JPS6113583B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for preventing fogging caused by pressure strain occurring in ultra-high-sensitivity silver halide color light-sensitive materials. In so-called internal color light-sensitive materials containing a color-forming coupler in the light-sensitive material, a dye having a sulfo group or a carboxyl group is used as a color sensitizer.
This is because when a color-forming coupler is added to the photosensitive material,
Although extremely large desensitization occurs, this desensitization can be almost prevented when dyes having sulfo groups or carboxyl groups are used. In order to obtain ultra-high-sensitivity color sensitive materials with particularly good graininess,
Desensitization, which tends to worsen graininess, must be avoided, so it is essential to use color-sensitizing dyes with sulfo groups or carboxyl groups in order to produce such ultra-high-sensitivity color sensitive materials. It was hot. However, an emulsion layer consisting of silver bromide containing 4 mol % or more of silver iodide and in which the average grain size of these silver halide grains is 1 μ or more (hereinafter referred to as an ultra-high-sensitivity emulsion layer)
When a spectral sensitizing dye having a sulfo group or a carboxyl group is used, fogging is extremely likely to occur due to pressure distortion. That is, when such photosensitive materials are bent or tightly rolled, extremely large fogging often occurs. Therefore, methods have been sought to reduce the sensitivity to pressure distortion in producing ultra-high-sensitivity color sensitive materials with good image graininess. As a result of research, it has been found that silver iodide containing 4 to 12 mole percent of silver iodide, which is color sensitized with a dye having at least one sulfo group or a carboxyl group, and has an average grain size of 1 micron or more. At least one silver halide comprising silver iodobromide grains, a dye-forming coupler, a binder, and a high-boiling organic solvent having a boiling point of 175° C. or higher at normal pressure in an amount of 20% by weight or more based on the binder. It has been found that this can be significantly reduced by a color photographic image forming method characterized by color-developing a color photographic light-sensitive material having an emulsion layer on a support. If too large a quantity of the above oil is added, coating becomes impossible or adhesion deteriorates, so the upper limit of the amount of oil added is determined by this limit. A preferable upper limit is about 100% of the binder. High boiling point organic solvents that can be used in the present invention include:
All of the following conditions (1) to (4) are satisfied. (1) The boiling point is higher than 175°C, preferably higher than 250°C at normal pressure (1 atm). (2) Solubility in water (at 25℃) is approximately 10% by weight
and (3) a water solubility (at 25°C) of less than about 10% by weight. (4) Be liquid or waxy at 100℃. However, even if one type of high-boiling point solvent is not in liquid or wax form at 100°C or higher, this does not apply if two or more types of high-boiling point solvent are in liquid or wax form. Examples of high-boiling organic solvents preferably used in the present invention include US Pat. No. 2,322,027 and US Pat.
No. 2835579, Special Publication No. 46-23233, U.S. Patent
No. 3287134, British Patent No. 958441, Japanese Unexamined Patent Publication No. 1973-
1031, UK Patent No. 1222753, US Patent No. 3936303,
JP-A-51-26037, JP-A-50-82078, US Pat. No. 2353262, US Pat. No. 2852383, US Pat.
No. 3676137, No. 3676142, No. 3700454, No.
No. 3748141, No. 3837863, OLS2538889, JP-A No. 51-27921, No. 51-27922, No. 51-26035
No. 51-26036, No. 50-62632, Special Publication No. 1977-
No. 29461, US Pat. No. 3,936,303, and US Pat. No. 2,56658. High boiling point organic solvents more preferably used in the present invention include esters (e.g. phthalates, phosphates, citric esters, benzoic esters,
Examples include fatty acid esters, carbonate esters, etc.), amides (eg, fatty acid amides, sulfonamides, etc.), ethers (eg, allyl ethers, etc.), alcohols, paraffins, and the like. Particularly preferably used high-boiling organic solvents include, for example, phthalate esters (e.g., dibutyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate, butyl phthalyl butyl glycolate, dibutyl monochloro phthalate, etc.), phosphate esters (e.g., tricresyl phosphate, tricylelyl phosphate, tris(isopropylphenyl) phosphate, tributyl phosphate, trihexyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, trioleyl phosphate, tris(butoxyethyl) phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, etc.), citric acid esters (e.g., o-acetyltriethyl (or butyl, hexyl, octyl) , nonyl, decyl)
citrate, triethyl (or butyl, hexyl, octyl, nonyl, decyl, tridecyl) citrate, etc.), benzoic acid esters (e.g.
Butyl (or hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyle, tetradecyl, hexadecyl, octadecyl, oleyl, etc.) benzoate, pentyl o-methylbenzoate, decyl p-methylbenzoate, octyl o-chlorobenzoate, lauryl p-chloro Benzoate, propyl 2,4-dichlorobenzoate, octyl 2,4-dichlorobenzoate,
Stearyl 2,4-dichlorobenzoate, oleyl 2,4-dichlorobenzoate, octyl p
-methoxybenzoate, etc.), fatty acid esters (e.g., hexadecyl, myristate, dibutoxyethyl succinate, dioctyl adipate, dioctyl azelate, decamethylene-1,
10-diol diacetate, triacetin, tributin, benzylcaprate, pentaerythritol tetracapronate, isosorbide dicaprylate, etc.), amides (e.g., N・N-dimethyllauramide, N・N-diethylcapryl) amide, N-butylbenzenesulfonamide, etc.), trioctyl trimellitate, and chlorinated paraffin. The above oils may be introduced into the silver halide emulsion layer using the method described in US Pat. No. 2,322,027.
For example, after dissolving in an organic solvent with a boiling point of about 30°C to 150°C, such as lower alkyl acetate such as ethyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., the hydrophilic Dispersed into colloids. Any of the above oils can be used as a dispersion medium for couplers. Therefore, when it is added, it can be added while increasing the amount of oil in the emulsion and improving the stability of the emulsion when preparing the emulsion of the coupler. In this case, the coupler is less likely to precipitate in the emulsion, and the effect of killing two birds with one stone can be achieved. The dye having at least one sulfo group or carboxyl group used in the present invention is represented by the following general formula (). Here, m and n each represent 1 or 2, p represents 1, 2 or 3, and q represents 1 or 2. L is a methine group (e.g., an alkyl group (e.g., methyl,
ethyl, etc.), aryl groups (e.g., phenyl, etc.)
), Z and Z ₁ each represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus, and examples of the heterocyclic ring include, for example, a thiazole nucleus (e.g. , thiazole, 4
-Methylthiazole, 4-phenylthiazole,
4,5-dimethylthiazole, 4,5-diphenylthiazole, etc.), benzothiazole nuclei (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 5-nitrobenzothiazole, 6-nitrobenzothiazole, 4-methylbenzothiazole,
5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-
Bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-
Carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5
-Chlor-6-nitrobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-
Methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, 5-
phenylbenzothiazole, etc.), naphthothiazole nucleus (e.g., naphtho[2.1
-d] thiazole, naphtho[1,2-d]thiazole, naphtho[2,3-d]thiazole, 5-methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 5-methoxynaphtho[2,3-d]thiazole, etc.), thiazoline nucleus (e.g., thiazoline, 4-methylthiazoline, 4-nitrothiazoline, etc.), oxazole nucleus ( For example, oxazole, 4-
Methyloxazole, 4-nitrooxazole,
5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, etc.), benzoxazole nucleus (benzoxazole,
5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5
-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole,
6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5.6
-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, etc.), naphthoxazole cores (e.g., naphtho[2.
1-d]oxazole, naphtho[1,2-d]oxazole, naphtho[2,3-d]oxazole, 5-nitronaphtho[2,1-d]oxazole, etc.), oxazoline nucleus (e.g., 4,4-dimethyl oxazoline, etc.), selenazole core (e.g., 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole, etc.), benzoselenazole core (e.g., benzoselenazole core, 5-chlorobenzoselenazole, 5 −
nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, etc.), naphthoselenazole core (for example, naphtho[2.
1-d]selenazole, naphtho[1,2-d]selenazole, etc.), 3,3-dialkylindolenine nucleus (e.g.,
3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5-nitroindolenine renin, 3,3-dimethyl-5-methoxyindolenine, 3,3'-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine, etc.), imidazole core (e.g., 1-alkylimidazole), , 1-alkyl-4-phenylimidazole, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichloro-benzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkylnaphtho[1.2-d]imidazole, 1-allyl-
5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlor Benzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-arylnaphtho[1.2-d]
imidazole, the aforementioned alkyl is especially 1 carbon atom
-8, such as unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hydroxyalkyl groups (eg, 2-hydroxyalkyl, 3-hydroxypropyl, etc.). The aforementioned aryl represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl, and the like. ), pyridine nucleus (e.g. pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.), quinoline nucleus (e.g. quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2
-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 6-ethoxy-4-quinoline , 6-nitro-4-quinoline, 8-chloro-4
-quinoline, 8-fluoro-4-quinoline, 8-
Methyl-4-quinoline, 8-methoxy-4-quinoline, isoquinoline, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6
-nitro-3-isoquinoline, etc.), imidazo[4,5-b]quinoxaline nuclei (e.g., 1,3
-diethylimida[4,5-b]quinoxaline,
6-chloro-1,3-diallylimidazo [4,5
-b] quinoxaline, etc.), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, etc. X represents an inorganic or organic acid anion such as chloride, bromide, iodide, p-trienesulfonate, methanesulfonate, methylsulfate, ethersulfate, perchlorate, and the like. R and R ₁ each represent an alcohol residue, such as an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms {unsubstituted alkyl group (for example, methyl, ethyl,
propyl, isopropyl, butyl, hexyl, dodecyl, octadecyl, etc.), substituted alkyl groups,
For example, aralkyl groups (e.g., benzyl, β-phenylethyl, etc.), hydroxyalkyl groups (e.g., 2-hydroxyethyl, 3-hydroxypropyl, etc.), carboxyalkyl groups (e.g.,
2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, etc.), alkyl groups substituted with sulfo groups (e.g. 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, etc.),
-Sulfobutyl, 2-[3-sulfopropoxy]
ethyl, 2-hydroxy-3-sulfopropyl,
3-sulfopropoxyethoxyethyl, etc.), sulfate alkyl groups (e.g., 3-sulfate propyl, 4-sulfate butyl, etc.)} or aryl groups (e.g., phenyl group, tolyl group,
(naphthyl group, methoxyphenyl group, chlorophenyl group, etc.). At least one of R, R ₁ , Z, Z ₁ and L contains at least one group selected from a group consisting of a carboxyl group or a sulfo group. When q is 1, the dye has a betaine type structure. mold. Representative examples of useful merocyanine dyes having at least one sulfo group or carboxyl group used in the present invention include those represented by the following general formula (). General formula () In the formula, Z ₂ has the same meaning as Z and Z ₁ described above. R ₂ and R ₃ have the same meaning as R and R ₁ . r has the same meaning as n. L has the same meaning as above. m ₁ represents 1, 2, 3 or 4; d represents 1, 2 or 3. Q ₁ is an oxygen atom, a sulfur atom, or

[Formula] (R ₄ is an aliphatic group as described above). Q represents a nonmetallic atom group necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus, and examples of the nuclear heterocycle include 2-pyrazolin-5-one nucleus (e.g., 3-methyl-1-phenyl). -2-pyrazolin-5-one nucleus, 1-phenyl-2-pyrazolin-5-one nucleus, 1-(2-benzothiazolyl)-3
-Methyl-2-pyrazolin-5-one nucleus, 1-phenyl-3-(2-sulfo-propyl)-2-pyrazolin-5-one nucleus, 1-(4-sulfophenyl)-2-pyrazolin-5-one ), isoxazolone nucleus (e.g. 3-(4-sulfophenyl)-5(4H)-isoxazolone nucleus, 3
-(4-sulfobutyl)-5-(4H)-isoxazolone nucleus, etc.); oxindole nucleus (e.g., 1-ethyl-
2,3-dihydro-2-oxindole nucleus, 1
-X-sulfoalkyl-2,3-dihydro-2-
oxindole nuclei, etc.), barbituric acid nuclei or 2-thiobarbituric acid nuclei such as 1-alkyl (e.g. 1-methyl, 1-ethyl, 1-propyl, 1-heptyl, etc.);
3-dialkyl {e.g. 1,3-dimethyl, 1,
3-diethyl, 1,3-dipropyl, 1,3-diisopropyl, 1,3 dicyclhexyl, 1,3
-di(β-methoxyethyl)}, 1,3-diaryl {e.g., 1,3-diphenyl, 1,3-di(p-chlorophenyl), 1,3-di(p-ethoxycarbonyl-phenyl)}, 1-sulfoalkyl {e.g. 1-(2-sulfoethyl); 1-(3-sulfopropyl); 1-(4-sulfoheptyl), etc.}, 1,3-disulfoalkyl {e.g. 1,3
-di(2-sulfoethyl); 1,3-di(3-sulfopropyl); 1,3-di-(4-sulfocyclohexyl etc.}, 1,3-di-(sulfoaryl) {e.g. 1.
3-di-(4-sulfophenyl), etc.}, barbituric acid nuclei or thiobarbituric acid nuclei containing 1-sulfoaryl {e.g., 1-(4-sulfophenyl), etc.}, rhodanine nuclei such as rhodanine nuclei, 3-sulfoalkylrhodanine nuclei {e.g. 3-2(-sulfoethyl)rhodanine nucleus, 3-(3-sulfopropyl)rhodanine nucleus, 3-(4-sulfobutyl)rhodanine nucleus, etc.}; 3-sulfoarylrhodanine nucleus {e.g. 3-(4- 3-alkylrhodanine nucleus {e.g., 3-ethylrhodanine nucleus, 3-allylrhodanine nucleus, etc.}, 3-carboxyalkylrhodanine nucleus {e.g., 3-(2-carboxyethyl)rhodanine nucleus) . sulfoethyl)-2-thio-2.4
-oxalidinedione nucleus, 3-(4-sulfobutyl)-2-thio-2,4-oxazozinedione nucleus, 3-ethyl-2-thio-2,4-oxazolinedione nucleus, 3-(3-carboxy propyl)-2
-Thio-2,4-oxazolidinedione nucleus, etc.;
2,4-thiazolidinedione nucleus e.g. 3-(4-
sulfophenyl)-2,4-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 3-ethyl-2,4-thiazolidinedione nucleus, 3-phenyl-2,4-thiazolidinedione nucleus, 3-α-naphthyl-2・4-thiazolidinedione nucleus, etc.; Thiazolidinone nucleus, e.g. 3-(2-sulfoethyl)-4-thiazolidinone nucleus, 3-(4-sulfophenyl)-4-thiazolidinone nucleus, etc.; 2,4-imidazolidinedione (hydantoin) nucleus, e.g. 3-(2-sulfoethyl)-2・4-
imidazolidinedione nucleus, 3-(4-sulfophenyl)-2,4-imidazolidinedione nucleus, etc.;
3-ethyl-2,4-imidazolidinedione nucleus,
3-phenyl-2,4-imidazolidinedione nucleus, 1,3-diethyl-2,4-imidazolidinedione nucleus, 1-ethyl-3-phenyl-2,4-imidazolidinedione nucleus, 1-ethyl-3 -Phenyl-
2,4-imidazolidinedione nucleus, 1,3-diphenyl-2,4-imidazolidinedione nucleus, etc., 2-thio-2,4-imidazolidinedione nucleus (i.e., 2-thiohydantoin nucleus), e.g. 2-thio -2,4-imidazolidinedione nucleus, 3-(4
-sulfobutyl)-2-thio-2,4-imidazolidinedione nucleus, 3-(2-carboxyethyl)-
2-thio-2,4-imidazolidinedione nucleus, 3
-Phenyl-2-thio-2,4-imidazolidinedione nucleus, 3-(3-sulfopropyl)-2-thio-2,4-imidazolidinedione nucleus, 1,3-diethyl-2-thio-2. 4-imidazolidinedione nucleus, 1-ethyl-3-phenyl-
2-thio-2,4-imidazolidinedione nucleus,
1,3-diphenyl-2-thio-2,4-imidazolidinedione nucleus, etc.; 2-imidazolin-5-one nucleus, such as 2-(3
-sulfopropyl)-2-imidazolin-5-one nucleus, etc. At least one of R ₂ , R ₃ , Z ₂ , Q ₁ , Q, and L contains at least one group selected from carboxyl or sulfo groups. Among the cyanine dyes contained in the general formula (),
Sulfo-substituted cyanine dyes represented by the following general formula (') are known to exhibit J-band sensitization in silver halide emulsions, and these sulfo-substituted cyanine dyes are particularly advantageous in the present invention. used. (′) Here, Z ₃ and Z ₄ are respectively -O-, -N-Ro,
Represents S, Se. (Ro is alkyl or substituted alkyl). Z ₅ and Z ₆ represent an atomic group forming a benzene ring or a naphthalene ring (the benzene ring and naphthalene ring may have a substituent). R _M is H
Alternatively, it represents a lower alkyl group (eg, methyl, ethyl, etc.), an aryl group (eg, phenyl, etc.), or a substituted aryl group. R and R ₁ have the same meanings as in the general formula (), but at least one of R and R ₁ is an alkyl group containing a sulfo group. P ₁ is 1 or 2. X and q have the same meanings as in general formula (). In the general formula ('), Z ₃ and Z ₄ are each -O
- or -N-R _O (R _O is a C ₁ to C ₄ alkyl group)
and Z ₅ and Z ₆ are chlorine, bromine, C ₁ to C ₄ alkyl, C ₁ to _{C 4} alkoxyhydroxy, aminoacetyl, C ₁ to _{C 4} alkoxycarbonyl, or a benzene ring having a phenyl group, or α・β・
It forms a ββ-naphthyl ring, and R _M is H or
C ₁ to C ₄ alkyl group, phenyl group, R,
A dye in which R ₁ is a C ₁ to C ₆ alkyl group having at least one sulfo group, P ₁ is 1 or 2, q is 1 or 2, and X is the same as in the general formula (). In this case, the effect of the present invention is particularly remarkable. Specific examples of spectral sensitizing dyes used in the present invention are:
It is as follows. Dye 1 Bis-[2-{3-(2-sulfoethyl)-5-phenylbenzoxazole}]-β-ethyltrimethinecyanine Pyridine salt Dye 2 Bis-[2-{3-(3-sulfopropyl)- 5-
phenylbenzoxazole}]-β-ethyltrimethine cyanine dye 3 [2-{3-(4-sulfobutyl)benzothiazole}][2-(3-ethylbenzothiazole)]-
β-Methyltrimethine cyanine dye 4 Bis-[2-{3-(4-sulfobutyl)benzothiazole}]-β-methyltrimethylcyanine
Pyridine salt dye 5 [2-(1,6-diethylquinoline)] [2-{3
-(4-sulfobutyl)-5-methoxybenzoselenazole}] methinecyanine dye 6 Bis-[2-{1-ethyl-3-(3-sulfopropyl)-5,6-dichlorobenzimidazole}]trimethine cyanine Sodium salt dye 7 Bis-[2-{3-(4-sulfobutyl)benzoselenazole}]-β-methyltrimethinecyanine Pyridine salt dye 8 [2-{3-(3-sulfobutyl)benzothiazole}] [2 -(3-ethylbenzothiazole)-β
-Methyltrimethine cyanine dye 9 [2-{3-(3-sulfopropyl-5-phenylbenzoxazole}] [2-{1-ethyl-3
-(3-sulfopropyl)-5,6-dichlorobenzimidazole}] trimethine cyanine dye 10 bis-[2-{3-(3-sulfopropyl)-5-
Methylbenzoselenazole}]-β-methyl-trimethinecyanine dye 11 [2-{1-(3-sulfopropyl)-6-methylquinoline}][2-({3-(3-sulfopropyl)-5 -methoxybenzoselenazole}] methinecyanine dye 12 bis[-2-{3(3-sulfopropyral)-5-
Chlor benzothiazole)]-β-ethyl trimethine cyanine pyridine salt dye 13 bis-[2-{3-(3-sulfopropyl)naphtho[1,2-d]thiazole}]-β-ethyl-trimethine Cyanine triethylamine salt dye 14 2-{3-(3-sulfopropyl)naphtho[1.
2-d]thiazole}][2-{1-ethyl-(3-
sulfoprovir)-5,6-dichlorobenzimidazole}]trimethinecyanine/triethylamine salt dye 15 [2-{3-(3-sulfobutyl)-5-chlorobenzoxazole}][2-{1-ethyl-3-
(3-sulfobutyl)-5,6-dichlorobenzimidazole}]trimethinecyanine/sodium salt dye 16 [2-{3-(3-sulfopropyl)-5-chlorobenzothiazole}][2-{3-( 3-sulfoprovir)-5-chlorobenzoxazole}-β
-ethyl-trimethine cyanine/pyridine salt dye 17 anhydro[2-{3-(3-sulfopropyl)
-5-phenylbenzoxazole}][2-(3
-ethyl-5-chlorobenzoxazole)]-β
-Ethyltrimethine cyanine/hydroxide dye 18 [2-{3-(3-sulfopropyl)nut[2,3-d]thiazole}][5-(1-ethylrhodanine)]-α-ethyl-tetra Methine merocyanine/sodium salt dye 19 [2-(3-ethyl-5-phenylbenzoxazole}][2-{1-ethyl-3-(3-sulfopropyl)5,6-dichlorobenzimidazole]trimethine Cyanine dye 20 [2-(3-ethyl, benzothiazole)] [2
-{3-(2-sulfoethyl)-5-phenylbenzo-oxazole]-β-methyl-trimethine cyanine dye 21 [2-{1-(3-sulfopropyl)quinoline}][2-(1-methyl quinoline) )] Methine-cyanine dye 22 [2-(3-ethyl benzoxazole)]
[2-{1-ethyl-3-(2-carboxyethyl)-5,6-dichlorobenzimidazole}]
-Trimethine cyanine bromine salt dye 23 {2-(3-ethyl naphtho(1,2-d)oxazole)} {2-{1-ethyl-3-(2-carboxyethyl)5,6-dichlorobenz imidazole}trimethine-cyanine bromine salt dye 24 [2-(1-ethylquinoline)][2-{3-(3
-sulfopropyl)-5-phenylbenzoxazole}] methinecyanine dye 25 [2-{3-(3-sulfopropyl)naphtho[1,2-d]thiazole}] [2-(3-ethyl-
naphtho[1,2-d]thiazole)}-β-phenyl trimethine cyanine dye 26 bis-[2-{3-(3-sulfopropyl)-5-
Chlor benzothiazole}] methinecyanine triethylamine salt dye 27 [2-{3-(2-sulfoxyethyl)benzothiazole}] [2-(1-ethylquinoline)] methinecyanine bromine salt dye 28 [2-{3- (2-sulfoxyethyl)-5-methoxy benzoselenazole} [2-(1-ethyl quinoline)] methinecyanine dye 29 [2-{3-(2-hydroxyethyl)-5-methylbenzothiazole} ] [2-{3-(3-sulfoxybutyl)-5-methyl benzothiazole}]
-β-ethyltrimethine cyanine dye 30 [2-{3-(3-sulfopropyl)-5-carboxybenzothiazole}] [2-{3-(3-sulfopropyl)-5-hydroxybenzothiazole}] -β-Ethyl-trimethine cyanine dye 31 Bis-[2-{3-(3-sulfopropyl)naphtho[1,2-d]thiazole}]-β-(2-carboxyphenyl)-trimethine cyanine sodium Salt dye 32 Bis-[2-{3-methyl-5-(4-sulfophenyl)benzoxazole}]-β-ethyl trimethine cyanine Dye 34 [2-{3-(3-sulfopropyl)-5-chlorobenzoxazole}] [5-{1-(2-(2-
hydroxyethoxy)ethyl)-3-phenyl-
2-thiohydantoin}] dimetine merocyanine dye 35 [2-(3-ethyl benzothiazole)] [2
-{3-ethyl-6-(δ-sulfobutoxy)benzothiazole]pentamethine cyanine dye 36 [4-(1-ethyl-8-fluoroquinoline)][2-{3-(2-carboxyethyl)- naphtho[2,1-d]thiazole}]trimethinecyanine bromine salt dye 37 2-(m-nitrostyryl)-1-(3-sulfopropyl)-6-ethoxyquinoline dye 38 bis-[2-{3- (3-sulfopropyl)-5.
6-dimethyl benzothiazole}]-γ-methyl pentamethine cyanine triethylamine salt dye 39 [2-{3-ethyl naphtho[1,2-d]thiazole}] [2-{3-(4-sulfobutyl) naphtho[2.1-d]oxazole}-γ-methyl-
Pentamethine cyanine dye 40 Bis-[2-(3-sulfoallylbenzothiazole)}trimethine cyanine Triethylamine salt dye 41 Bis-[2-(3-ethylbenzothiazole)]-
β-(γ-sulfopropoxy), trimethine cyanine When the use of the present invention is essential, 4 mol% to 12
mol% (the effect of the present invention is particularly remarkable is 6 mol%)
When using an ultra-high-sensitivity emulsion made of silver bromide containing iodine (~10 mol%), an ultra-high-sensitivity emulsion layer in which the average grain size of all silver halide grains in that layer is 1 μ or more is used. It's time to set it up. In such a case, according to the present invention, the pressure fog can be prevented or reduced by dispersing and adding the above-mentioned oil to the above-mentioned ultra-high sensitivity emulsion layer. The mechanism of this action is that as the silver halide grains of the present invention increase in size, they become more susceptible to deformation due to external pressure and fog increases, whereas the dispersed oil It is presumed that this is because plasticizing the material reduces deformation caused by external pressure. Additionally, various oils can be used to achieve the objectives of the present invention, taking advantage of the physical properties associated with the oil being microdispersed in a hydrophilic binder such as gelatin. Further, the ultra-high sensitivity emulsion layer may contain two or more emulsions, and even in this case, the effects of the present invention remain unchanged. The above average particle size is described in "The Theory of the Photographic Process" by CEK Mies et al. (published by Macmillan), from the bottom 7 lines of the right column on page 36 to line 18 of the left column on page 38, and in "Particle Size Analysis". (1966) no.
It can be measured by the particle size measurement method described on pages 45 onwards. The present invention has made it possible to fully achieve the following objects. To provide an ultra-highly sensitive color photosensitive material that has good graininess and does not fog due to pressure strain.
To provide an ultra-highly sensitive color photosensitive material using a silver bromide emulsion having an average grain size of 4 mol% or more and containing 4 mol% or more of silver iodide. The grain size distribution of the emulsion used in the present invention may be narrow or wide. 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), VL Zelikman 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 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 of the simultaneous mixing methods, it is also possible to use a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, a so-called controlled double jet method. 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 copper salt thereof, an iron salt or an iron complex salt, etc. may be present. In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, in addition to the ultra-high-sensitivity emulsion described above, any of silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. may also be used. Preferred silver halide is silver iodobromide or silver iodochlorobromide containing 2 mol % or more of silver iodide. Since almost all currently known color image-forming couplers have the side effect of desensitization to varying degrees, the present invention provides a solution for cases where commonly known couplers are used, i.e. ultra-high sensitivity. This effect is exhibited when applied to color photosensitive materials. Representative examples of color image forming couplers that can be used in the present invention include the following. Examples of the yellow color-forming coupler include known open-chain ketomethylene couplers. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is U.S. Pat. No. 2,875,057.
No. 3265506, No. 3408194, No. 3551155,
3582322, 3725072, 3891445, West German Patent No. 1547868, West German Patent Application (OLS) 2213461
No. 2219917, No. 2261361, No. 2263875,
This is described in No. 2414006, etc. Examples of the magenta coloring coupler include pyrazolone compounds, indazolone compounds, and cyanoacetyl compounds, with pyrazolone compounds being particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. Pat.
No. 3062653, No. 3127269, No. 3311476,
3419391, 3519429, 3558319, 3519391, 3519429, 3558319,
No. 3582322, No. 3615506, No. 3834908, No.
3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, OLS No. 2417945, OLS No. 2418959
No. 2424467, Special Publication No. 1973-6031, etc. Examples of cyan color-forming couplers include phenol compounds and naphthol compounds. Specific examples are US Patent Nos. 2369929 and 2434272.
No. 2474293, No. 2521908, No. 2895826,
Same No. 3034892, No. 3311476, No. 3458315, Same No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, West German Patent Application (OLS) No. 2414830,
It is described in No. 2454329 and Japanese Patent Application Laid-Open No. 1983-59838. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, specification of patent application No. 49-98469, 50-
Specification No. 118029, West German patent application (OLS) 2418959
Examples include those listed in No. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
3790384, 3632345, West German patent application (OLS) 2414006, 2454301, 2454329
Examples include those described in British Patent No. 953454 and Japanese Patent Application No. 146570-1970. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development, such as those described in U.S. Pat. No. 3,297,445, U.S. Pat. can. Two or more of the above couplers may be contained in the same layer. The same compound may be contained in two or more different layers. In order to introduce the coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2,322,027 can be used. In this case, any of the oils mentioned above can be used as a coupler solvent. or dissolved in an organic solvent with a boiling point of about 30°C to 150°C, such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. It is then dispersed into hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. 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. These couplers are generally added in an amount of 2 x 10 ^-3 mol to 5 x 10 ^-1 mol, preferably 1 x 10 ^-2 mol to 5 x 10 ^-1 mol, per mol of silver in the emulsion layer. 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. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.
As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent No. 2614928, U.S. Patent No. 3132945,
3186846, 3312553, British Patent No. 861414,
It is described in No. 1033189, No. 1005784, and Japanese Patent Publication No. 42-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferred. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. Typical synthetic hydrophilic polymer substances include West German Patent Application (OLS) No. 2312708 and U.S. Patent No. 3620751.
No. 3879205 and Special Publication No. 7561 of 1973. The use of polymer latex in the present invention further enhances the effect. Examples of such polymer latexes include acrylic ester polymers, methacrylic ester polymers, other α-substituted acrylic ester polymers, acrylamide derivative polymers, methacrylamide derivative polymers, and α-substituted acrylamide derivative polymers. polymers, vinyl ester polymers, halogenated vinyl polymers, halogenated vinylidene polymers, styrene and styrene derivative polymers, ethylene polymers, propylene polymers, butylene polymers, butadiene polymers, vinyl ether polymers, acrylonitrile polymers, etc. There are vinyl polymers, which may be homopolymers or copolymers of these monomers or with other vinyl compounds. The aqueous dispersion of a vinyl polymer that is more effective when used in the present invention contains a dispersant for emulsion polymerization of 0.1 to 20% by weight based on the vinyl polymer monomer, the above-mentioned vinyl monomer, and the vinyl monomer. Emulsify water with about 4 to 10 times the amount of degassed nitrogen, add other additives necessary for normal emulsion polymerization, and finally start emulsion polymerization, such as hydrogen peroxide, potassium persulfate, etc. It can be obtained by adding an agent and carrying out emulsion polymerization according to a conventional method. The choice of vinyl polymer has considerable latitude and is not particularly critical, but particularly good are homopolymers or copolymers of acrylic esters and methacrylic esters. In general, polymers that are insoluble in water and have a relatively low elastic modulus are recommended, and polymers with a glass transition point below room temperature are particularly preferred.
In this sense, acrylate monomers, higher methacrylate monomers, and higher vinyl ester monomers are preferred, especially copolymers, which show good results. In addition, in order to improve the compatibility with the silver halide gelatin emulsion, emulsion polymerization is carried out in advance by adding an appropriate amount of gelatin,
It may be carried out in a system in which a water-soluble polymer such as polyvinyl alcohol or polyacrylamide is dissolved. In order not to impair the transparency of the emulsion film formed after coating and drying these aqueous vinyl polymer dispersions and silver halide gelatin, the particle size of the vinyl polymer dispersions is determined by Although sufficient care must be taken to prevent the polymer from becoming too large, it is relatively easy to achieve the desired product using standard emulsion polymerization techniques, such as adjusting the surfactant concentration, monomer concentration, stirring speed, polymerization temperature, and other factors. get. Generally, it is desirable that the value is at least 1μ or less, preferably 0.05~
It is within 0.01μ. Next, an example of producing an aqueous vinyl polymer dispersion will be shown.
The inside of 25 closed reaction vessels made of glass lined with a temperature controller, a stirrer, a reflux condenser, a heating device, and a gas inlet were replaced with nitrogen gas, and 12 degassed and nitrogen-substituted distilled water were added. Add 3 kg of vinyl monomer from which the polymerization inhibitor has been removed by purification. Next, the above-mentioned dispersant [] (type and number of grams are shown in the table below) is added and the reaction mixture is vigorously stirred at 500 to 800 rpm to emulsify. Next, 0.15 g of potassium persulfate as a polymerization initiator and other stabilizers are added, and the mixture is heated and maintained at 90 to 100°C while stirring. If the reaction is continued for 6 hours, the polymerization will be completely completed. By carrying out steam distillation for 1 hour to remove some residual monomer, the desired stable aqueous vinyl polymer dispersion can be obtained. The particle size of the solid vinyl polymer dispersed in these aqueous dispersions is approximately 0.05~
They were spherical particles with a diameter of 0.2μ and most of them were approximately 0.1μ. A film obtained by adding an aqueous gelatin solution to these aqueous dispersions and coating and drying is an optically transparent and very good film. Therefore, even when these aqueous dispersions are added to silver halide gelatin emulsions, they can be dispersed very easily and uniformly. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have 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 necessary. 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 soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known Nudel water washing method in which gelatin is gelatinized may be used as a means for this purpose. Utilizing inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may also be used. The process of removing soluble salts may be omitted. Silver halide emulsions do not undergo chemical sensitization,
Although so-called primitive emulsions can be used, they are usually chemically sensitized. For chemical sensitization, please refer to the above-mentioned book by Glafkides or Zelikman et al. or Die Grundlegen der edited by H. Frieser.
Photographischen Progesse mit
Silberhalogeniden (Akademische
Verlagsgesellschaft, 1968) can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
Described in Nos. 2278947, 2728668, and 3656955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include US Pat. Nos. 2487850, 2419974,
Described in Nos. 2518698, 2983609, 2983610, and 2694637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in the periodic table group such as platinum, iridium, and palladium can be used.
It is described in issues such as No. 618061. The photographic light-sensitive material produced using the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. Examples include 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.) ), activated vinyl compound (1.
3,5-Triacryloyl-hexahydro-s-
triazine, bis(vinylsulfonyl)methyl ether, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), isoxazole kind,
Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, and the like can be used alone or in combination. Specific examples include U.S. Patent No. 1870354, U.S. Patent No. 2080019, U.S. Patent No. 2726162, U.S. Pat.
No. 2870013, No. 2983611, No. 2992109, No.
No. 3047394, No. 3057723, No. 3103437, No. 3047394, No. 3057723, No. 3103437, No.
No. 3321313, No. 3325287, No. 3362827, No. 3321313, No. 3325287, No. 3362827, No.
No.3539644, No.3543292, British Patent No.676628, No.3543292, British Patent No.676628,
No. 825544, No. 1270578, Dotsu Patent No. 872153, No.
It is described in No. 1090427, Special Publication No. 34-7133, No. 46-1872, etc. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsion dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast Various known surfactants may be included for various purposes such as sensitization, sensitization), etc. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) , polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and non-ionic materials such as urethanes or ethers. surfactants; triterpenoid saponins, alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates,
Alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine imides, Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used. Specific examples of these surfactants are listed in the U.S. patent.
No. 2240472, No. 2831766, No. 3158484, No.
3210191, 3294540, 3507660, British Patent No. 1012495, 1022878, 1179290, British Patent No.
No. 1198450, Japanese Unexamined Patent Publication No. 117414, US patent
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, British Patent No. 1397218, US Patent No. 3133816, No. 3441413
No. 3475174, No. 3545974, No. 3726683,
No. 3843368, Belgian patent No. 731126, British patent
No. 1138514, No. 1159825, No. 1374780, Tokko Akira
40-378, 40-379, 43-13822, U.S. Patent No. 2271623, 2288226, 2944900, U.S. Pat.
No. 3253919, No. 3671247, No. 3772021, No.
3589906, 3666478, 3754924, West German patent application OLS 1961638, Japanese Patent Application Laid-Open No. 50-59025, etc. Next, examples will be described below to explain the present invention in detail, but the present invention is not limited to these examples. Example 1 A silver iodobromide emulsion containing 8 mol% silver iodide (average grain size 1.2μ, gelatin 70g/Kg emulsion) was prepared using spectral sensitizing dye 1 alone or a mixture of compound 1 and compound 42. and spectrally sensitized as shown in the table. Next, add 100g of the coupler shown below. Dissolve in 200 c.c. of ethyl acetate, add various amounts of tricresyl phosphate, and use sodium dodecylbenzenesulfonate as an emulsification dispersion aid to prepare a 10% aqueous gelatin solution in a homoblender.
g to prepare emulsions A to E shown below.

【table】

[Table] These emulsions were added to the above spectrally sensitized emulsion according to the table, and the coating solution thus prepared was coated on a triacetate cellulose film support at a silver coating weight of 5.
It was coated so that the amount was g/m ² . At this time, as a hardening agent, 2,4-dichloro-6-hydroxy 1.
3 g of 3.5 triazine soda was added as an aqueous solution to 1 kg of emulsion.

[Table] 1 Color development 3 minutes 15 seconds (38℃) 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 the process is as follows. Color developer Sodium nitrilotriacetate 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 Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium 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 Measure the concentration of the magenta pressure fog that occurred at the folded part of the sample after processing through a green filter Measured using a self-recording densitometer. The results are shown in the table.

[Table] Here, ΔD is the value obtained by subtracting the fog density value of the unfolded portion from the maximum density value of the folded portion. (The smaller this value is, the smaller the pressure fog is.) Also, oil/gel represents the weight ratio of oil and gelatin contained in the sample. Sample (1
~6)~(1~10) have a large ΔD because supersensitization occurs and the sensitivity is high. As is clear from the table, the larger the oil/gel is, the more the fogging caused by pressure strain, which is very likely to occur in ultra-high-sensitivity emulsions, can be significantly suppressed. Example 2 Here, a case will be described in which the ultra-high sensitivity emulsion used in Example 1 is mixed with an emulsion of lower sensitivity. The same results as in Example 1 are obtained, but since a low-sensitivity emulsion is mixed, the occurrence of pressure fog is suppressed compared to when an ultra-high-sensitivity emulsion is used alone. Silver iodobromide emulsion containing 8 mol% silver iodide (average grain size 0.8
Sample 2-1 was prepared in the same manner as in Example 1 for an emulsion prepared by mixing 300 g of gelatin (70 g/Kg emulsion).
2-10 was prepared and the pressure fog density was measured. The results are shown in the table.

【table】

[Table] Example 3 Here, the case where a polymer latex was added to the emulsion used in Example 1 will be described. Samples 3-1 to 3-5 were prepared in the same manner as samples 1-6 to 1-10 by dispersing an ethyl acrylate polymer in an aqueous solution using a homoblender as a polymer latex and adding 30 g of this per 1000 g of emulsion. . These samples were subjected to the measurement of the density of pressure buildup at the folded portion in the same manner as in Examples 1 and 2. The results are shown in the table.

[Table] As you can see from the table, △D is the same in the table.
It is smaller than △D of oil/gel. In other words, by adding the ethyl acrylate polymer, the occurrence of pressure build-up can be further suppressed. Example 4 Here, in order to examine the effect of increasing oil/gel in the red-sensitive emulsion layer, samples 1-1 to 1 shown in Example 1 were used.
Compound 12 and emulsion 1Kg instead of the dye used in -5
Emulsions F to J were prepared in the same manner as in Example 1, except that 0.1 g was used per sample and the couplers shown below were used as couplers, and Samples 4-1 to 4-
5 was produced. Samples 4-1 to 4-5 were folded and the density of the fogged portion was measured through a red filter, and the results are shown in the table.

[Table] As can be seen from the table, even in the red-sensitive emulsion layer,
The larger the oil/gel, the more pressure build-up can be suppressed. Example 5 The examples described so far were for a single emulsion layer, but this example describes the case of multilayer coating.The following layers 1 to 11 were coated as the first layer on a cellulose triacetate film support. Samples 5-1 to 5-5 were obtained. Sample 5-1 was prepared as follows. First layer: antihalation layer...contains colloidal silver halide. 2nd layer: Layer mainly composed of gelatin 3rd layer: Low-sensitivity red-sensitive emulsion layer...A low-sensitivity silver halide emulsion prepared by a conventional method (gelatin 70g/
Spectral sensitization was performed by adding 0.17 g of Compound 12 to 1000 g of Kg emulsion). Next, 300 g of emulsion F was added to the above spectrally sensitized emulsion. The coating liquid thus prepared was applied to give a coating weight of 2.8 g/m ² of silver. 4th layer: Highly sensitive red-sensitive emulsion layer... 1000g of the silver iodobromide emulsion shown in Example 1 was spectrally sensitized in the same manner as in Example 4, and 90g of the emulsion F of Example 4 was added thereto as a hardening agent. 1 g of 2,4-dichloro-6-hydroxy-1,3,5-triazine soda was added.
The coating solution prepared in this way has a silver coating amount of
It was applied at a weight of 3.0 g/m ² . 5th layer: Layer mainly composed of gelatin 6th layer: Low-sensitivity green-sensitive emulsion layer...Low-sensitivity silver halide emulsion gelatin prepared by a conventional method 70g/Kg
Add 0.3g of compound 1 and compound 42 to 1000g of emulsion.
Spectral sensitization was performed by adding 0.045 g. Next, 400 g of emulsion B shown in Example 1 was added to the above spectrally sensitized emulsion. The coating liquid thus prepared was applied to give a coating weight of 1.9 g/m ² of silver. 7th layer: Highly sensitive green-sensitive emulsion layer...The silver iodobromide emulsion shown in Example 1 was spectrally sensitized in the same manner as Samples 1-6 to 1-10, and emulsion A of Example 1 was added thereto. 150
g and 1 g of 2,4-dichloro-6-hydroxy 1,3,5 triazine soda as a hardening agent were added. The coating liquid thus prepared was applied to give a coating weight of 1.8 g/m ² of silver. 8th layer: Yellow filter layer: A yellow colloidal silver dispersion was coated in gelatin so that the coating amount of silver was 0.1 g/m ² . 9th layer: Low-sensitivity blue-sensitive emulsion layer...Low-sensitivity silver halide emulsion prepared by the usual method (gelatin 70g/
Kg emulsion), add 100g of the yellow coloring coupler shown below to 200c.c. of ethyl acetate. 100 g of dissolved tricresyl phosphate and sodium dodecylbenzenesulfonate were added as dispersion aids, and 1200 g of an emulsion obtained by emulsifying and dispersing the mixture in 1000 g of a 10% gelatin aqueous solution using a homoblender was added. The coating liquid thus prepared was applied to give a coating weight of 0.8 g/m ² of silver. 10th layer: Highly sensitive blue emulsion layer...350g of the emulsion used in the 9th layer was added to 1000g of the silver iodobromide emulsion shown in Examples 1 and 2, and 2.4 dichloro- 1 g of 6-hydroxy 1,3,5 triazine soda was added. The coating liquid thus prepared was applied to give a coating weight of 0.9 g/m ² of silver. 11th layer: Protective layer...10% gelatin aqueous solution with 2,4 dichloro-6-hydroxy as a hardening agent.
3 g of 1.3.5 triazine soda was added and coated so that the gelatin coating amount was 1.5 g/m ² . Among the above layers, the silver halide emulsion layer contains 4-hydroxy6-methyl-1.3.
Add 3a/7-tetrazyden to the first to third layers.
Sodium dodecylbenzenesulfonate was added to layer 11 as a coating aid. In the case of preparing sample 5-2, 93g of emulsion G was added per 1000g of emulsion instead of emulsion F in the fourth layer of sample 5-1, and emulsion B was added per 1000g of emulsion instead of emulsion A in the seventh layer. Added 156g per serving. Similarly, in the case of creating sample 5-3, 100 g of emulsion H was added to the fourth layer, and 167 g of emulsion C was added to the seventh layer.
In the case of sample 5-4, 107 g of emulsion I was added to the fourth layer.
178g of emulsion D was added to the seventh layer. In the case of sample 5-5, 113 g of emulsion J was added to the fourth layer, and 189 g of emulsion E was added to the seventh layer. Samples 5-1 to 5-5 thus obtained were folded as shown in Examples 1 to 3, and then the density of the developed fogging area was measured. The results are shown in the table.

[Table] As can be seen from the table, fogging caused by pressure strain can be suppressed by increasing the oil/gel ratio even in photosensitive materials coated in multiple layers.

Claims (1)

[Claims] 1 Iodobromide containing 4 mol percent to 12 mol percent silver iodide color sensitized with a dye having at least one sulfo group or carboxyl group and having an average grain size of 1 micron or more At least one silver halide emulsion layer containing silver particles, a dye-forming coupler, a binder, and a high boiling point organic solvent having a boiling point of 175° C. or higher at normal pressure in an amount of 20% by weight or more based on the binder. A method for forming a color photographic image, which comprises color-developing a color photographic light-sensitive material held on a support.