JPH0435054B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color reversal photosensitive material, and particularly to a silver halide color reversal print photosensitive material. (Prior Art) In color photographic films, there is a strong desire to improve color reproduction, and it is widely known that the multilayer effect is used as a method to improve color reproduction, especially saturation, of silver halide color photosensitive materials. ing. One of the methods for producing this multilayer effect is to adjust the content of development inhibitors liberated during development for each emulsion layer. In color reversal photography, the most common development inhibitor is iodide ions, and by adjusting the silver iodide content of silver halide emulsions for each emulsion layer, sensitive materials are designed to obtain desired color reproduction. be done. For example, a color in which a red-sensitive emulsion layer (hereinafter referred to as a red-sensitive layer), a green-sensitive emulsion layer (hereinafter referred to as a green-sensitive layer), and a blue-sensitive emulsion layer (hereinafter referred to as a blue-sensitive layer) are coated on a support in this order. One of the methods for increasing red color saturation and saturation in light-sensitive materials is to increase the silver iodide content of the silver halide emulsion used in the red-sensitive layer compared to the other two emulsion layers. be. The mechanism for enhancing the multilayer effect in this method is roughly as follows. When silver halide containing iodine in the red-sensitive layer is developed in the first development (black-and-white development), iodine ions diffuse from this emulsion layer to the green-sensitive layer and the blue-sensitive layer. This suppresses the development of unexposed silver halide in the green and blue sensitive layers. Due to this effect, the amount of silver halide in the green and blue sensitive layers to be developed in the second development (color development) increases, and the magenta density in the green sensitive layer constituting the red color and the yellow density in the blue sensitive layer increase. Concentration increases. Therefore, the saturation of red color is improved. One of the problems in designing conventional photosensitive materials for increasing the saturation by such a method is that it is difficult to easily create a multilayer effect from the lower layer (layer close to the support) to the upper layer. That is, in the development process, the developer permeates from the upper layer to the lower layer, so the higher the silver halide layer is, the earlier the development starts, and the less effective is the suppression of development from the lower layer to the upper layer. This drawback is significant in rapid processing. Further, if the silver iodide content of the silver halide in the lower layer is greatly increased in order to compensate for this drawback, disadvantages arise in photographic properties and processability. For example, in the characteristic curve (D-logE), adverse effects such as softening of highlight parts and reduction of desilvering and fixing speed occur. Therefore, a method of increasing the interlayer effect from the lower layer to the upper layer without significantly increasing the total silver iodide content of the light-sensitive material has been desired. (Objective of the Invention) One object of the present invention is to increase the development inhibition effect from the lower layer to the upper layer and to increase the color saturation of the emulsion layer. The other is to mutually increase the development inhibitory effect between emulsion layers with different spectral sensitivities and increase the color saturation of each emulsion layer without increasing the total silver iodide content in a multilayer sensitive layer. It is to let (Structure of the Invention) The object of the present invention is to have on a support at least two silver halide emulsion layers having substantially different average grain sizes and substantially the same spectral sensitivity;
Further, the silver halide grains of each emulsion contained in the emulsion layer contain silver iodide on the surface, and the silver iodide content of the silver halide grains having a larger average grain size is higher than that of the silver halide grains having a smaller average grain size. It has an emulsion layer having a larger spectral sensitivity (hereinafter referred to as a silver iodide content control emulsion layer) and a silver halide emulsion layer having a spectral sensitivity different from that of this emulsion layer. This is achieved by a silver halide color reversal light-sensitive material having at least one non-photosensitive intermediate layer containing a compound represented by the following general formula (1) between a sensitive silver halide emulsion layer. General formula (1)

[Formula] R ₁ and R ₂ each represent an alkyl group, a sulfonyl group, a sulfoalkyl group, a carboxyl group, a carboalkyl group, or an alkylsulfonyl group having 1 to 18 carbon atoms. However, the total number of carbon atoms in R ₁ and R ₂ is 7 or more. ” represents an alkyl group or an alkylsulfonyl group. However, the total number of carbon atoms in R ₁ and R ₂ is 7 or more. (Effects of the Invention) According to the present invention, the effect of inhibiting development between emulsion layers having different spectral sensitivities can be enhanced without substantially increasing the silver iodide content.
Particularly, preferred color reproduction can be obtained in a color reversal print photosensitive material with a soft tone (gamma value of 0.8 to 1.5). (Description of the Invention) In the present invention, the silver iodide content control emulsion layers have substantially different average grain sizes, have substantially the same spectral sensitivity, and iodization of the emulsion layers having a large average grain size. At least two emulsion layers satisfying the relationship that the silver content is larger than that of the emulsion layer with a small silver content (hereinafter referred to as a group of silver iodide content control emulsion layers)
It is particularly preferable that the In the present invention, it is particularly preferable to have two or more silver iodide content control emulsion layers or groups thereof having different spectral sensitivities, since the development inhibition properties of both layers can be mutually enhanced. The silver iodide content of each emulsion grain of the silver halide emulsion used in the present invention can be determined, for example, by
It can be measured by analyzing the composition of each particle using an analyzer. A specific method for measuring the silver iodide content of each grain is as follows. First, the sample emulsion is diluted 5 times with distilled water, a protease such as pronase is added, and the mixture is kept at 40°C for 3 hours to decompose the gelatin. Next, the sample is centrifuged to sediment the emulsion particles, and after removing the supernatant, distilled water is added again to redisperse the emulsion particles in the distilled water. After repeating this water washing operation twice, the sample is dispersed on the sample stage. After drying, carbon evaporation is performed and the sample is subjected to measurement using an X-ray microanalyzer. As the X-ray microanalyzer, a commercially available general device may be used, and no special specifications are required. In the present invention, an X-ray micro analyzer EMX-SM manufactured by Shimadzu Corporation was used. The measurement is performed by irradiating individual particles with an electron beam and measuring the characteristic X-ray intensity of each element in the particles excited by the electron beam using a wavelength dispersive X-ray detector. In order to determine the silver iodide content of a grain from the characteristic X-ray intensity of each element, perform similar measurements on grains with a known silver iodide content in advance to prepare a calibration curve. It can be calculated from the calibration curve. In the present invention, all of the red-sensitive, green-sensitive and blue-sensitive emulsion layers may be composed of emulsion layers having the above-mentioned relationship or a group thereof. When two or more silver iodide content control emulsion layers or groups thereof are present, the average silver iodide content of the emulsion layer or groups present on the side closer to the support is greater than the average silver iodide content of the emulsion layer or groups present on the side farther from the support. Greater than that of the silver oxide content control emulsion layer or layers thereof is desirable. Further, the emulsion layer of the present invention or a group thereof may be located at any position, but preferably the emulsion layer of the present invention or an emulsion layer belonging to a group thereof is not far from the support. The effect of the present invention is remarkable when an emulsion with a narrow grain size distribution is used, and it is particularly preferable when a so-called monodisperse emulsion is used in at least one layer or all layers. In the present invention, the difference in average particle size is desirably 0.05μ or more, preferably 0.1μ or more, and the effect of the present invention is significant if it is 0.3μ or more. Here, the grain size of silver halide is expressed by the grain diameter when the grain is a sphere or a shape that can be approximated to a sphere, and is expressed by the edge length x √4 when the grain is cubic. This is a value calculated from the projected area. For more information on particle size measurements please visit CE
McCs and T.H. James, “The Theory of
Photographic Process” 3rd edition pp. 36-43 (1966
(1979) "Basics of Photographic Engineering (Silver Halide Photography Edition)" published by McMillan, edited by the Photographic Society of Japan, pp. 277-278 (1979); "The Photo-graphic" published by Corona Publishing, etc.
Journal, Vol. 79, pp. 330-338. Also, the average grain size of silver halide is
This is the arithmetic average of the particle sizes determined by the method described above for at least 500 particles. In the present invention, when the silver iodide content control emulsion layer is composed of two or more layers, the silver iodide content is the average silver iodide content of each silver halide emulsion layer, and the iodine content is the average silver iodide content of each silver halide emulsion layer. It is the proportion of atoms. The value of the larger silver iodide content is 1.2 of that of the smaller one.
It is preferably at least 1.5 times, preferably at least 1.5 times. Further, the silver iodide-containing silver halide grains contained in the silver iodide content control emulsion layer also contain silver iodide on their surfaces. Having substantially the same spectral sensitivity means that the spectral sensitivity of the emulsion layer is close enough to be said to have the same sensitivity when the three colors of blue, green, and red are displayed. Often, it is not necessary that the spectral sensitivity distributions be exactly the same. In the present invention, the silver halide coating amount of each emulsion layer belonging to the same silver iodide content control emulsion layer group is preferably within 9 times, preferably within 3 times, the maximum coating amount and the minimum coating amount. In the sensitive material of the present invention, it is desirable to use colloidal silver in the non-photosensitive layer, and it is particularly desirable to use two or more layers containing colloidal silver. The total coating weight of colloidal silver is preferably at least 0.1 g/m ² . In the light-sensitive material of the present invention, providing a non-photosensitive gelatin-containing layer (intermediate layer) between the blue-sensitive layer, green-sensitive layer, and red-sensitive layer is very effective for enhancing the effects of the present invention. . Furthermore, one of the compounds represented by the general formula (1) is added to the non-photosensitive intermediate layer.
It is desirable to contain one or more of 50 mg/m ² or more. Examples of compounds included in the compound represented by general formula (1) include, but are not limited to, the following compounds. The efficiency of the present invention is considered to be due to the fact that when the development speeds of particles are compared in the first development step in the development process, particularly in the reversal process, the development speed of large particles is usually faster than that of small particles. Most of the iodine ions that exhibit development inhibition behavior are
Since it is released by the development of silver halide grains, it is thought that relatively increasing the silver iodide content of large silver halide grains exhibits a more effective development inhibiting effect. . As a result, even without increasing the overall silver iodide content, the concentration of iodide ions, which exhibit development inhibiting properties, increases, thereby increasing the development inhibiting properties of other layers and improving color reproducibility. The present invention is particularly effective when processed with a developer containing a silver halide solvent such as sodium sulfite, potassium thiocyanate, or thioethers, and the first developer in reversal processing is one specific example. . The preferred amount of these silver halide solvents added is 0.1 g, particularly preferably 0.5 g or more, and the upper limit is the saturated dissolution amount. Moreover, it is preferable to use two or more types in combination. In addition, the effect of the present invention is especially great in processing that requires speed, especially in high temperature (33°C or higher), short-term processing, especially when the first development time is less than 6 minutes.
It is particularly desirable that the time is within 3 minutes. The color reversal film processing process usually consists of the following steps: black and white development (first development) → stop → water washing → reversal → water washing → color development → stop → water washing → adjustment bath → water washing → bleaching → water washing → fixing → water washing → stabilization → drying. be treated as such. This step may further include a prebath, a predural bath, a neutralization bath, and the like. Furthermore, the steps of stopping, reversing, color development, conditioning bath, and washing with water after bleaching may be omitted. The reversal bath can be replaced by re-exposure or can be omitted by adding a brushing material to the color developing bath. Furthermore, the conditioning bath can also be omitted. The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination. In addition to the silver halide solvent mentioned above, this developer contains carbonates, borates, phosphates, sulfites, bromides,
Development inhibitors or antifoggants such as iodides and organic antifoggants may be included.
If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride,
Auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723, OLS
It may contain antioxidants such as those described in No. 2622950. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N −
β-methoxyethylaniline, etc.) can be used. In addition, LFA Meson's “Photography
"Processin Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent 2193015
No. 2,592,364, JP-A-48-64933, etc. may be used. In addition, it is possible to contain the additives described in the black and white developer. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromic acid, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. The silver halide in the silver iodide content control emulsion layer used in the present invention is preferably silver iodobromide containing 15 mol % or less of silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 12 mol % silver iodide. The average grain size of the silver halide grains in the photographic emulsion is not particularly limited, but is preferably 3 μm or less. The silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape, or may have an irregular crystal structure such as a spherical shape or a plate shape. It can also be a composite of shapes. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique
(Paul Montel, 1967), by GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include the one-sided mixing method, the simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die” edited by H. Frieser.
Grundlagender Photographischen Prozesse
mit Silberhalogeniden”
(Akademische Verlagsgesellschaft, 1968) 675
The method described on pages 734 to 734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. For more information about gelatin production, see Arthur Vuis, The Macromolecular Chemistry of Gelatin, (Academic Press,
Published in 1964). The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl tauric acid, sulfosuccinic acid Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon is fused to these nuclei;
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus , benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention contains, in addition to the compounds of the present invention, other dye-forming couplers, i.e., aromatic primary amine developers (e.g. , phenylenediamine derivatives, aminophenol derivatives, etc.) may be used. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloimidazole couplers, pyrazolo pyrazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, closed acylacetonitrile couplers, etc. Examples of yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.
In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in two or more different layers. Of course it doesn't matter. A known method such as the method described in US Pat. No. 2,322,027 can be used to introduce a coupler that can be used in the present invention into a silver halide emulsion layer.
For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate) or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, 2
butyl alcohol, methyl isobutyl ketone,
After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. The present invention will be explained in more detail with reference to Examples below. Example 1 A color reversal photographic material was prepared by coating the first to twelfth layers on a triacetate film base in the following order. First layer; antihalation layer (gelatin layer containing black colloidal silver). Second layer; gelatin middle layer. Third layer: low sensitivity red-sensitive emulsion layer. Gold-sulfur sensitized low-sensitivity silver iodobromide emulsion (silver iodide
6.0 mol%, average particle size approximately 0.5μ), a sensitizing dye [5,5'-dichloro-3,3'-di(3-sulfobutyl)-9-ethylthiacarbocyanine sodium salt], and a cyan coupler emulsion. [Coupler; 2-(heptafluorobutyramide)-5-{2'-(2'4''-di-t
-aminophenoxy)butyramide}-phenol coupler solvent; tricresyl phosphate] was added. However, the silver/coupler molar ratio is 10.0
The amount of silver coated was 0.7 g/m ² . 4th layer; high sensitivity red-sensitive emulsion layer. Gold and sulfur sensitized high-sensitivity silver iodobromide emulsion (silver iodide 6.0 mol%, average grain size approximately 0.7μ),
The same sensitizing dye and cyan coupler emulsion as in the third layer were added. However, the silver/coupler molar ratio is 10.0,
The amount of silver coated was 0.9 g/m ² . Fifth layer: gelatin middle layer. 6th layer: low-speed green-sensitive emulsion layer. A sensitizing dye [5,5'-diphenyl-9-ethyl-3,3'- disulfopropyloxacarbocyanine sodium salt] and magenta coupler emulsion [coupler; 1-(2,4,6-trichlorophenyl)-3-[3-(2,4
-di-t-amylphenoxyacetamido)benzamide]-5-pyrazolone coupler solvent; tricresyl phosphate] was added. However, the silver/coupler molar ratio is
10.0, the amount of silver coated was 0.6 g/m ² . 7th layer: Highly sensitive green-sensitive emulsion layer. A highly sensitive silver iodobromide emulsion (silver iodide 4 mol%, average grain size approximately 0.9μ) sensitized with gold and sulfur was
The same sensitizing dye and magenta coupler emulsion as in the layer were added. However, the silver/coupler molar ratio was 10.0, and the coating amount was 0.9 g/m ² . 8th layer; gelatin middle layer. Ninth layer; yellow filter layer (gelatin layer containing yellow colloidal silver). 10th layer; low-speed blue-sensitive emulsion layer. A yellow coupler emulsion [Coupler; α-pivaloyl-α-(1-
benzyl-5-ethoxy-3-hydantoynyl)-2-chloro-5
-hexadecyl-sulfonylaminoacetanilide coupler solvent; triisononyl phosphate] was added. However, the silver/coupler molar ratio is 7.0.
The amount of silver applied was 0.6 g/m ² . Layer 11: Highly sensitive blue-sensitive emulsion layer. A gold- and sulfur-sensitized high-sensitivity silver iodobromide emulsion (silver iodide 4 mol%, average grain size approximately 1.0μ) was
A yellow coupler emulsion similar to the layer was added. However, the silver/coupler molar ratio was 7.0 and the amount of silver coated was 1.2 g/m ² . Layer 12: Gelatin protective layer. However, each emulsion layer further contains a stabilizer; 4-hydroxy-6-methyl-1,
3,3a,7-tetrazaindene hardener; 1,3-bis-vinylsulfonylhydroxypropane coating aid; sodium p-dodecylbenzenesulfonate; sodium p-nonylphenoxypoly(ethyleneoxy)propanesulfonate; 2,5-di-t-
Sample 101 was prepared by adding and coating 70 mg/m ² of oxytylhydroquinone. Sample 101 except that the silver iodide content of the third, fourth, sixth, and seventh layers was changed to Table 1, and the sensitivity gradation was adjusted to be the same for each sample.
Samples 102, 103, and 104 were prepared in exactly the same manner as Sample 101. One simple method to quantitatively measure the interlayer effect is to expose a sample of the color reversal photosensitive material through a wedge with monochromatic light corresponding to the spectral sensitivity of the emulsion layer whose interlayer effect is to be investigated; There is a method of uniformly exposing to monochromatic light corresponding to the spectral sensitivity of other emulsion layers. In this example, in order to quantitatively determine the degree of the multilayer effect, the difference ΔD between the density Dh of the part of the emulsion layer that has been uniformly exposed and which has been affected by the multilayer effect and the density Ds of the part that has not been affected by the multilayer effect is ΔD. was measured. Also,
Since the way in which the interlayer effect is received varies depending on the exposure amount of the emulsion layer that is uniformly exposed, the exposure amount was adjusted so that the density of the area not affected by the interlayer effect was D=1.5. This evaluation method is shown in Figure 1. For Samples 101 to 104, based on the evaluation method for the multilayer effect as described above, in order to determine the degree of the multilayer effect from the A red-sensitive layer to the green-sensitive layer, wedge exposure W was applied to red monochromatic light, and then green A sample was given a uniform exposure U with monochromatic light, and a wedge exposure W was given with a monochromatic green light to determine the degree of the multilayer effect from the green-sensitive layer to the red-sensitive layer B, and then uniform exposure U was given with monochromatic red light. The following processing was carried out on the samples given the following conditions, and the density difference (ΔD _G , ΔD _R ) between the emulsion layers uniformly exposed was measured for each of the processed samples. The results are shown in Table 1.

【table】

[Table] First developer using the following composition: Water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl-4 -Hydroxylmethyl-3-pyrazolidone 29 Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml (pH 10.1) Reverse solution Water 700ml Nitrilo-N-N-N-trimethylene Phosphonic acid/6Na salt 3g Stannous chloride (dihydrate) 1g p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water 1000ml Color developer Water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Tertiary phosphorus Sodium acid (12 hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 1.5g N.ethyl-N-(β-methanesulfonamidoethyl)-3.methyl-4 -Aminoaniline・
Sulfate 11g Ethylenediamine 3g Add water to 1000ml Adjustment solution Water 700ml Sodium sulfite 12g Ethylenediamine, sodium tetraacetate (2
8g Thioglycerin 0.4g Glacial acetic acid 3ml Add water to 1000ml Bleach solution Water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ammonium ethylenediaminetetraacetate (dihydrate) 120.0g Potassium bromide 100.0g Add water 1000ml Fixer Water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stabilizer Water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0ml Add water 1000ml

[Table] As is clear from Table 1, in sample 102 of the present invention, compared to sample 101, the magenta density of the green-sensitive layer in the part where the red-sensitive layer was exposed to red monochromatic light is increased. This indicates that a large layer effect has occurred from the red-sensitive layer to the green-sensitive layer. In addition, in sample 104, both the magenta density of the green-sensitive layer where the red-sensitive layer was exposed to red monochromatic light and the cyan density of the red-sensitive layer where the green-sensitive layer was exposed to green monochromatic light were both compared to sample 101. This indicates that the mutual layering effect between the red-sensitive layer and the green-sensitive layer is increasing. Example 2 A color photographic material was prepared by coating the first layer (lowest layer) to the 11th layer on a paper support laminated on both sides with polyethylene. (Sample 201) First layer: antihalation layer (gelatin layer containing black colloidal silver). 2nd layer; low-sensitivity red-sensitive emulsion layer Gold-sulfur sensitized low-sensitivity silver bromide emulsion (silver iodide 3.0 mol%, average grain size approximately 0.4μ)
red sensitizing dye 5,5' dichloro-3,
3'-di(3-sulfobutyl)-9-ethylthiacarbocyanine sodium salt and cyan coupler An emulsified dispersion of the dioctylphthalate in the coupler solvent dioctyl phthalate was added. However, the silver/coupler ratio is 3.0, and the amount of coated silver is
It was applied at a weight of 0.18 g/m ² . 3rd layer: High-sensitivity red-sensitive emulsion layer High-sensitivity silver iodobromide emulsion sensitized with gold-sulfur (silver iodide 3.0 mol%, average grain size approx.
The same sensitizing dye and coupler emulsion dispersion as in the second layer were added to 0.6μ). However, the silver/coupler ratio was 3.0 and the amount of silver coated was 0.18 g/m ² . 4th layer: anti-halation layer (gelatin layer containing colloidal silver to prevent green halation) 5th layer: low-sensitivity green emulsion layer low-sensitivity silver iodobromide emulsion sensitized with gold and sulfur (silver iodide 3.0 Mol%, average particle size approx.
Sensitizing dye 5,5'-diphenyl-
9-ethyl-3,3'-disulfopropyloxacarbocyanine sodium salt and magenta coupler An emulsified dispersion of the solution in the coupler solvent trioctyl phosphate along with an antifade agent was added. However, the silver/coupler molar ratio is 10.0, and the amount of coated silver is 0.3.
It was applied so that it became g/ ^m2 . 6th layer: High-sensitivity green emulsion layer High-sensitivity silver bromide emulsion sensitized with gold and sulfur (silver iodide 3.0 mol%, average grain size approx.
The same sensitizing dye and coupler emulsion dispersion as in the fifth layer were added to 0.6μ). However, the silver/coupler molar ratio is 10.0 and the coated silver is 0.3 g/m ²
It was applied so that 7th layer: Yellow filter layer Gelatin layer containing yellow colloidal silver 8th layer: Low-sensitivity blue-sensitive emulsion layer Low-sensitivity silver iodobromide emulsion sensitized with gold and sulfur (silver iodide 3.0 mol%, average grain size
0.45μ), yellow coupler An emulsified dispersion of trinonyl phosphate in the coupler solvent was added. However, the silver/coupler molar ratio was 4.0, and the coating amount was 0.2 g/m ² . 9th layer: High-sensitivity blue-sensitive emulsion layer Gold-sulfur sensitized high-sensitivity silver iodobromide emulsion (silver iodide 3 mol%, average size 1.0μ),
The same coupler dispersion as in layer 8 was added. However, the silver/coupler molar ratio is 4.0,
The amount of silver coated was 0.25 g/m ² . 10th layer; gelatin protective layer The molar ratio of silver iodide in the 2nd, 3rd, 5th, 6th, 8th, and 9th layers of sample 201 was changed as shown in Table 2, and sample 202
~205 were made. Further, 60 mg/m ² of Compound 1-10 was added to the fourth and seventh layers of Samples 203, 204, and 206. However, it was produced in exactly the same manner as Sample 201 except that the sensitivity gradation was adjusted to be the same. For each sample, the original slide with the red, green, and gray color charts was exposed to light so that the gray color density on the print was 1.5, and after the following processing, the red, green, and gray charts on the print were photographed. Table 3 shows the results of measuring the cyan and magenta density values. Processing step 1st development (black and white development) 38℃1'15'' Water washing 38℃2'15'' Reverse exposure At least 100 Lux or more Color development 38℃1'30'' Water washing 38℃45'' Bleach-fix solution 38℃2' Water Washing 38℃2'15'' Total 10' [Processing solution composition] First developer (black and white development) Sodium tetrapolyphosphate 3.0g Sodium hydrogen carbonate 2.3g 1-phenyl-3-pyrazolidone 0.45g Anhydrous potassium sulfite 47g Hydroquinone 6g Carbonic acid Potassium 25g Sodium bromide 1.4g Potassium iodide (0.1%) 3ml Polyethylene glycol 20.0ml Polyethylene glycol 400 5.0g Add water 1 Add caustic soda to make it (pH: 10.2) Color developer Benzyl alcohol 12ml Sodium tetrapolyphosphate 3.0g Anhydrous sodium sulfite 7.5g Potassium carbonate 32.0g Potassium bromide 0.3g Potassium iodide (0.1%) 90.0ml Caustic soda 2.3g 3-Methyl-4-amino-N-ethyl-N
-β-methanesulfonamidoethylaniline 11.0g Ethylene glycol 20ml Add water 1 (pH: 10.75) Bleach-fix solution 5-amino-2-mercapto-1,3,4
-Thiadiazole 3.0g Ammonium bromide 50.0g Aqueous ammonia (28%) 30.0ml Ethylenediaminetetraacetic acid iron () ammonium monohydrate 45g Ethylenediaminetetraacetic acid disodium dihydrate 2g Anhydrous sodium sulfite 10g Ammonium thiosulfate 160.0ml Glacial acetic acid 5.9 Add 1 ml water (pH: 6.7)

【table】

[Table] As is clear from Table 3, when looking at the red coloring density, in the present invention samples 203 and 204 and the comparative example sample 205, the cyan density D _R in red decreased, and the magenta density D _G ,
Yellow density D _B is increasing. That is, it can be seen that the saturation of red color is extremely high. Next, looking at the green color density, in samples 203 and 204 of the present invention, the magenta density in the green decreased, and the cyan density increased.
Yellow density is increasing. That is, it can be seen that the saturation of green color is extremely high. The conventionally known method of improving the interlayer effect using silver iodide content was effective for red colors, but less effective for green colors. The use of the compound of the present invention was also effective for green color. The reason for this is that simply increasing the silver iodide content of the emulsion in the third layer delays development and does not provide much of an interlayer effect. Further, the effect of Compound 1-10 added to the fourth and seventh layers to prevent color mixing occurring in the color developing bath cannot be explained alone. Therefore, compound 1-10 added to the fourth layer is probably the first layer.
In development, it is presumed that by accelerating the development of the high iodine emulsion in the third layer, the release of iodine is accelerated, thereby increasing the multilayer effect from the lower layer to the upper layer through a synergistic effect. In addition, when comparing the development delay of the bottom layer (red-sensitive emulsion layer) with the value of sample 201 as the degree of softening of highlights at a processing time of 60 seconds, we can see that the development delay due to the previously known silver iodide content is Effect improvement method (sample
It can be seen that the development delay that occurs in 202, 206) does not occur. On the other hand, it can be seen that samples 203 and 204 of the present invention have particularly small development delay.

[Brief explanation of drawings]

FIG. 1 shows characteristic curves measured using a sample subjected to wedge exposure and uniform exposure, and using a filter with the same color as the exposed light. W is the characteristic curve of the wedge-exposed layer;
U is that of a uniformly exposed layer.

Claims (1)

[Scope of Claims] 1. A silver halide emulsion layer having on a support at least two silver halide emulsion layers having substantially different average grain sizes and having substantially the same spectral sensitivity, and each of the silver halide emulsion layers contained in the emulsion layer. An emulsion in which the silver halide grains of the emulsion contain silver iodide on the surface, and the silver iodide content of the silver halide grains with a larger average grain size is higher than that of the silver halide grains with a smaller average grain size. and a silver halide emulsion layer having a spectral sensitivity different from this emulsion layer, and between the emulsion layer and the silver halide emulsion layer having a different spectral sensitivity, the emulsion layer is represented by the following general formula (1). A silver halide color reversal photosensitive material having at least one non-photosensitive intermediate layer containing a compound. General Formula (1) [Formula] R ₁ and R ₂ each represent an alkyl group, a sulfonyl group, a sulfoalkyl group, a carboxyl group, a carboalkyl group, or an alkylsulfonyl group having 1 to 18 carbon atoms. However, the total number of carbon atoms in R ₁ and R ₂ is 7 or more.