters or phosphoric acid conductors, alkylbetaines, aminimides or Amino oxides and the like and cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary Ammonium salts such as pyridinium or imidazolium and the like, or aliphatic or heterocyclic phosphontum - Or sulfonium salts and the like. To be used.

Those carried out with the photosensitive materials according to the invention Color development treatment essentially comprises the steps of color development, Bleaching, fixation. In this case, each stage can be run independently separately or two or more of the stages can be applied in a treatment a treatment solution with effects for both stages. For example a one-bath bleach-fixing solution is used in such a case.

Furthermore, if necessary, each stage can be divided by a subdivision the same can be carried out in two or more parts. It is possible a combination of color development, first fixation and bleach fixation to apply.

Development treatment is combined with other treatment stages if necessary, such as a pre-hardening bath, a neutralizing bath, a first development (black and white development), an image stabilizing bath, a water wash and the like. Combined. The treatment temperature is determined within a preferred range according to those used sensitive materials or the composition of the treatment solutions and amounts sometimes 18 or lower, but often 18 or higher. A range from 20 to 60 is particularly preferred and recently a range of 30 has been used to 60 a-6 now. It is not always necessary that the treatment temperatures the treatment stages are equal to each other.

The color developing solution consists of an alkaline aqueous solution having a pH of 8 or more, and preferably 9 to 12, being a developing agent contains.

A developing agent is a compound that is a primary one Has amino group on the aromatic ring and has an ability to develop exposed Silver halide or a precursor containing such a compound supplies. Preferred examples of developing agents include 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-f3-hydroxy-ethylaniline, 5-diethyl-4-amino-N-ethyl-N-ß-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-ß-methanesulfonamidoethylaniline, 4-amino-N, N-dimethylaniline, 4-amino-3-methoxy-N, N-diethylaniline, 4-amino-3-methyl-N-ethyl N-B-methoxyethylaniline, 4-Amino -3-methoxy-N-ethyl-N-methoxyethylaniline, 4-amino-3-ß-methanesulfoamidoethyl-N, N-diethylaniline and salts thereof, for example sulfates, hydrochlorides, sulfites or p-toluenesulfonates and the like. Further compounds are disclosed in U.S. Patents 2,193,015 and 2,592,364, of the JA patent application 64 933/73 and Photographic Prccessing Chemistry, pages 226-229, L.F.A. Mason, Focal Press -London, 1966.

Furthermore, the compounds listed above can be combined with 3-pyrazolidones can be used. If necessary, can be of different types of additives can be added to the color developing solution. Examples include alkaline agents, for example hydoxides, carbonates or phosphates of alkali metals or ammonium, pH adjusters or buffering agents, e.g. weak acids, such as acetic acid or boric acid, weak bases or salts thereof, development accelerators, for example, those in U.S. Patents 2,648,604, 3,671,247, 2,533,990, 2,577,127 and 2 950,970, British Patent Nos. 1,020,032 and 1,020,033, and U.S. Patent 3,068,097 Materials, antifoggants, for example alkali bromides, alkali iodides, nitrobenzimidazoles corresponding to US-PS 2,496,940 and 2,666,271, mercaptobenzimidazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole and antifoggants according to US Pat. No. 3,113,864, 3342596, 3295976, 3615522 and 3597199, GB-PS 972 211, the JA patent publication 4167/71 and Kagakushashin Binran, Volume 2, pages 29 to 47, patch-or Anti-sludge agents corresponding to U.S. Patents 3,161,513 and 3,161,514 and British Patents 1,030,442, 1,144,481 and 1 251 558 and preservatives, for example sulfites, acid sulfites, hydroxylamine hydrochloride, Form sulfite or alkanolamine sulfite addition products and the like.

In these stages of the color development treatment, it is possible to carry out an intensification process as described in DT-OS 2,226,770 and US-PS 3 826 652 indicated.

After color development, the photographic emulsion layers become usually bleached. The bleaching treatment can be carried out simultaneously with the fixing treatment can be carried out or can be separated from the fixing treatment. As a bleach are compounds of polyvalent metals such as iron (1II), cobalt (III), chromium (VI) or copper (II) and the like, peracids, quinones and nitroso compounds are used. For example, it is possible to use ferricyanides, bichromates, organic complex salts of To use iron (III) or cobalt (III), for example complex salts of organic Acids, such as aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid or 1,3-diamino-2-propanol tetraacetic acid and the like, citric acid, tartaric acid or Malic acid and the like, persulfates, permanganates and nitrosophenol and the like thereof are potassium ferricyanide, sodium iron (III) ethylenediamine tetraacetate and ammonium iron (III) ethylenediamine tetraacetate particularly preferred. The iron (III) complex salts of ethylenediaminetetraacetic acid are valuable for both the bleach solution and a one-bath bleach-fix solution.

Not just those in U.S. Patents 3,042,520 and 3,241,966 and JA patent publications 8506/70 and 8836/70, but also various ones species other additives can be added to the bleaching solution or the bleach-fixing solution can be added.

The present invention is described in detail below with reference to FIG Examples explained.

--Example 1 The following layers 1 through 11 were made starting with the first layer applied to a cellulose acetate film with a primer layer, to get samples 1 - 1 to 1 - 6.

1st layer (inhalation layer) gelatin layer with black colloidal Silver.

2nd layer (intermediate layer) gelatin layer, which is an emulsion of Contains 2,5-DiZtert.-octylhydroquinone.

3rd layer (low-sensitive red-sensitive emulsion layer) Low-sensitivity silver iodobromide emulsion (silver iodide 6 mol%, average Particle size 0.8μ, gelatin 70g / kg emulsion) Amount of silver applied: 2.2 g / m2 of sensitizing dye 1 per mole of silver 3.0 x 10 4 moles of sensitizing dye II per mole of silver 0.8 x 10 moles of coupler A 160 x 10 5 moles / m2 of coupler B 19 x 10-5 moles / m2 DIR coupler F 2 x 10-5 mol / m² 4th layer (highly sensitive red-sensitive emulsion layer) Highly sensitive silver iodobromide emulsion (silver Iodide 5 mol%, average particle size 1.2μ, gelatin 70 g / kg emulsion) amount of applied Silver: see Table I sensitizing dye I per mole of silver 1.5 × 10 4 moles of sensitizing dye II per mole of silver 0.4 x 10 4 moles of coupler A amount see table I 5th layer (intermediate layer) Same layer as the 2nd layer 6th layer (low-sensitive, green-insensitive Emulsion layer) Low-sensitivity silver iodobromide emulsion (silver iodide 7 mol%, average particle size-0.8p, gelatin 70g / kg emulsion) amount of applied Silver 1.9 g / m2 sensitizing dye III per mole of silver 4.0 x 10 4 moles of sensitizing dye IV per mole of silver 0.5 x 10-4 moles of coupler C 74 x 10-5 moles / m2 of colored coupler D 12 x 10-5 mol / m2 DIR coupler F 3.6 x 10-5 mol / m2 7th layer (highly sensitive, green-sensitive Emulsion layer) Highly sensitive silver iodobromide emulsion (silver iodide 8 mol%, average particle size 1.2μ, gelatin 70 g / kg emulsion) amount of applied Silver 1.8 g / m2 sensitizing dye III per mole of silver 2.0 x 10 4 moles of sensitizing dye IV per mole of silver 0.3 x 10 4 moles of coupler C 22 x 10 5 molXm2 of colored coupler D 4 x 10 5 mol / m2 8th layer (yellow filter layer) A gelatin layer with the content on yellow colloidal Silver and an emulsified dispersion of 2,5-di-tert. -octylhydroquinone.

9th layer (low-sensitivity blue-sensitive emulsion layer) Low-sensitivity silver iodobromide emulsion (silver iodide 7 mol%, average Particle size 0.8, gelatin 70 g / kg emulsion) Amount of silver applied 0.8 g / m2 coupler E 150 x 10 5 mol / m2 DIR coupler F 2 x 10-5 mol / m2 10th layer (highly sensitive blue-sensitive emulsion layer) Highly sensitive silver iodobromide emulsion (silver iodide 8 mol%, average particle size 1.3μ, gelatin 70 g / kg emulsion) amount of the applied silver 0.9 g / m2 coupler E 22 x 10 5 mol / m2 11th layer (protective layer) Gelatin layer.

Each layer contained a hardener for the gelatin and coating aids and the like except for the above composition.

Table I Sample Amount of Applied Amount of Coupler A No. Silver in the silver iodobromide emulsion ~~~~~~~~~~~~~~~~~~~~~~ 1 - 1 4.0 g / m 27 x 10 5 mol / m² 1-2 3.0 "" 1-3 2.4 n n 1-4 2.0 n @ n 1- 5 1.5 "1 - 6 1.0 § Inserted Raw materials: Sensitizing dye I: Anhydro-5,5'-dichloro-3,3'-disulfopropyl-9-ethyl-thiacarbocyanine hydroxide, pyridinium salt.

Sensitizing dye II: anhydro-9-ethyl-3, 3 -di (3-sulfopropyl) -4, 5, 4 ', 5'-dibenzothiacarbocyanine hydroxide triethylamine salt.

Sensitizing dye III: anhydro-9'-ethyl-5,5'-dichloro-3,3-disulfopropyloxacarbocyanine sodium salt.

Sensitizing dye IV: anhydro-5, 6, 5 ', 6'-tetrachloro-1,1'-diethyl-3,3'-di- (sulfopropoxyethoxyethyl) -imidazolocarbocyanine hydroxide, sodium salt.

Coupler A: 1-Hydroxy-N - (# - (2,4-di-tert-amylphenoxypropyl))) -2-naphthamide.

Coupler B: 1-Hydroxy-4- (2- (2-hexyldecyloxycarbonyl) phenylanzo) -2- (N- (1-naphthyl)) naphthamide.

Coupler C: 1- (2,4,6-Trichlorophenyl) -3- (3- (α- (2,4-di-tert-amylphenoxy) acetamido) benzamide-5-pyrazolone.

Coupler D: 1- (2,4,6-trichlorophenyl) -3- (3- (α-2,4-di-tert-amylphenoxy) acetamide) benzamide) -4-methoxyphenylazo-5-pyrazolone.

Coupler E: α- (2,4-Dioxo-5,5'-dimethyloxazolidinyl) -α-pivaloyl-2-chloro-5- (α- (2,4-di-tert. -amylphenoxy) butylamide) acetanilide.

Coupler F: a- (5 (6) - (3-Methyl-2-benzothiazolylideneamino) -1 -benzotriazolyl) -a- (4-octadecyloxybenzoyl) -2-ethoxyacetanilide.

The coupler emulsions listed above were each passed through Dissolution of the coupler in a mixture of dibutyl phthalate and tricresyl phosphate and dispersing the obtained solution in a gelatin solution using of sorbitan monolaurate, Turkish red oil and sodium dodecylbenzenesulfonate as emulsifiers to form an O / W type emulsion.

After exposing these photographic elements to light (1/50 sec, 10 C.M.S.) by a sensitometer, they were subjected to the following development treatment (A), (B) or (c) at 384.

(A) (B) (C) 1st final development 2 min and 3 min and 4 min and 15 sec 15 sec 15 sec 2nd bleaching 6 min and also 30 sec 3rd water washing 3 min and also 15 sec (A) (B) (C) 4th fixation 6 min and the same also 30 sec 5th water wash 3 min and also also 15 sec 6th stabilization 3 lin and also 15 sec. The treatment solutions used in each stage had the following compositions.

Color developing solution: sodium sulfite 4.0 g sodium carbonate 30.0 g potassium bromide 1.4 g of hydroxylamine sulfate, 2.4 g of 4- (N-ethyl-N-ß-hydroxyethylamino) 4 5 g of 2-methylaniline sulfate Water to 11 bleach solution: anonium bromide 160.0 g aqueous ammonia solution (28%) 25.0 ml sodium-iron-ethylenediamine tetraacetate 130 g glacial acetic acid 14 ml water to 11 fixing solution: Sodium tetrapolyphosphate 2.0 g sodium sulfite 4.0 g ammonium thiosulfate (70%) 175.0 ml sodium bisulfite 4.6 g laser for 11 Stabilizing solution: formalin (40%) 8.0 ml of water to 11 The color developing solution was made using water with a content of 3 ppm iron (III) ions. The permeability densities of the color negative samples after completion of the photographic processing were identified as optical densities measured by passing through red, green, or blue color separation filters was conducted.

The assessment was made by changing the relative logarithmic Minimum density sensitivity + 0.2 (sensitivity is reported as by changing the development time and by changing (# G10) the difference the density of SO 2 and the density of logarithmic exposure, which are 1.0 higher than it was the density given above, this difference being subsequently referred to as 1.0 D, with the following results being obtained.

Table II Sample Amount of # S @@ # @ Gemes Silver in 0.2 @@ 1.0 sene of the 4th layer (B) - (A) (C) - (B) (B) - (A) (C) - (B) Density 1 @ 1 4.0 g / m2 0.28 0.14 0, 15th 0.06 Red density 1 - 2 3.0 g / m2 0.32 0.16 0.15 0.10 n 1 - 3 2.4 g / m2 o.33 0.17 0.13 0.10 n 1 - 4 2.0 g / m2 0.35 o, 19 o, 11 o, 10 n 1 - 5 1.5 g / m2 o.37 0.20 0.10 0.10 n 1 - 6 1.0 g / m2 0.41 0.20 0.10 O, tO "1-1b. 1-6 - 0.25 0.15 0.13 0.04 Green density 1-1 b. 1-6 - 0.22 0.15 0.14 0.06 blue density S # @ (B) - (A) difference between S @ @ in the case of development for 3 minutes and 15 seconds and SO 2 in the case the development for 2 min and 15 sec.

# SO, 2 (C) - (B) difference between SO 2 in the case of developing during 4 min and 15 sec and SO 2 ii case of development during 3 min and 15 sec.

# G1.0 (B) - (A) Difference between G1.0 in the case of developing during 3 minutes and 15 seconds and 50 in the case of development for 2 minutes and 15 seconds.

# G1.0 (C) - (B) Difference between G1.0 in the case of developing during 4 min and 15 sec and in the case of development for 3 min and 15 sec.

As is clear from Table II, if the amount of silver is in the 4th layer (highly sensitive, red-sensitive emulsion layer) within of the range according to the invention is the change (# S0,2) in sensitivity (S0,2) with a change in development time close to the change in green density and that of the blue density, and consequently the balances of the densities become less damaged.

Example 2 Samples 2-1 to 2-4 were prepared in the same manner vi. produced in example 1, but the 4th layer (highly sensitive, red sensitive Emulsion layer) of Example 1 was modified in the following manner.

Table III Sample Amount of Silver Applied Amount of Coupler A No. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~ 2 - 1 3.0 g / m2 27 x 10-5 mol / m2 2 - 2 3w0 40 x x 10-5 2 - 3 3.0 "53 x 10 2 - 4 3.0" 73 x 10-5 Samples 2 - 1 to 2 - 4 were developed in the same manner as in Example 1, using that in the following Results listed in Table IV were obtained.

Table IV Sample Amount of Kup- # S0.2 # G1.0 Gemespler A in the ------------ --------------- 4th layer (B) - (A) (C) - (B) (B) - ( A) (C) - (B) wicks 2 - 1 27x10-5 mol (m2 0.32 0.16 0.15 0.10 bulk density 2 - 2 40x10-5 mol / m2 0.32 0.18 0.20 0.13 Red density 2 - 3 53x10-5 mol / m2 0.32 0.20 0.25 0.18 Red density 2 - 4 73x10-5 Mol / m2 0.30 0.20 0.34 0.19 Red density 2-1 to -2-4 0.25 0.15 0.13 0.04 Green density 2-1bls - 0.22 0.15 0.14 0.06 Blue density 2-4 - SO 2 (B) - (A) Describes the difference between SO 2 in the case of development for 3 minutes and 15 seconds and SO 2 in the case the development for 2 min and 15 sec.

# S0,2 (C) - (B) Denotes the difference between S0,2 in the case of Development during 4 min and 15 sec and SO 2 in the case of development during 3 min and 15 sec.

(B) - (A) indicates the difference between G1.0 in the case of development for 3 min and 15 sec and G1.0 im for 2 min and 15 sec.

(C) - (B) denotes the difference between in the case of development for 4 min and 15 sec and G1 o in the case of development for 3 min and 15 sec.

As is clear from Table IV, if the amount of the coupler in the 4th layer (highly sensitive, red-sensitive emulsion layer) higher than 40 x 10 5 mol / m2, the gradation change (# G1.0) of red sensitivity is large and the balance between the red sensitivity and the green and blue sensitivities is remarkably damaged.

If in contrast to this, the amount of the coupler is 40 x 10 5 mol / m2 or less, the gradation change W of the red density becomes small and lies close to the gradation changes (# G1.0) of the green density and the blue density, so that as a result the balances of the densities are less damaged.

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Claims (1)

Patent claim Highly sensitive multilayer photosensitive Color negative materials consisting of a carrier and the following formed thereon Layers (1) a red-sensitive light-sensitive silver halide layer, the at least one silver halide emulsion layer having a non-diffusible one Cyan couplers wherein the silver halide particles have a numerical average particle size of more than 1.0µ, (2) a green-sensitive light-sensitive silver halide emulsion layer, the at least one silver halide emulsion layer having a non-diffusible one Magenta coupler wherein the silver halide particles have a numerical average particle size From less than I, O \ L have (3) a yellow filter layer and (4) a blue-sensitive one light-sensitive silver halide emulsion layer comprising at least one silver halide emulsion layer with a nondiffusible yellow coupler wherein the silver halide particles have a numerical mean particle size greater than I'Op, characterized in that that at least one of the silver halide emulsion layers is a development inhibitor releasing compound contains and the red-sensitive light-sensitive silver halide layer is built up from at least two silver halide emulsion layers, the numerical Average particle size of the red-sensitive in the furthest from the wearer Emulsion layer contained silver halide particles is more than 1.0µ and they are red-sensitive Emulsion layer at least 1.8 g / m² of silver and 40 x 10 5 mol / m² or less of the coupler forming the cyan dye, and the numerical average particle size of the silver halide particles in the other red-sensitive emulsion layer 1.0µ or less.