JPH0356618B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photosensitive material,
In particular, the present invention relates to a technique for suppressing fogging of photosensitive materials during storage without impairing development progress. It is a well-known fact that various heterocyclic compounds are effective as antifoggants for suppressing the occurrence of fog during storage of color photosensitive materials. Regarding these prior art techniques, please refer to TH
“The Theory of Photographic” by James
Specifically, the following compounds are known: Azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, Chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl- 5-mercaptotetrazole); mercaptopyrimidines; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetrazaindenes),
Compounds such as pentaazaindenes; benzenethiosulfones, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be mentioned. However, conventionally known fog suppressants have the disadvantage that, although they exhibit a remarkable fog suppressing effect, they are accompanied by a desensitizing effect or that the increase in sensitivity is small when the development time is extended. Further, a compound having a repeating unit of the general formula () (described in Japanese Patent Publication No. 15471/1983), which will be described later, has similar drawbacks when used alone. In addition to the above-mentioned heterocyclic compounds, dyes such as monomethine cyanine dyes and merocyanine dyes are known as compounds that suppress the occurrence of fog during storage of color light-sensitive materials.
Publication No. 50-37538, Japanese Unexamined Patent Publication No. 153626/1983,
54-119917, etc.). However, these compounds alone cannot provide a sufficient fog suppressing effect. In general, in silver halide color light-sensitive materials, even if two types of compounds are used together, the effects of each of the two types of compounds are not necessarily produced in an additive manner. Therefore, when two types of compounds are used together, extremely high selectivity is required. The present invention has been made to solve these problems, and the first object is to provide a silver halide color light-sensitive material that has little desensitization effect, suppresses fog, and is stabilized. A second object is to provide a silver halide color light-sensitive material that is less prone to fogging even when stored for a long period of time after production. A third object is to provide a silver halide color light-sensitive material that exhibits a large increase in sensitivity when the development time is extended. The object of the present invention is to add a compound having a repeating unit of the following general formula () and monomethine represented by the general formula () to a silver halide color light-sensitive material having a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer. This was achieved by the simultaneous presence of a cyanine dye. General formula () Here, R ₁ is −OR, −SR,

[Formula], R and R' are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group,
Sulfoalkyl (or salt thereof) group, carboxyalkyl (or salt thereof) group, aralkyl group, or sulfo (or salt thereof)-, carboxyl (or salt thereof)-, alkyl having 1 to 4 carbon atoms,
Alkoxy or halogen having 1 to 4 carbon atoms
6 to 12 carbon atoms with or without substituents
represents an aryl group or a cycloalkyl group,
Alternatively, R and R' may both form an alkylene ring or an alkylene ring containing -O-, and R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom or an alkyl having 1 to 4 carbon atoms. represents a group, and Y ₁ , Y ₂ , Y ₃ and Y ₄ each have 2 carbon atoms.
~12 polymethylene group, C2-12 polymethylene group substituted with C1-4 alkyl group, or sulfo (or salt thereof)-, carboxyl (or salt thereof)-, alkyl group having 1-4 carbon atoms represents an arylene group or a cycloalkylene group with or without a substituent of - or halogen-, Z represents -O-, _-SO2- or _-CH2- , l and m represent 0 or 1; represent. General formula () In the above formula, Y ₅ and Y ₆ are each a nonmetal necessary to form a nitrogen-containing heterocyclic nucleus selected from the group consisting of benzothiazole, naphthothiazole, benzoselenazole, naphthoselenazole, benzoxazole, and naphthoxazole. Represents a group of atoms, and these heterocyclic nuclei include halogen atoms,
A lower alkyl group, a lower alkoxy group, a phenoxy group, or a phenyl group may be substituted. R ₆ and R ₈ each represent an aliphatic group which may be substituted and whose carbon chain may be interrupted by an oxygen atom or a sulfur atom, and at least one of R ₆ or R ₈
1 represents the aliphatic group having any one of a hydroxyl group, a carboxyl group, and a sulfo group. R ₇ represents a hydrogen atom or a lower alkyl group. Preferably, in the general formula (), R ₁ is

[Formula] is represented, and R and R' are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, or a sulfoalkyl group (or a salt thereof).
group, carboxyalkyl (or salt thereof) group, aralkyl group, or sulfo (or salt thereof)-,
Carboxyl (or its salt) -, carbon number 1-4
represents an aryl group having 6 to 12 carbon atoms with or without an alkyl, alkoxy having 1 to 4 carbon atoms, or halogen substituent, or a cycloalkyl group, or both R and R' are an alkylene ring. Alternatively, an alkylene ring containing -O- may be formed, R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and Y ₁ , Y ₂ , Y ₃ and Y ₄ are a polymethylene group having 2 to 4 carbon atoms, and a polymethylene group having 1 to 4 carbon atoms, respectively.
A polymethylene group having 2 to 4 carbon atoms substituted with 4 alkyl groups, or sulfo (or a salt thereof)-,
Carboxyl (or its salt) -, carbon number 1-4
represents an arylene group with or without an alkyl or halogen substituent, or a cycloalkylene group, Z represents -CH ₂ -, and l
and m represents 0 or 1. Further, the heterocyclic nucleus formed by Y ₅ and Y ₆ may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a phenyl group. Furthermore, R ₆ and R ₈ each have 1 to 1 carbon atoms.
8 alkyl group, and at least one of R ₆ or R ₈ has a hydroxyl group, carboxyl group or sulfo group. Next, typical compounds having a repeating unit of the general formula () used in the present invention are shown,
The compounds used in the present invention are not limited to these. (However, n indicates the number of S-tricine rings contained in the molecule. The same applies hereinafter) Next, typical compounds of the general formula () used in the present invention are shown, but the compounds used in the present invention are not limited to these. The compound having a repeating unit represented by the general formula () of the present invention is a known compound, and is
It can be easily synthesized by the method described in JP-A-15471. The compounds of the present invention represented by the general formula () are also known and can be easily synthesized by conventionally known methods. Specifically, British Patent No.
It can be easily synthesized according to the methods described in US Pat. No. 660,408, US Pat. No. 3,149,105, and the like. The amount of the compound having the repeating unit of general formula () is not particularly limited, but when used in a silver halide emulsion layer, it is 0.01 to 50 g/mol Ag, and when used in a protective layer or intermediate layer, it is 0.05 to 50 g/mol Ag. 250g/Kg
Gelatin is preferred. There is no particular limit to the amount of the compound represented by general formula (), but when using it in a silver halide emulsion layer,
0.01-1.0 g/mol Ag is preferred. The compound of general formula () is more preferably used in a blue-sensitive emulsion layer, and it is particularly preferable to use a compound having a repeating unit of general formula () and a compound of general formula () in the same emulsion layer. A compound having a repeating unit of general formula () or a compound represented by general formula () can be incorporated into a photographic emulsion by a conventional method. It is usually dissolved in a solvent such as methanol, ethanol, water, or ketones soluble in cellosolve water and added to the emulsion. It may be added at any stage in the emulsion manufacturing process, but it is generally preferable to add it after chemical ripening. In the photographic emulsion layer of the photographic light-sensitive material of the present invention, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubes and octahedrons, or irregular crystal shapes such as spherical and plate shapes. It may be a crystalline substance or a compound of these crystalline forms.
It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Makig 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 one-sided mixing method, 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).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with 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 present. In the photographic emulsion used in the present invention, for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of light-sensitive materials,
Various compounds can be included. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted 1,3,3a,7) tetrazaindenes), pentaazaindenes, etc.; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. Many compounds can be added. For example, those described in US Pat. No. 3,954,474, US Pat. No. 3,982,947 and Japanese Patent Publication No. 52-28660 can be used. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a nude water washing method in which gelatin is gelatinized may be used, and inorganic silver chlorides, anionic surfactants, anionic polymers (e.g. A precipitation method (flocculation) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example H. Frieser ed. Die
Grundlager der Photographischen Prozesse
mit Silberhalogeniden (Akrdemische
Verlagsgesellschaft.1968) pages 675-734 can be used. Namely, 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, reduction sensitization using noble metal compounds (e.g., gold complex salts,
Complex salts of periodic table group metals such as Pt, Ir, and Pd)
A noble metal sensitization method using a sensitizer can be used alone or in combination. Specific examples of these include U.S. Patent No. 1574944, U.S. Pat.
No. 2728668, No. 3656955, etc., and U.S. Patent Nos. 2983609 and 2419974 for reduction sensitization methods.
The precious metal sensitization method is described in US Pat. No. 2,399,083, US Pat. No. 2,448,060, British Patent No. 618,061, etc. 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 for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives,
It may also contain imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent No. 2400532,
No. 2423549, No. 2716062, No. 3617280, No.
Those described in No. 3772021, No. 3808003, British Patent No. 1488991, etc. can be used. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. The photographic emulsion used in the present invention may be spectrally sensitized in the blue, green, and red regions using methine dyes or the like. Useful sensitizing dyes include, for example, German Patent No. 929080;
U.S. Patent No. 2493748, U.S. Patent No. 2503776, U.S. Patent No. 2519001
No. 2912329, No. 3656959, No. 3672897,
No. 3694217, No. 4025349, No. 4046572, British Patent No. 1242588, Special Publication No. 14030, No. 52-
It is described in No. 24844. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
No. 3397060, No. 3522052, No. 3527641, No. 3527641, No. 3522052, No. 3527641, No.
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3814609, No. 3837862, No. 4026707, British Patent No. 1344281, British Patent No. 1507803, Special Publication No. 43-4936,
No. 53-12375, JP-A No. 52-110618, No. 52-
Described in No. 109925. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390, 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color is formed by oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) during a color development process. Examples of compounds that can be used include magenta couplers, 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
There are cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, etc., yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include:
There are naphthol couplers, phenol couplers, etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. 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 may contain a colorless DIR coupling compound that is colorless and releases a development inhibitor. In order to introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 can be used. 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 (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lauramide), fatty acid esters (e.g. di- butoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., 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, After being dissolved in secondary butyl alcohol, methyl isobutyl ketone, 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 mixed and used. The color light-sensitive material of the present invention may contain various other known additives, such as dyes, hardeners, surfactants, antifading agents, development accelerators, UV absorbers, matting agents, and optical brighteners. can be mentioned. For specific information on these, please refer to research, for example.
Research Disclosure
No. 176, RD-17643, etc. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic light-sensitive materials. be done. Also useful as flexible supports are:
Films, baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymer paper coated or laminated with The support may be colored using dyes or pigments. It may be black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. Specific examples of the silver halide color light-sensitive material of the present invention include color films for photography such as color negative films and color reversal films, as well as light-sensitive materials for printing such as color paper. For photographic processing of the photosensitive material of the present invention, for example, Research Disclosure Co., Ltd.
Any of the known methods and known treatment liquids, such as those described in RD-17643, No. 176, No. 28-30 (RD-17643), can be applied. Processing temperatures are usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may be used. When forming a dye image, conventional methods can be applied.
For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 667-701); developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other A color reversal method in which a dye-positive image is obtained by performing appropriate fog treatment and subsequent development; a silver image in which a photographic emulsion layer containing a dye is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dye. A basic bleaching method is used.The color developer generally consists of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer, such as phenynediamines (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-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. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. The color developer may also contain a PH buffer, a development inhibitor or an antifoggant, and the like.
In addition, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, and antioxidants are added. It may also include. These additives and specific examples are described in Research Disclosure (RD-17643) as well as in U.S. Patent No.
It is described in No. 4083723, OLS No. 2622950, etc. After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be carried out at the same time as the fixing treatment, or may be carried out separately. Examples of bleaching agents include iron (), cobalt (), chromium (), copper (),
Compounds of polyvalent metals such as, peracids, quinones, nitrone compounds, etc. are used. 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. Example 1 A sample was prepared by coating the following emulsion layers or auxiliary layers on a triacetyl cellulose support in the following order. 1st layer; antihalation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; 2,5-di-t-octylhydroquinone;
1 kg of the emulsion obtained by dissolving 100 c.c. of dibutyl phthalate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of water-soluble 10% gelatin is mixed with 1 kg of 10% gelatin to obtain a dry film thickness. It was applied like this. 3rd layer; low-sensitivity red-sensitivity emulsion layer 100 g of cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2″,4″-di-t-aminophenoxy)butyramide}-phenol
and 500 g of an emulsion obtained by dissolving 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of a 10% aqueous gelatin solution to form a red-sensitive low-iodophilic silver bromide emulsion. 1 kg (70 g, containing 60 g of gelatin, iodine content: 4.0 mol%) was mixed and coated to a dry film thickness of 2 μm (silver amount: 0.5 g/m ² ). 4th layer: Highly sensitive red-sensitive emulsion layer 100 g of cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2'',4''-di-t-aminophenoxy)butyramide}-phenol
and 1000 g of an emulsion obtained by dissolving 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of a 10% aqueous gelatin solution to form a red-sensitive, low-iodine silver bromide emulsion. 1 kg (containing 70 g of silver, 60 g of gelatin, and iodine content of 4.0 mol%) was mixed and coated to a dry film thickness of 2 μm (silver amount: 0.8 g/m ² ). 5th layer; middle layer 2,5-di-t-octylhydroquinone,
1 kg of the emulsion obtained by dissolving 100 c.c. of dibutyl phthalate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of water-soluble 10% gelatin is mixed with 1 kg of 10% gelatin to obtain a dry film thickness. It was applied like this. 6th layer; low edge sensitivity emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is a magenta coupler instead of a cyan coupler
Emulsion obtained in the same manner as the emulsion of the first layer except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
500g of edge-sensitive, low-iod silver bromide emulsion (1kg of silver 70
g, gelatin (60 g, iodine content: 2.5 mol%) and coated to a dry film thickness of 2.0 μm (silver amount: 0.7 g/m ² ). 7th layer: highly sensitive emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is magenta coupler instead of cyan coupler
Emulsion obtained in the same manner as the emulsion of the first layer except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
1000g of edge-sensitive, low-iodation silver bromide emulsion (1kg of silver 70
g, gelatin (60 g, iodine content: 2.5 mol%) and coated to a dry film thickness of 2.0 μm (coated silver amount: 0.7 g/m ² ). 8th layer; middle layer 1 kg of emulsifier used in the 3rd layer was mixed with 1 kg of 10% gelatin.
Kg and applied to a dry film thickness of 1 μm. Ninth layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of 1 μm. 10th layer; Low-sensitivity blue-sensitive emulsion layer. Yellow coupler instead of cyan coupler, α-(pivaloyl)-α-(1-benzyl-5
-Ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the first layer was mixed with blue-sensitive low-iodobromide silver. Emulsion 1
Kg (contains 70g silver, 60g gelatin, iodine content is
2.5 mol %) and coated to give a dry film thickness of 2.0 μm (coated silver amount: 0.6 g/m ² ). 11th layer; Highly blue-sensitive emulsion layer. Yellow coupler is used instead of cyan coupler, α-(pivaloyl)-α-(1-benzyl-5
-Ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the first layer was mixed with blue-sensitive highly iodobromide silver. Emulsion 1
Kg (contains 70g silver, 60g gelatin, iodine content is
2.5 mol %) and coated to give a dry film thickness of 2.0 μm (coated silver amount: 1.0 g/m ² ). 12th layer; 2nd protective layer 1 kg of emulsifier used in the 3rd layer was mixed with 1 kg of 10% gelatin.
Kg and applied to a dry film thickness of 2 μm. 13th layer; 1st protective layer Fine grain emulsion that is not chemically sensitized (grain size
A 10% gelatin aqueous solution containing 0.15μ, 1 mol% silver iodobromide emulsion) was added to a silver coating amount of 0.3g/m ² and a dry film thickness of 1μ.
It was applied so that The sample prepared as described above will be designated as sample number 101, and will be used as a comparative sample from now on. Various compounds having repeating units of the general formula () described in the text and various compounds represented by the general formula () are mixed into a 10th layer, a low-sensitivity blue-sensitive emulsion layer and an 11th layer, a high-sensitivity blue-sensitivity emulsion layer. Sample 102 was added to each of the following as shown in Table 1.
~127 were prepared. The obtained sample was exposed to a light source of 4800 〓, and the illuminance of the exposed surface was
Color images were obtained by exposure through a sensitometric wedge with white light at 1000 lux, followed by inversion as described below. Also, 60℃×60%
After aging at RH for 2 days, the same exposure and processing were performed to obtain a color image. The treatment steps and treatment liquid used here are as follows. Processing process Process Time (minutes) Temperature 1st development 6 38℃ Water washing 2 〃 Inversion 2 〃 Color development 6 〃 Adjustment 2 〃 Bleaching 6 〃 Fixing 4 〃 Water washing 4 〃 Stable 1 Room temperature Drying <First developing bath> Water 700ml Tetrapolyline Sodium acid 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl 4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) Add 2 ml water to 1000 ml <Reverse bath> Water 700 ml Nitrilo-N-N-N-trimethylenephosphonic acid 6Na salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Hydroxide Sodium 8g Glacial acetic acid 15ml Add water to 1000ml <Color developing bath> Water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium triphosphate (12 hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Water Sodium oxide 3g Citrazic acid 1.5g N-ethyl-N-(β-sulfamidoethyl)-
3-Methylaminoaniline sulfate 11g Ethylenediamine 3g Add water to 1000ml <Adjustment bath> Water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water to 1000ml <Bleaching bath> Water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Iron()ammonium ethylenediaminetetraacetate (dihydrate) 120.0g Potassium bromide 100.0g Add water 1.0 <Fixing bath> Water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0 g Sodium bisulfite 5.0g Add water 1.0 <Stabilization bath> Water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0ml Add water 1.0ml The optical density of the yellow image of the obtained sample was measured using a blue filter. The anti-fogging effect was evaluated by measuring the A constant concentration (D=
Sensitivity was also expressed as the reciprocal of the exposure amount required to obtain a yellow density of 1.00). The results obtained are shown in Table-1. From Table 1, it can be seen that by using a compound having a repeating unit of the general formula () in combination with a compound represented by the general formula (), the desensitizing effect is reduced and fog is suppressed. It can also be seen that even when a fog suppressing effect equivalent to that achieved when a compound having a repeating unit of the general formula () is used alone, the sensitivity increases significantly after 10 minutes of development.

[Table] Example 2 A multilayer color photosensitive material was prepared on a cellulose triacetate film support, comprising each layer having the composition shown below. 1st layer; antihalation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; 3rd layer; 1st red-sensitive emulsion layer; Silver emulsion (silver iodide; 5 mol%)... Silver coating amount 1.79 g/m ² Sensitizing dye... 6 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...... per 1 mol of silver
1.5×10 ^-5 mol Coupler A...0.04 mol per 1 mol of silver Coupler C...0.003 mol per 1 mol of silver Coupler D...0.0006 mol per 1 mol of silver 4th layer; second red sensation Emulsion layer Silver iodobromide emulsion (silver iodide; 4 mol%)...Silver coating amount 1.4 g/ ^m2 Sensitizing dye...3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...1 silver against mole
1.2×10 ^-5 mol Coupler E: 0.02 mol per mol of silver Coupler C: 0.0016 mol per mol of silver 5th layer; Intermediate layer 6th layer, same as the 2nd layer; 1st green-sensitive emulsion Layer Silver iodobromide emulsion (silver iodide; 4 mol%)...Amount of coated silver 1.5 g/ ^m2 Sensitizing dye...3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...1 mol of silver Coupler B: ^0.05 mol per mol of silver Coupler M: 0.008 mol per mol of silver Coupler D: 0.0015 mol per mol of silver 7th layer; 2 Green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 5 mol %)... Coated silver amount 1.6 g/m ² Sensitizing dye... Per 1 mol of silver
2.5×10 ^-5 mol Sensitizing dye...for 1 mol of silver
0.8×10 ^-5 mol Coupler B...0.02 mol per mol of silver Coupler M...0.003 mol per mol of silver Coupler D...0.0003 mol per mol of silver 8th layer: Yellow filter layer Gelatin Yellow colloidal silver and 2,5-
and an emulsified dispersion of di-t-octylhydroquinone. 9th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol %)... Coating amount silver 1.5 g/m ² Coupler Y... 0.25 mol per mol of silver 10th layer; Second blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol%)...Amount of coated silver
1.1 g/m ² Coupler Y...0.06 mol per mol of silver 11th layer; Protective layer Trimethylmethanoacrylate particles (diameter approx.
Apply a gelatin layer containing 1.5μ). In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. The sample prepared as described above was designated as sample 101. Compound sensitizing dye used to prepare the sample: anhydro-5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)-4, 5, 4', 5'-
Dibenthiacarbocyanine hydroxide/triethylamine salt sensitizing dye: anhydro-9-ethyl-5.5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
-Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
{β-[β-(γ-sulfopropoxy)ethoxy]
Ethylimidazolocarboxyanine hydroxide sodium salt The sample prepared as described above will be designated as sample number 201, and this will be used as a comparative sample thereafter. Various compounds having a repeating unit of the general formula () described in the text and various compounds represented by the general formula () are added to each of the 9th layer, the first blue-sensitive emulsion layer, and the 10th layer, the second blue-sensitive emulsion layer. Sample 202 was added as shown in Table 2.
~227 were prepared. The obtained sample was exposed to a light source of 4800 〓, and the illuminance of the exposed surface was
Color images were obtained by exposure through a sensitometric wedge with white light at 1000 lux and subsequent processing as described below. Further, after aging at 60° C. x 60% RH for 2 days, the same exposure and processing were performed to obtain a color image. The development process used here was carried out at 38°C as described below. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stabilization... 3 minutes 15 seconds each The composition of the treatment liquid used in this step is as follows. <Color developer> Sodium nitrotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline Sulfate 4.5g Add water 1 <Bleach solution> Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-sodium tetraacetic acid iron salt 130g Glacial acetic acid 14ml Add water 1 <Fixer> Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 <Stabilizing solution> Formalin 8.0ml Add water 1 Change the optical density of the yellow image of the obtained sample to blue It was measured through a filter to evaluate the anti-gabbing effect. Based on the characteristic curve, the sensitivity was expressed as the reciprocal of the exposure amount required to obtain a yellow density of "minimum density 0.2". Further, the fog value represents the value obtained by subtracting the mask density from the minimum density. The results obtained are shown in Table-2. From Table 2, it can be seen that by using the compound represented by the general formula () and the compound represented by the general formula () in combination, the desensitizing effect is small and the antifogging effect can be obtained. Furthermore, the sensitivity increases significantly when the development time is extended.

【table】

Claims (1)

[Scope of Claims] 1. A silver halide color light-sensitive material having a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer, and a compound having a repeating unit of the following general formula () and a compound represented by the general formula () A silver halide color photosensitive material characterized by containing a compound. General formula () Here, R ₁ represents -OR, -SR, [Formula], and R and R' are respectively a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group,
Sulfoalkyl (or salt thereof) group, carboxyalkyl (or salt thereof) group, aralkyl group, or sulfo (or salt thereof)-, carboxyl (or salt thereof)-, alkyl having 1 to 4 carbon atoms,
Alkoxy or halogen having 1 to 4 carbon atoms
6 to 12 carbon atoms with or without substituents
represents an aryl group or a cycloalkyl group,
Alternatively, R and R' may both form an alkylene ring or an alkylene ring containing -O-, and R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom or an alkyl having 1 to 4 carbon atoms. represents a group, and Y ₁ , Y ₂ , Y ₃ and Y ₄ each have 2 carbon atoms.
~12 polymethylene group, C2-12 polymethylene group substituted with C1-4 alkyl group, or sulfo (or salt thereof)-, carboxyl (or salt thereof)-, alkyl group having 1-4 carbon atoms represents an arylene group or a cycloalkylene group with or without a substituent of - or halogen-, Z represents -O-, _-SO2- or _-CH2- , l and m represent 0 or 1; represent. General formula () In the above formula, Y ₅ and Y ₆ are each a non-containing member selected from the group consisting of benzothiazole, naphthothiazole, benzoselenazole, naphthoselenazole, benzoxazole, and naphthoxazole. Represents a group of metal atoms, and these heterocyclic nuclei include halogen atoms,
A lower alkyl group, a lower alkoxy group, a phenoxy group, or a phenyl group may be substituted. R ₆ and R ₈ each represent an aliphatic group which may be substituted and whose carbon chain may be interrupted by an oxygen atom or a sulfur atom, and at least one of R ₆ or R ₈
1 represents the aliphatic group having any one of a hydroxyl group, a carboxyl group, and a sulfo group. R ₇ represents a hydrogen atom or a lower alkyl group.