JPS5952420B2 - Color photographic image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a color photographic image, and more specifically, to a method for forming a color photographic image. The present invention relates to a photographic image forming method.

Conventionally, as a subtractive color photographic image formation method, silver halide in an exposed silver halide emulsion layer is processed using an aromatic primary amine developing agent, particularly an N-N-disubstituted paraphenylenediamine developing agent. A method is known in which color photographic images are produced by reduction with a developer, and the oxidized products of the developing agent produced at the time couple with couplers to form cyan, magenta, and yellow dyes.

Active aromatic primary amines are conventionally widely used as color developing agents in color photographic image forming processes.

However, recent trends have required high-temperature, rapid processing and resource conservation in color photographic image forming methods, and even more active developing agents have been required. Conventionally used developing agents cannot completely convert the silver halide grains with the latent image into metallic silver and image dye, and a considerable amount of the silver halide that has formed the latent image is not effectively utilized. This is because it dissolves in the fixer and is discarded as a result. Therefore, if silver halide grains are effectively converted into silver and dyes without waste, excellent color photographic images with higher contrast can be obtained, and the amount of silver can be reduced accordingly. This is because a number of advantages should be obtained, such as the ability to make the photosensitive material a thin film and, therefore, rapid development processing. However, it is certain that when an active developing agent is used, it also has a number of drawbacks. For example, the magenta emulsion layer may be fogged, and oxidation products of the developing agent may diffuse into other emulsion layers, causing a color reaction. This color development results in so-called color mixing, which is a serious drawback in terms of color reproduction and, therefore, a fatal drawback in color photographic image formation. In order to correct this color mixing, which is a fatal defect in color reproduction, there are methods of increasing the thickness of the non-light-sensitive gelatin intermediate layer conventionally provided between emulsion layers, using a basic polymer in the gelatin intermediate layer, or using a gelatin intermediate layer. A method in which a small amount of fine grain non-photosensitive silver halide is added thereto is conventionally known.

However, these methods cannot completely prevent color mixing, and instead have the disadvantage of impairing the sensitivity, sharpness, resolution, etc. of colored images. As yet another improvement method, a number of methods have been proposed in which a reducing compound is used in the non-photosensitive gelatin layer or emulsion layer.

For example, monoalkylhydroquinones as described in US Pat. No. 2,722,556, US Pat. No. 2,728,659, US Pat. No. 3,062,884, US Pat. There is a method using However, none of these methods has achieved sufficiently satisfactory effects. Accordingly, the first object of the present invention is to provide a method for forming highly sensitive color images without color fogging or color mixing by performing color development with a color developer containing a color developing agent with higher development activity. There is something to do.

The second object is to provide a method for forming a color image that exhibits excellent color reproducibility and good image stability.

Thirdly, it is an object of the present invention to provide a color photographic image forming method that is excellent in suitability for high-temperature rapid processing. Fourthly, a color that does not cause any problems even when benzyl alcohol, which has been conventionally used in color photographic developers but is undesirable because it causes pollution, is reduced or removed. A method of forming a photographic image is provided.

The above object and other objects which will become obvious from the following description are a red-sensitive emulsion layer containing a cyan coupler;
Green-sensitive emulsion layer containing magenta coupler and yellow
A blue-sensitive emulsion layer containing a coupler is provided on a support, and the red-sensitive emulsion layer and the green-sensitive emulsion layer each have a 100%
After imagewise exposure of a color photographic material containing 1 mg to 10 mg of silver halide per cm, the following general formula [I]
This is achieved by a method for forming a color photographic image, which is characterized by developing with a developer containing a compound represented by the formula or a salt thereof, and forming a color photographic image in response to the imagewise exposure.

General formula [I] [Wherein, R is the formula -(R,O)m-(R,O)n-R.

(In the formula, R. and R each represent a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms, and R8 is a hydrogen atom, a substituted or unsubstituted aryl group, an aralkyl group, or a carbon atom number 1 represents an alkyl group of 6 to 6, m and n are each an integer of 0 or more, and the sum of m and n is an integer of 1 or more, but when the sum of m and n is 1, R. , is a straight chain alkylene group having 1 to 6 carbon atoms having a substituent.), and R. represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a group represented by the above R, R,,R. and R are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxy group, an alkoxy group, a sulfonamide group, an alkylsulfonamide group, an acylamide group,
Represents an amino group or a mono- or dialkylamino group. ] The silver halide color photographic light-sensitive material used in the present invention has three light-sensitive silver halide emulsion layers with different photosensitive regions on a support, and a red-sensitive halogen containing a cyan color-forming coupler on the support. a silver halide emulsion layer, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler, a blue-sensitive emulsion layer containing preferably a 2-equivalent alpha acylacetamide yellow-forming coupler, and having a green sensitivity and a red sensitivity. The emulsion layer contains 1 to 10 mg/100 cm of silver halide. If there is any deviation from the silver halide content range of the green- and red-sensitive emulsion layers or a change in the developing agent represented by the general formula [I], the above object cannot be achieved. It will become clear from the description. Furthermore, in addition to the above-mentioned essential emulsion layer, the color photographic light-sensitive material used in the present invention may be provided with non-photosensitive auxiliary layers such as a surface protective layer and an intermediate layer as necessary. Although the silver halide content in the blue-sensitive emulsion layer is not limited,
When the amount is 1 to 10 mg per 2, the effect of the present invention is doubled.

Silver halide in the light-sensitive silver halide emulsion layer of the silver halide photographic light-sensitive material used in the present invention includes silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloride, etc. Any of those used in conventional silver halide photographic emulsions are included.

These silver halides may be coarse grained or fine grained, and can be prepared by any known method.
, Publication of Special Publication No. 46-J Camo V2, etc., U.S. Patent No. 25922
50, 3276877, French patent 1557289
, U.S. Patent Nos. 3,317,322, 2,222,264, and 33
20069, 3271157, 3206313, 3367778, 3447927, 2996382
, 2184013, 2541472, 35013
07, 2563785, 2456953, 286
1885, British patent 723019, French patent 152
0821 etc., “Journal of Photographic Science (J.PhOt, Sci), No. 1
Volume 2, No. 5 (September and October issues), 1964, 242-
Those described in "Page 251" can be used. It is also possible to mix and use silver halides prepared by different methods. It is preferable that soluble salts be removed from the silver halide emulsion used in the present invention, but those without removal may also be used. In the silver halide photographic light-sensitive material of the present invention, hydrophilic colloids advantageously used to prepare a light-sensitive silver halide emulsion include gelatin, colloidal albumin, agar, gum arabic, alginic acid, and hydrolyzed cellulose. Acetate acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, such as British Patent 52
366L West German Patent No. 2255711, No. 2046632, U.S. Pat. , phthalated gelatin or U.S. Pat. No. 2,548,520, 2
831767), and gelatin is graft-polymerized with polymerizable monomers having ethylene groups such as acrylic acid, styrene, acrylic esters, methacrylic acid, and methacrylic esters, etc. Hydrophilic colloids are also advantageously used for producing constituent layers of photographic materials that do not contain silver halide, such as filter layers, protective layers, interlayers, etc.

The silver halide emulsion applied to the silver halide photographic light-sensitive material used in the present invention can be sensitized with various chemical sensitizers.

Sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate), selenium sensitizers (N-N-dimethylselenourea, selenourea), and reduction sensitizers. Sensitizers (triethylenetetramine, stannic chloride), noble metal sensitizers such as gold sensitizers, (potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride), etc. are used. It will be done.

When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent. Other palladium, platinum, and iridium salt sensitizers (ammonium chloroparadate,
Potassium chloroplatinate, sodium chloroplatinate), etc. can be used alone or in appropriate combinations. The blue-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion used in the silver halide photographic light-sensitive material of the present invention are optically sensitized using appropriate sensitizing dyes in order to impart photosensitivity to the desired wavelength range. It is felt.

Various sensitizing dyes can be used, and one type or a combination of two or more types of sensitizing dyes can be used. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, useful sensitizing dyes generally include methine dyes and styryl dyes such as cyanine, merocyanine, heminanine, rhodacyanine, oxonol, and hemioxonol. More specifically, the sensitizing dyes described in the following patents or literature are effective. United States Patent (hereinafter referred to as US) 184630LUS1846302,
USl9392Ol, USl99O5O7, US2
O729O8, US2ll2l4O, US2l653
38, US22l3995, US2269234,
US227O378, US24427IO, US24
54629, US2493748, US25O37
76, US25l9OOl, US266676l,
US2739l49, US2739964, US294
5763, British Patent (BP) 424559, BP4
3842O, BP45O958, BP5O5979, West German patent (DP) 929080, DP2O49967
, Special Publication 1025L Special Publication 10252
, Special Publication No. 43-1382L Special Publication No. 44-32753, Special Publication No. 45-27672, Special Publication No. 45-27673, Special Publication No. 45-27674, Special Publication No. 45-27675, Special Publication No. 46-18106, Special Publication No. 46-18108, Special Publication No. 4
7-874L Special Publication No. 47-23573, Special Publication No. 47-3
7443, Japanese Patent Publication No. 48-78930, Mies/James, The Theory of the Photographic Process, 3rd edition (1966). Cyaninized and Related Compounds by Harmer (
(1964).

Among these patents or documents, US22l3995, US25O3776, US294
5763, DP929O8O, DP2O49967, Special Publication No. 43-1382L Special Publication No. 44-32753, Special Publication No. 46-18108, Special Publication No. 47-1874L Special Publication No. 4
The sensitizing dyes described in JP-A No. 7-37443 and JP-A No. 48-78930 are particularly effective in the present invention.

Couplers useful in the silver halide photographic material used in the present invention include open-chain ketomethylene yellow couplers, pyrazolone magenta couplers, and phenolic or naphthol cyan couplers. It is also possible to use an azo-type compound, an osazone-type compound, a development-diffusible dye-releasing coupler, and the like. Typical yellow couplers that can be used in the present invention include those represented by the following general formula [10]. General formula [11] In the formula, R represents a substituted or unsubstituted aliphatic hydrocarbon group, aryl group or hezero ring group, and R and O represent a substituted or unsubstituted aryl group or hezero ring residue. where Z represents a hydrogen atom or a coupling-off group.

Among the yellow couplers represented by the general formula [11],
In the present invention, a more preferable effect is obtained when, in the general formula [11], R and O are substituted or unsubstituted phenyl groups, and Z is a coupling-off group, and as a substituent of the phenyl group. is a halogen atom, amino group, acylamino group, trifluoromethyl group, sulfonamide group, ureido group, alkyl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, carbamoyl group, sulfo group, sulfamoyl group or imide The groups may be mentioned as preferred.

Further, as mentioned above, alpha acylacetanilide type couplers exhibit more preferable effects in the present invention, and among these, pivalyl acetanilide type and benzoylacetanilide type couplers are particularly preferred.

As the pivallylacetanilide type 4-equivalent yellow coupler, those described in French Patent No. 1291110 are effective, and as the benzoylacetanilide type 4-equivalent yellow coupler, those described in Japanese Patent Publication No. 19031/1983 and US Pat. No. 2,875,051 are effective. 2-equivalent couplers, such as those described in U.S. Pat. No. 3,408,194, in which the active point is substituted with -o monoallyl; U.S. Pat. No. 3,4479
-o-acyl substitution at the active point described in JP-A-48-29432; hydantoin compound substitution at the active point described in JP-A-48-66834; Thing: Special Public Service 1977-1
The active point substituted with a succinimide compound as described in JP-A No. 3576; the active point substituted with a monooxoimide compound as described in JP-A-50-28834;) JP-A-49-10
The active point substituted with a pyritazone compound as described in Publication No. 736; The active point substituted with fluorine as described in British Patent No. 944490; The active point substituted with chlorine or bromine as described in British Patent No. 780507; British patent No. 1092
506 specification with 0-sulfonyl substitution; active point substitution as described in JP-A-51-3631; active-point substitution as described in JP-A-50-65231; JP-A-50-65231; In the present invention, the active point replacement described in JP-A No. 50-34232; the active point replacement described in JP-A-50-117423; the active-point replacement described in JP-A-51-50734, etc. more effective. These can be synthesized according to the descriptions in each publication or specification. Further, particularly preferred 2-equivalent yellow couplers are those disclosed in JP-A-48-29432 and U.S. Pat.
8194, JP-A-50-28834, or JP-A-48-66834. Magenta couplers that can be used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and intazolone-based compounds.

US3l272 is a pyrazolone magenta coupler.
69, US26OO788, US35l9429, US
34l939l, US3O62653, BPll425
53, DP2l62778, JP-A-49-29639,
The pyrazolotriazole magenta coupler described in Japanese Patent Publication No. 48-27930 is DPl8l.
O464, Pelkey patent (BELG) 792525
Pyrazolinopenzimidazole magenta couplers are described in US3O6l432, Japanese Patent Publication No. 46-60479, DP2l56lll, and intazolone magenta couplers are B.
The one described in ELG769ll6 is used.

Other Japanese Patent Publications No. 49-11163L No. 49-129538
, 49-74027, 49-74028, 49
1122335, 50=13041, . 50-1
59336, 50-60233, 51-3233
, 51-26541) 51-36938, DP3
36498 and 211018 can also be effectively used in the present invention. These can be synthesized according to the descriptions in each publication or specification. A particularly preferable magenta coupler in the present invention is
27930 and the 3-anilinopyrazolone magenta coupler described in US 3127269.

Useful cyan couplers that can be used in the present invention include, for example, US242373O, US28O
Phenol compounds described in ll7LUS2895826, BELG7795l2, US2474293, BPl
Active point-0-aryl substituted naphthol compound described in O8448O, JP-A-47-4480, JP-A-47-37
425, Japanese Patent Application Publication No. 1983-10135, Japanese Patent Application Publication No. 1983-2
5228, JP-A-50-1112038, JP-A-50-1
20334, JP-A-117422, JP-A-50-
Examples include the phenol and naphthol compounds described in 13044L 51-655LDP129201.

These can be synthesized according to the descriptions in each publication or specification. Couplers contained in the photographic material used in the present invention include, but are not limited to, the following.

YELLOW COUPLER The yellow coupler, magenta coupler or cyan coupler used in the present invention may be present in a blue-sensitive, green-sensitive or red-sensitive emulsion layer, respectively, at a concentration of 8x10 per mole of silver halide.
Preferable effects can be obtained when the amount is contained in the range of -"mol to 3 x 10-"mol.

Each emulsion layer may contain two or more couplers forming the same color. For example, as described in U.S. Pat. No. 2,322,027, it can be incorporated by dissolving in a high boiling point solvent, or as described in U.S. Pat. No. 2,801,170. As shown in the figure, the coupler and the high-boiling point solvent can be separately dispersed into fine particles and then mixed together for use, and in these dispersion methods, it is also preferable to use a low-boiling point solvent.

In this case, the compound represented by the above general formula used in the present invention can be mixed and dispersed with the coupler, or can be used separately from the coupler, and when a low boiling point solvent is used, It is also possible to remove the low boiling point solvent from the dispersion by the method described in US Pat. No. 2,801,171 or Japanese Patent Application No. 76,273/1980. Particularly preferred among the applicable solvents are dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, triphenyl phosphate, torqueresyl phosphate, diethyl lauryl amide, dibutyl lauryl amide, benzyl phthalate, monophenyl phthalate, and high boiling point solvents. P-t-butylphenyl phosphate, phenoxyethanol, diethylene glycol monophenyl ether, dimethoxyethyl phthalate, hexamethylphosphoramide, and U.S. Pat.
779765, JP-A-49-90523 Publication 258,
Examples include high-boiling organic solvents that are immiscible with water and are described in Japanese Patent Publication No. 48-29060.

Examples of low boiling point solvents include methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy triglycol acetate, acetone, methyl acetone, methanol, ethanol, acetonitrile, dioxane,
Dimethylformamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, isopropyl acetate, butanol, chloroform, cyclohexane, cyclohexanol, fluorinated alcohol, etc. can be mentioned, and these low boiling point solvents can be used in place of high boiling point solvents. In addition, these solvents can be used in combination with a high boiling point solvent, and each of these solvents can be used alone or in combination of two or more. Alternatively, in the case of a coupler having a water-soluble group and a compound represented by the above general formula, it is also possible to use it by dissolving it in a Fischier type, that is, an alkaline solution; It is also possible to add one to the same layer by a dispersion method and the other by a fissure type method.

As the colorless magenta coupler, a compound in which the active site of the colorless magenta coupler is arylazo-substituted or hezeroarylazo-substituted is used, such as US3O
O57l2, US29836O8, US28Oll7L
The compound described in BP93762l, Japanese Patent Application No. 44-8433 is used.

Colortone uncouplers include US3O34892, US252l9O8, and BPl with arylazo substitution at the active site.
255llL Compound described in Japanese Patent Application No. 46-55665,
Furthermore, patent application No. 48-57829, patent application No. 48-6986
6. Patent application 1977-16057, patent application 1977-25388
It is also possible to use a type of masking coupler in which the dye flows out into the processing bath by reacting with the oxidized developer, as described in Japanese Patent Application No. 49-37160, BPlO8448O.

In order to incorporate these couplers into a silver halide color photographic light-sensitive material, the above-mentioned various known techniques conventionally used for couplers can be applied.

In the present invention, various photographic additives can be contained in the light-sensitive emulsion layer or the adjacent layer.

For example, as a hardening agent, commonly used photographic hardening agents such as aldehyde type, aziridine type, [for example, P
B Report 1992L US Patent (hereinafter referred to as US) 2950
197, US29644O4, US29836ll, U
S327ll75, described in Japanese Patent Publication No. 46-40898], isoxazole type (e.g. US3316O9
5), epoxy systems (e.g. US3O47
394, West German Patent (hereinafter referred to as DP) 1085663, British Patent (hereinafter referred to as BP) 1033518, Japanese Patent Publication No. 48-3549
5), vinyl sulfones (e.g. PB Report 19920, DPllOO942, BPl25l)
O9L patent application 1977-54236, patent application 1977-110
996, patent application No. 115745, US-3539
644, US349O9ll), acryloyl type (for example, Japanese Patent Application No. 48-27949, US364
O72O), carbodiimides (e.g., those described in US2938892, Japanese Patent Publication No. 46-38715, and Japanese Patent Application No. 49-15095), maleimides (e.g., those described in US2992lO9, US3232763), acetylene-based (e.g., DP2l3O483). ), methanesulfonic acid esters (e.g. those described in US2726l62, US28l6l25), mucohalogen acids (e.g. US3llO597,
(described in Japanese Patent Application No. 48-30948), polymer systems (for example, US3O58827, BP822O6l, B
PlO49O83, BPl2O2O52, BPl23O
354), triazine-based (e.g. US 3
No. 288775 and the one described in Japanese Patent Application No. 108497/1983), but particularly as a hardening agent that can obtain more desirable effects in the present invention, US No. 2726l can be mentioned.
62, Patent Application 1973-30948, PB Report 1992
1, Special Publication No. 46-40898, Special Application No. 48-10849
7. Patent application 1977-54236, patent application 1977-11099
6, Patent Application 1974-115745, PB Report 1992
0, patent application No. 48-27949, patent application No. 49-15096
, BPl25lO9l, and when used in combination with these hardeners, silver halide color photographs that have particularly good color purity and graininess, and have good hardeners that can withstand high-temperature rapid processing. A photosensitive material can be obtained.

In addition, in order to apply these hardeners to silver halide color photographic light-sensitive materials, they may be added and mixed into the coating solution in advance, or they may be applied using an apparatus such as that described in US 3,286,992. It is also possible to use means for continuously mixing it into the coating liquid immediately before coating.

The silver halide color photographic light-sensitive material used in the present invention contains various photographic additives commonly used in the silver halide emulsion layer or auxiliary layer, such as tone adjusters,
Development accelerator, stabilizer, ultraviolet absorber, latent image stabilizer, formalin resistance improver, image stabilizer, fluorescent whitening agent, antistain agent, lubricant, sequestering agent, surfactant, mordant, electrostatic charge It may contain an inhibitor, a color turbidity inhibitor, a thickener, a gelatin plasticizer, a latex, a matting agent, and the like.

As the tone adjusting agent, metals of group 8 (for example, rhodium, norethenium), cadmium, thallium, etc. can be used.

Benzyl alcohol and polyoxyethylene compounds can be used as development accelerators, and these compounds are effective even when added to the processing bath. US as a stabilizer
2444677, US27l6O62, US35l
2982, DPll8938O, DP2O58626,
DP2ll84lL Special Publication Showa 43-4133, US33
42596, Special Publication Showa 47-4417, DP-21497
89, Special Publication No. 39-2825, Special Application No. 45-J Camo V07
Compounds described in 2 can be used. Particularly preferred compounds include 5,6-tetramethylene-J[hydroxy-1S-triazolo (1,5-a)pyrimidine, 5,6-tetramethylene-J[hydroxy-1S-triazolo (1,5-a)pyrimidine, -Methy-J
Me[hydroxy-1S-triazolo (l・5-a)pyrimidine, 7-hydroxy-1S-triazolo (1・5-
a) Pyrimidine, 5-methyl-6-promoJ[hydroxy-S-triazolo (1.5-a) pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), Mercaptans (1-phenyl-5-menolecaptotetrazone, 2-menolecaptobenzthiazole), benztriazoles (5-bromobenztriazole, 4-methylbenztriazole), benzimidazoles (6-nitrobenztriazole), imidazole), etc. As ultraviolet absorbers, there are JP 48-763, JP 48-5496, JP 48-41572, JP 4.
8-30492, Special Publication No. 48-31255, US32
Compounds described in 5392LBP3O9349 can be used, among them Tinupin PS, Tinupin 320, Tinupin 326, Tinupin 3 manufactured by Ciba Kirkey.
It is effective to use UV absorbers such as 27 and Tinupin 328 alone or in combination. DP2 as a latent image stabilizer
In addition to the sulfur-containing amino acid compounds described in 2l7l53 and DP22l7895, JP-A-49-14120 and JP-A-49-2
The nitrogen-containing heterocyclic compounds described in No. 9835 can be used. BELG8Ol as a formalin resistance improver
533, Patent Application 1974-134036, Special Publication 1977-34
Among them, B which is a combination of a vinyl sulfone hardener and an acyclic urea derivative can be used.
ELG8Ol533 and patent application No. 134036
Those listed in are valid. US3 as an image stabilizer
Chroman compounds described in 4323OO, US3574
Chroman and coumaran compounds described in Japanese Patent Publication No. 627, bisphenol compounds described in Japanese Patent Publication No. 48-31256 and Japanese Patent Publication No. 48-31625, phosphite ester compounds described in Japanese Patent Publication No. 48-32728, and the like can be used. Among them, Tokuko Sho 48-31256 and Tokko Sho 48-31
Compounds described in 625 are effective, for example 6.
6'-butylidenepis (2-t-butyl-4-methylphenol), 4.4'-methylenebis (2.6-di-t-butylphenol), 2.2'-dimethyl-
4 ・4'-dihydroxy-5 ・5'-di-t-
Examples include butyl diphenyl sulfide. As a fluorescent bleach, for example, Japanese Patent Publication No. 34-7127
Compounds described in can be used. As the lubricant, wax, glycerade of higher fatty acids, higher alcohol esters of higher fatty acids (for example, those described in US 312106O), etc. can be used. Ethylenediaminetetraacetic acid or DPI is used as a sequestering agent.
l6O3O2, DPll7O777, DPll87l3
2. Compounds described in US Pat.
094 is effective. Surfactants include coating aids, emulsifiers, permeability improvers for processing liquids, etc.
Anionic, cationic, nonionic, or amphoteric antifoaming agents or materials for controlling various physical properties of photosensitive materials can be used. For example BP548532, BPl2l6389, US
3O262O2, US35l4293, Special Publication Showa 44-
26580, Special Publication No. 43-1 17922, Special Publication No. 43-1
7926, Special Publication No. 40-376, Special Publication No. 43-1316
6, Japanese Patent Publication No. 43-43130, Japanese Patent Publication No. 48-2078
5. Japanese Patent Application Publication No. 47-18338, Patent Application No. 47-8963
0, FP2O25688, BELG773459, etc. are effective, but particularly preferred among them are sodium-alkyl sulfosuccinate (
For example, sodium di-2-ethylhexyl sulfosuccinate or sodium amyludecyl sulfosuccinate), sodium alkylbenzenesulfonate (for example, sodium dodecylbenzenesulfonate, etc.), sodium alkylnaphthalenesulfonate (for example, sodium triisopropylnaphthalene sulfonate, etc.) or nonionic surfactants containing saponin, polyethylene glycol, alkyl phenoxy polyethylene glycol, alkyl phenoxy polyglycidol, sucrose fatty acid ester, organosiloxane (for example, Poron SR, Union, manufactured by Shin-Etsu Chemical Co., Ltd. Carbide L-
N-
Alkyl-N-N-dipolyoxyethylene-N-carboxymethyl-betaine (e.g. N-lauryl-N-
Amphoteric activators such as N-dipolyoxyethylene-N-carboxymethyl-betaine, etc., or nonionic, anionic, cationic, and betaine-type activators having a fluorine-containing alkyl group (for example, 3M's FC-134, FC -172
etc.), and these activators can be used alone or in combination as disclosed in JP-A-48-101118.
As a mordant, US2882l56, DP2ll
N-guanylhydrazone compounds described in 338l, U
S2548564, US3444l38, BP7865
92, quaternary onium salt compounds described in Japanese Patent Publication No. 43-10254, US26753l6, BPl22ll95, B
Tertiary amine compounds or quaternary onium salt compounds described in Pl22ll3l can be used, among which DP2l
Compounds described in 1338LUS2548564 are effective. As antistatic agents, JP 46-124159, JP 46-39312, JP 48-43809, JP 49-4853, JP 49-64, JP 47-8
742, Japanese Patent Publication No. 48-43130, Japanese Patent Publication No. 48-899
79, JP-A-48-9039L JP-A-48-20785
, Japanese Patent Publication No. 47-33627, Patent Application No. 47-11564L
Compounds described in US2882157 and US2979535 can be used, among them JP-A-48-89
979, Japanese Patent Publication No. 48-9039L Special Publication No. 46-241
59, those described in JP-A-47-33627, such as diacetyl cellulose, styrene-perfluoroalkyl sodium maleate copolymer, reaction product of styrene-maleic anhydride copolymer and P-aminobenzenesulfonic acid Alkaline salts, P-xylidene dichloride and N
A polyadduct of -N-N'/N'-tetramethyltrimethylenediamine is effective. Prevents color from becoming cloudy (
As agents for preventing desilvering failure, polymers containing vinylpyrrolidone monomers (for example, compounds described in BPlO52487), polymers containing vinyloxazolidinone monomers (
(e.g. compounds described in BPlO7O685), polymers containing vinylimidazole monomers (e.g. BPl8
8O976) and the like can be used. Matting agents include those described in BPl22l98O, such as polymethyl methacrylate, polystyrene, and the alkali-soluble polymers described in US2992lOl.
For example, methacrylic acid-methyl methacrylate copolymer is effective. It is also possible to use colloidal silicon oxide. In addition, latexes added to improve film properties include US2956884 and FP139.
Copolymers of acrylic esters, vinyl esters, etc. and other ethylene group-containing monomers as described in Japanese Patent Publication No. 48-43125 and the like can be used.

Glycerin or US296 as a gelatin plasticizer
O4O4, Special Publication No. 43-4939, Special Publication No. 45-154
62, Japanese Patent Publication No. 48-63715, DPl9O46O4
, BELG762833, etc. can be used. As thickeners, styrene-sodium maleate copolymer, alkyl vinyl ether-maleic acid copolymer, US376741O, BELG558
143 can be used.

The silver halide photographic light-sensitive material used in the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and an erasure layer. Alternatively, it may contain a bleaching dye.

As such dyes, dyes such as cyanine, merocyanine, styryl, benzylidene, cinnamylidene, oxanol, azo, anthraquinone, and triphenylmethane are typically used. Dyes that can be effectively used in the present invention include USl884O35 and US2l5.
O695, US2l72262, US224l239
, US229873l, US2298733, US
2322OO6, US2527583, US2Oll
696, US2622O82, US2O9l579
, US2739888, US2865752, US
2956879, US3247l27, Special Publication No. 28-5
731, Special Publication No. 31-5920, Special Publication No. 31-1057
8, Special Publication No. 39-22069, Special Publication No. 43-13168
, BP396646, BP446583, BP5O63
85, BP5l5998, BP646l25, BPll
Examples include those described in 28ll3. Among them, USl8
84O35, US2865752, US2956879
, Special Publication No. 39-22069, Special Publication No. 43-13168
, BP5O6385 is effective. The silver halide photographic material used in the present invention is prepared by coating a silver halide emulsion layer and other constituent layers containing various photographic additives as described above on a support. It is manufactured by Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate,
There are cellulose night sheets, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polyamide finolems, polycarbonate finolems, polystyrene films, etc., and these supports are used for silver halide photographic light-sensitive materials. It is selected as appropriate depending on the purpose of use. These supports are subjected to undercoat processing if necessary.

Typical undercoat materials include copolymers of vinyl chloride or vinylidene chloride, copolymers of vinyl alcohol esters, copolymers of acrylic acid or methacrylic esters, copolymers containing unsaturated carboxylic acids, Copolymers of dienes such as butadiene, copolymers of acetals,
Copolymers of unsaturated carboxylic acid anhydrides such as maleic anhydride, especially copolymers with vinyl alcohol esters such as vinyl acetate or styrene, or ring-opened products thereof with water, alcohols or amines, such as nitrocellulose, diacetyl There are cellulose derivatives such as rose, compounds containing epoxy groups, gelatin or gelatin modified products, and polyolefin copolymers.
8-9965, Special Publication No. 48-3564, Special Publication No. 48-1
4185, Special Publication No. 47-35458, Special Publication No. 47-35
459, JP-A-47-3792L JP-A-47-1427
4, JP-A-48-24723, JP-A-48-93672
, JP-A-48-89979, etc. These undercoating materials can be used alone or in combination as necessary. Also, Tokuko 48-43122, Tokuko 48-43122, Tokuko 48-43122
As described in JP-A-8-24270 and JP-A-48-26124, it is also possible to use gelatin or polyols in combination. Furthermore, it is also possible to use monovalent or polyvalent phenols, halogen-substituted products thereof, crosslinking agents (hardening agents), metal oxides, etc. (for example, JP-A-48-23862, JP-A-47-592). When actually undercoating the support,
The above materials may be used alone, but a layer consisting of the above materials, a mixed layer of gelatin and the above materials, and a gelatin layer may be applied in this order, or one layer of the former two may be removed and a gelatin layer applied thereon. It is possible to increase the number of layers and apply weight if necessary, and any method can be used depending on the purpose. Furthermore, as described in JP-A-48-8973L, JP-A-48-85126, JP-A-48-93672, and JP-A-47-19824, corona discharge, glow discharge, and other electronic It is also possible to perform treatments such as impact treatment, fire treatment, surface roughening, ultraviolet irradiation, etc. singly or in combination with each other, and it is also possible to perform these surface treatments in combination with the above-mentioned material processing. In the present invention, the above-mentioned silver halide photographic material is subjected to color development after exposure.

In the reversal method, the image is first developed with a black-and-white negative developer, then subjected to night color exposure or treated with a bath containing a fogging agent, and then color developed with an alkaline developer containing a color developing agent. There are no particular restrictions on the processing method, and any processing method can be applied. For example, a representative example is a bleach-fixing treatment after color development as described in US 3,582,322, followed by washing with water and stabilizing treatment if necessary. The method described in US Pat.

There are also known methods of processing low silver content light-sensitive materials using amplifiers such as hydrogen peroxide and cobalt complex salts, and these methods can also be used for processing.

In addition, these treatments may be carried out at high temperatures in order to perform them quickly, or may be carried out at room temperature or lower in special cases. When carrying out the high temperature treatment, a prehardening treatment can also be carried out, for example as described in US Pat. No. 3,342,596.

Depending on the type of treatment agent used, auxiliary baths such as various neutralization baths may be required in some cases.
These auxiliary baths can be used as needed.
Practical examples of these treatments include Eastman Kodak's Flexicolor Chemica Norez, Three Chemikanorez, and ME-4 treatments. The present invention exhibits sufficient effects when these treatments are applied, but it also exhibits sufficient effects when these treatments are modified or improved. Various methods can be used to transport the photosensitive material during processing, and various types of processing equipment are used accordingly.

For example, hanger method, cine method, roller conveyance method,
There are various methods such as the parser mat method, and special methods such as the Japanese Patent Publication No. 1885-1885 and the Special Publication No. 36-1698.
9, US3l89452, Special Publication No. 46-40908, U
The silver halide photographic material of the present invention can also be used in methods such as those described in S36O7277, which do not immerse the photosensitive material in a processing bath, but instead apply or spray a processing solution onto the photosensitive material. It is effectively used for processing. In addition, methods have been developed to reuse processing liquids and to recover chemicals that are important in terms of pollution or resources, such as developers and heavy metal silver, and some processing equipment is equipped with these devices. It can also be processed using

In the present invention, the color developing solution contains a compound represented by the general formula [I] shown above.

In the compound represented by the general formula [I], R is one (R
.

O)m-(R,O)n-R. represents a group represented by
R here. and R, is a substituted or unsubstituted carbon number of 1 to 6
represents a straight-chain alkylene group. Examples of substituents that may substitute one or more hydrogens in the alkylene group include methyl group, ethyl group, propyl group, isopropyl group,
Alkyl groups such as butyl group, t-butyl group, nonyl group, etc., aryl groups such as phenyl group, naphthyl group, etc., aralkyl group such as benzyl group in which one or more hydrogens of the above alkyl group are replaced with the above aryl group. group, methoxy group,
Typical examples include alkyloxy groups such as ethoxy, pentyloxy, and octyloxy groups, aryloxy groups such as phenoxy, and halogen atoms. Two or more hydrogen atoms may be further substituted with other substituents. Further, R represents a hydrogen atom, a substituted or unsubstituted aryl group, an aralkyl group, or an alkyl group having 1 to 1 carbon atoms. m and n are each an integer of 0 or more, and the sum of m and n is an integer of 1 or more. However, when the sum of m and n is 1, R(6) and R(
7) is a straight chain alkylene group having 1 to 6 carbon atoms and having a substituent as described above. Moreover, in the general formula [I], R.

represents a hydrogen atom, a substituted or unsubstituted aryl group, an aralkyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by R(1) above. Typical examples of substituents for aryl groups, aralkyl groups, and alkyl groups include hydroxy groups, substituted or unsubstituted amino groups, alkoxy groups, acylamido groups, carbamyl groups, aryloxy groups, and alkylsulfonamide groups. can be mentioned. Furthermore, in the formula, R,,R.

and R each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, such as a hydroxyalkyl group, an acylamidoalkyl group, an alkylsulfonamidoalkyl group, or a substituted or unsubstituted aminoalkyl group. It represents a substituted alkyl group, an alkoxy group, an amino group, a mono- or dialkylamino group, a sulfonamide group, an alkylsulfonamide group or an acylamide group. When R or R5 is an alkyl group having 1 to 6 carbon atoms, it is extremely useful as a color developing agent in the present invention. The compounds represented by the general formula [I] have been described in detail above, but among these, the compound represented by the following general formula [111
).

General formula [110 In the formula, R.

represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or aralkyl group; R3, R; and R. are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a hydroxy group, an alkoxy group,
R represents a sulfonamide group, an alkylsulfonamide group, an acylamide group, an amino group, or a mono- or dialkylamino group; R6 and R each represent a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms;
represents a substituted or unsubstituted aryl group, aralkyl group, or alkyl group having 1 to 6 carbon atoms, p and q are integers of 0 or more, and the sum of p and q is 2 or more, and even more preferably The sum of p and q is 3 or more. Next, typical examples of the developing agent represented by the general formula [I] used in the present invention will be shown.

Note that the above compounds may be used, for example, sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, alkylbenzenesulfonic acid, benzenesulfonic acid,
Salts made with naphthalenesulfonic acid, alkylsulfonic acids, and other organic or inorganic acids can also be effectively used in the present invention in the same way as the above-mentioned exemplified compounds.

As shown in the above general [I] according to the present invention. To synthesize a color developing agent, for example, N-alkylaniline, N-alkyl-3-alkylaniline, N-alkyl-3-alkoxyaniline, N-alkyl-3-
Alkylsulfonamide aniline, N-alkyl-3-
Monoalkyl N such as acylamide aniline, N-alkyl-3-hydroxyaniline, N-alkyl-3-acylamidoalkylaniline, N-alkyl-3-hydroxyalkylaniline or N-alkyl-3-alkylsulfonamidoalkylaniline Monosubstituted anilines are available and used, in which case these monoalkyl N-substituted anilines and, for example, 1-halogen-2
-(2-methoxyethoxy)ethane, 1-halogen-2-[2-(2-methoxyethoxy)ethoxy]ethane, 1-halogen-l-methyl-2-methoxy-ethane, 1-halogen-1-methyl- 2-[2-(2-methoxyethoxy)ethoxy]ethane, 1-halogen-2
-(l-methyl-2-methoxyethoxy)ethane, 1
-Halogen- ω- of 2-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}ethane, etc.
The corresponding N-N-disubstituted anilines can be synthesized by reacting with halides or, for example, first diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol,
A corresponding p-toluenesulfonic acid ester is synthesized by reacting alkylene glycols such as tripropylene glycol or monoalkyl ethers thereof with p-toluenesulfonic acid halide, and then reacting this with the monoalkyl N-substituted aniline. Corresponding N-N-
Di-substituted anilines can be synthesized and used.

Also, 3-alkylaniline, 3-alkoxyaniline, 3
- Anilines such as alkylsulfonamide aniline, 3-acylamidoaniline, 3-hydroxyaniline, 3-hydroxyalkylaniline, 3-alkylsulfonamidealkylaniline, or 3-acylamidoalkylaniline and the above ω-halide or P- N-N-disubstituted aniline can be synthesized and used by reacting it with toluenesulfonic acid ester.

To synthesize the color photographic developer according to the present invention from the N-N-disubstituted aniline, first, a diazonium compound obtained by diazotizing substituted or unsubstituted aniline is coupled to the N-N-disubstituted aniline. First, an azo dye is synthesized, and then hydrogenated using a catalyst such as palladium-carbon or nickel to obtain the corresponding P.
-P-phenylenediamine-based compounds can be synthesized, or the N-N-disubstituted aniline can be first nitronized and then reduced to synthesize the corresponding P-phenylenediamine-based compounds. P− obtained in this way
A phenylenediamine-based compound can be used as a color photographic developer according to the present invention, and a salt formed by binding an organic acid or an inorganic acid to this compound can also be used as a developing agent used in the present invention. .

To synthesize the latter salt-formed developing agent, the P-phenylenediamine compound and a necessary amount of hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, alkylbenzenesulfonic acid,
A mixed reaction with an organic or inorganic acid such as benzenedisulfonic acid, alkylsulfonic acid or naphthalenedisulfonic acid may be performed to precipitate crystals of a salt of the corresponding P-phenylenediamine compound.

A typical method for synthesizing the color photographic developer used in the present invention is disclosed in Japanese Patent Application No. 17246/1983 and Japanese Patent Application No. 1573/1983.
It is described in the specification of No. 15.

The color photographic developer used in the present invention is a free base of a P-phenylenediamine compound, or a salt with an organic or inorganic acid, such as a hydrochloride, a sulfate, a phosphate,
Those formed of oxalate, alkylbenzenesulfonate, benzene disulfonate, alkylsulfonate or naphthalene disulfonate are used.

Although some free bases are stable, in general, salts with the above-mentioned organic acids or inorganic acids are preferred from the viewpoint of solubility in alkaline aqueous solutions and development action, particularly hydrochlorides, sulfates, and alkylsulfonic acids. Salts, p-toluenesulfonate and the like are preferred from the viewpoint of solubility. In order to form a salt of a P-phenylenediamine compound using such an acid, it is best to form a salt by combining about 1 to 4 moles of acid to 1 mole of the P-phenylenediamine compound base. preferable.

To prepare a developer using the color photographic developer of the present invention, the amount of the developer is 0.001 to 0.0 per 11 of the developer.
A range of 2 mol, particularly a range of 0.002 to 0.01 mol, is preferred.

Examples of additives other than the developer in the developer used in the present invention include alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfites, alkali metal sulfates, alkali metal carbonates, alkali Metal hydroxide, alkali metal metaporate, alkali metal phosphate, ethylenediamine, citradinic acid, other antifoggants such as 5-nitrobenzimidazole, development aids such as 1-phenyl-3-pyrazolidone, benzyl alcohol, Examples of stabilizers for the developer include diethylhydroxyamine, dihydroxylacetone, glycolaldehyde, glyceraldehyde, dihydroxymaleic acid, and sodium hexametaphosphate.

Furthermore, the external developer contains a diffusible phenol and naphthol cyan coupler, a ketomethylene yellow coupler, and a 5-pyrazolone magenta coupler. Next, as typical internal color photographic developers, there are the following, for example.

[Color photographic developer]

Add water to adjust the pH to 11, and adjust the pH to 10.0 to 14 using an alkali metal hydroxide or alkali metal carbonate, for example.
．． Adjust to 0.

In the present invention, a developer excluding benzyl alcohol can also be used satisfactorily.

Bleaching agents include dichromates, red blood salts, permanganates, iron chlorides, halogens, persulfuric acid, hydrogen peroxide or aminopolycarboxylic acid metal salts, such as DP8666O.
Iron complex salts of EDTA (ethylenediaminetetraacetic acid) as described in No. 5, ferrate trinitroacetate, or iron tartrate, cobalt salts as described in DP954475 and BP777635, and the like can be used.

In addition, examples of quinone-based bleaches include US25O7
183, US252998l, as nitroso compounds, for example, US27O52Ol
Examples of copper complex salts include BP7.
74l94, Special Publication No. 35-1478, BPlO32O2
Examples of the halogen acid compounds described in No. 4 include US Pat.
8, and these bleaching agents can also be used effectively. As a fixing agent, thiosulfate,
Known fixatives such as thiocyanate and e.g. US2748
It is described in OOO. For example, thioether polycarphonic acid is described in JP-A-47-330. For example, a bissulfonyl alkane fixing agent may be used. In addition, various bleaching or fixing accelerators can be effectively used.

These accelerators are often used in bleach-fixing baths, and typical examples include polyethylene oxide, thiourea, mercapto, amine, onium, and selenium accelerators, such as BP746567.
, Special Publication No. 45-8506, BPll38842, Special Publication No. 45-8836, Special Publication No. 46-556, DPl394O
Particularly effective are those described in JP-A-46-280, JP-A-47-7324, and JP-A-47-7325. In order to create an actual treatment solution using these chemicals, various auxiliary chemicals are required, such as phosphoric acid, acetic acid, citric acid, tartaric acid, boric acid, and their alkali metal salts or ammonium salts for pH adjustment. is used.

In addition, developers usually contain antioxidants, development accelerators, etc., and in the present invention, various processing steps using these various chemicals are effectively used. be able to. In the silver halide photographic light-sensitive material according to the present invention, the amount of the compound represented by the above general formula to be used depends on the main purpose of application, such as inter-image effect or intra-image effect, the type of emulsion, and the amount of the compound used. Although it varies depending on the type, it is generally preferable to use an amount equivalent to 0.1 to 10 g per 1 kg of emulsion, and a significantly larger image effect can be obtained even with a smaller amount than conventional development-suppressing release type compounds.

Next, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereby.

Example 1 A color photographic material [I] was prepared by sequentially coating and drying the following layers on a polyethylene laminate support.

Layer-1 Blue-sensitive silver halide emulsion containing yellow coupler (silver chloroiodobromide emulsion containing 1 mol % silver iodobromide and 80 mol % silver bromide, 4 gelatin per mol silver halide)
00g containing 2.5x sensitizing dye per mole of silver halide
sensitized with 10-' moles of exemplified coupler (Y-20) per mole of silver halide, dissolved and dispersed in dibutyl phthalate, at a coated silver level of 4. It was applied at a concentration of 0 mg/100 cm2.

Layer-2 Gelatin layer (intermediate layer) was coated to a thickness of lμ.

Layer-3 A green-sensitive silver halide emulsion containing a magenta coupler (a silver chlorobromide emulsion containing 80 mol% silver bromide, containing 500 g of gelatin per mol of silver halide, and a sensitizing dye per mol of silver halide) sensitized using 2.5 x 10-'' moles of exemplary coupler (M-3) per mole of silver halide, dissolved and dispersed in tricresyl phosphate. The amount of silver applied was 4.0 mg.
/100cm2.

Layer-4 Gelatin layer (intermediate layer) Layer-5 Red-sensitive silver halide emulsion containing cyan coupler (silver chlorobromide emulsion containing 80 mol% silver bromide, containing 50 g of gelatin per mol of silver halide) , sensitized with 2.5 x moles of IOH sensitizing dye per mole of silver halide, and an exemplary coupler (C-10) dissolved and dispersed in tricresyl phosphate at 2.5 x moles of IOH per mole of silver halide. Coated silver amount: 2.5 mg/
It was applied to a thickness of 100 cm.

Layer-6 Gelatin layer (protective layer) As a comparative sample, the coating silver amount of layer-1 was 15mg/100-
A photosensitive material [11] was prepared in exactly the same manner except that the amount of silver coated in Layer-3 was 15 mg/Cm· and the amount of silver coated in Layer-5 was 15 mg/100 cm.

These samples [I] and [11] were subjected to wedge exposure using a conventional method through blue, green and red filters, and were then exposed to a developer according to the present invention using the following two types of exemplified compounds and a developer ( B), for comparison, processed with four types of developer (C) and developer I using the following two types of developer, and then processed with the following bleach-fix solution and stabilizing solution to produce four types of color. A sample with an image was created.

[Color photographic developer]

Benzyl alcohol 5.0ml Sodium hexametaphosphate 3.00g Anhydrous sodium sulfite 1.85g Sodium bromide 1.40g Potassium bromide 0.50g Borax (Na.

B, O, ・IOH. O) 39.10g of the following color photographic developer Add 0.01 mol of water to make it 11, and add PHIO. with sodium hydroxide. Adjusted to 3.

[Developer for color photography]

Developer (Self) P-toluenesulfonate developer of Exemplified Compound (3) (B) P-Toluenesulfonate developer of Exemplified Compound (6) (C) N-Ethyl-N-[2-
(methylsulfonamido)ethyl]-3-methyl-4-
Aminoaniline sulfate developer (D) N-ethyl-N-(2-methoxyethyl)-3-methyl-4-aminoaniline-P-toluenesulfonate [bleach fixer] Iron ammonium ethylenediaminetetraacetate 61.0 g
Ethylenediaminetetraacetic acid-2-ammonium 5.0
g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Sodium bisulfate 2.7g Water was added to make the solution 11, and the pH was adjusted to 6.5.

[Stabilizing liquid]

Glacial acetic acid (trihydrate) 20ml 800ml of pure water was added, and the pH was adjusted to 3.5-40 using sodium acetate trihydrate.

The three color densities of yellow, magenta and cyan were measured for these samples using a PD-7R densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and the photographic performance obtained is shown in Table 1. From Table 1, photosensitive material-[I] was mixed with developer A, . The characteristics obtained when processed with B are better than those processed with conventional developers C and D, and whereas when photosensitive material [11] was processed with developers A and B, fogging was large, compared to the results obtained with the present invention. It is understood that things are good.

Note that the sensitivity is expressed as a relative value to 100, which is the sensitivity of the photosensitive material [11] processed with the developer (self). Example 2 The sample of Example 1 was developed in exactly the same manner except that benzyl alcohol, which is undesirable from a pollution standpoint, was removed from the developing solution used in Example 1. As a result, the sensitivity and fog were the same as in Example 1. A positive image with excellent characteristics and even higher color purity was obtained.

Example 3 A color photosensitive material [110] was prepared by sequentially coating the following layers on a polyethylene laminate support.

Layer-1 Blue-sensitive silver halide emulsion containing yellow coupler (silver chloroiodobromide emulsion containing 1 mol % silver iodide and 80 mol % silver bromide, containing 4 gelatin per mol silver halide)
00g, 2.5 sensitizing dyes per mole of silver halide
x 10-'' mole of exemplified coupler (Y-13) dissolved and dispersed in dibutyl phthalate (containing 2 x 10-'' mole per mole of silver halide) in a coated silver amount of 5. It was applied at a concentration of 0 mg/100 cm2.

Layer-2 Gelatin layer (intermediate layer) was coated to a thickness of 1 μm.

Layer-3 A green-sensitive silver halide emulsion containing a magenta coupler (silver chlorobromide emulsion containing 80 mol% silver bromide, using 2.5 x 10-' mol of sensitizing dye per mol of silver halide) The exemplary coupler (M-4), sensitized by
Coated silver amount: 4.5
It was applied at a concentration of mg/100cm2.

Layer-4 Gelatin layer (intermediate layer) Layer-5 Red-sensitive silver halide emulsion containing cyan coupler (silver chlorobromide emulsion containing 80 mol% silver bromide, containing 500 g of gelatin per mol of silver halide) , the exemplary coupler (C-20), sensitized with 2.5 x 10-mmole of sensitizing dye per mole of silver halide and dissolved and dispersed in tricresyl phosphate, was added to 1 mole of silver halide. Coated silver amount: 4.0 m
It was applied so that the amount was 100 g/100 cm2.

Layer-6 A gelatin layer (protective layer) was applied.

As a comparative sample, the coating silver amount of layer-1 was 15 mg/100
The coating silver amount of d layer-3 was 13.5 mg/100 cm2,
A photosensitive material [IV] was prepared in exactly the same manner except that the coating amount of layer-5 was 12 mg/100 cm<2>. This sample was subjected to wedge exposure through blue, green, and red filters in the usual manner, and the following processing step was carried out using a developer (E) using the developer according to the present invention.
) and developer (F), and the following bleaching solution, fixing solution, and stabilizing solution were used to perform four types of processing. [Processing process] 38℃
Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds [Developer for color photography] Anhydrous sodium sulfite 0.14 g Hydroxyamine. 1/2 sulfate 1.98g sulfuric acid
0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate) 1.20
g Potassium hydroxide 1.48 g The following color photographic developer 0.01 mol of water was added to make it 11.

[Developer for color photography]

Developer (E) P-toluenesulfonate developer of Exemplified Compound (D-17) (F) Sulfate of Exemplified Compound (D-18) These samples were subjected to the following method using a PD-7R densitometer. Measurements were therefore made to examine the occurrence of color turbidity in each light-sensitive emulsion layer caused by the influence of adjacent light-sensitive emulsion layers.

That is, for a yellow image, the magenta density (D
G) is measured using a green filter 1, and for magenta images, magenta density 1 measured using a green filter 1.
．． The yellow density (DB) and cyan density (DR) of the portion corresponding to 0 were measured using a blue filter 1 for the former and a red filter 1 for the latter, and for the cyan colored portion, a red filter 1 was used for the cyan color development area. The magenta density (DGI) of a portion corresponding to the measured cyan density of 1.0 was measured using a green filter. The results are shown in Table 2.

As is clear from Table 2, it can be seen that Material 111 of the present invention causes less color turbidity than Material IV and can provide a brightly colored image.

Example 4 The following layers were sequentially coated on a polyethylene terephthalate film from the support side to produce a color photosensitive material. [V] was created.

Layer-1 A red-sensitive silver halide emulsion containing a cyan coupler (a high-sensitivity silver iodobromide emulsion containing 7 mol% silver iodide, containing 200 g of gelatin per mol of silver halide, increasing the amount per mol of silver halide) An exemplary coupler (C
-1) was coated at a rate of 1.5 x 10-1 per mole of silver halide, giving a molar coated silver amount of 10 mg/100 cm2.

Layer-2 Gelatin layer (intermediate layer) Layer-3 Green-sensitive silver halide emulsion containing magenta coupler (high-sensitivity emulsion containing 7 mol% silver iodide, containing 200 g of gelatin per mol of silver halide, containing halogen The exemplary coupler (M-7) was sensitized using 2.5 x 10-' moles of sensitizing dye per mole of silveride and dissolved and dispersed in a mixed solvent of tricresyl phosphate and ethyl acetate. The coating solution was coated at a concentration of 10 mg/Cm.

Layer-4 Yellow filter layer Layer-5 A blue-sensitive silver halide emulsion containing a yellow coupler (a high-sensitivity silver iodobromide emulsion containing 7 mol% silver iodide, containing 200 g of gelatin per mol of silver halide, Exemplary coupler (Y-20) dissolved and dispersed in a mixed solvent of dibutyl phthalate and ethyl acetate was coated at a coating silver amount of 1.5 x I'mole per mole of silver halide, 10 mg/cm2.

Layer-6 A gelatin layer (protective layer) was applied. As a comparison sample, the coating silver amount of layer-1 was 20 mg/100 cm2, and layer-
A photosensitive material (VIJ) was prepared in exactly the same manner except that the amount of silver applied in Layer 3 was 20 mg/100 cm 2 and the amount of silver applied in Layer 5 was 15 mg/100 cm 2 . This sample was wet exposed in the usual manner through blue, green, and red filters and developed with the same developer used in Example 3 above. The results are shown in Table 3.

The values of the three-color density ratio are shown as DGl for the yellow image, DB for the magenta image, and D6l for the cyan image.

When material [VI] is developed as shown in Table 3, FOg is generated with any developer, and developer J. Although the color mixture becomes large in K, the material [V] shows good sensitivity and fog characteristics, and the three-color density ratio also shows an excellent value, indicating that the color mixture is improved and good color reproduction is possible. .

Claims (1)

[Scope of Claims] 1. A red-sensitive emulsion layer containing a cyan coupler, a green-sensitive emulsion layer containing a magenta coupler, and a blue-sensitive emulsion layer containing a yellow coupler on a support, and the red-sensitive emulsion layer and the green-sensitive emulsion layer are each 100 cm^2
After imagewise exposure of a color photographic light-sensitive material containing 1 mg to 10 mg of silver halide per unit, it is developed with a developer containing a compound represented by the following general formula [I] or a salt thereof, to produce a material corresponding to the imagewise exposure. A method for forming a color photographic image, characterized in that a color photographic image is formed by using a color photographic image. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is the formula -(R_6O)_m-(R_7O)
_n-R_8 (wherein R_6 and R_7 each represent a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms, and R_8 is a hydrogen atom, a substituted or unsubstituted aryl group, an aralkyl group, or a carbon atom number represents an alkyl group of 1 to 6, m and n are each an integer of 0 or more, and the sum of m and n is an integer of 1 or more, but m
and when the sum of n is 1, R_6 and R_7 are linear alkylene groups having 1 to 6 carbon atoms and having a substituent. ), R_2 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a group represented by R_1 above, and R_3, R_4 and R_5 each represent a hydrogen atom, a halogen atom, It represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxy group, an alkoxy group, a sulfonamide group, an alkylsulfonamide group, an acylamido group, an amino group, or a mono- or dialkylamino group. ]. 2. The color photographic image forming method according to claim 1, wherein the yellow coupler is a 2-equivalent alpha acylacetamide yellow coupler. 3. The content of cyan coupler in the red-sensitive emulsion layer and the content of magenta coupler in the red-sensitive emulsion layer are each from 8 x 10^-^2 to 3 x 10^-^1 mol per mol of silver halide. A color photographic image forming method according to scope 2. 4 The content of silver halide in the blue-sensitive emulsion layer is 100
1 mg to 10 mg per cm^2, and the content of the 2-equivalent alpha acylacetamide yellow coupler in the layer is from 8 x 10^-^2 mol to 3 x 10^-^1 mol per mol of silver halide. A color photographic image forming method according to claim 3.