JPH03288847A - Processing method for color photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow the processing of the color photographic sensitive material having an excellent desilvering property by executing the bleaching and fixing processing of the color photographic sensitive material contg. at least one kind of specific compds. with single-bath processing after color development processing and confining the processing time to <=125 seconds. CONSTITUTION:The bleaching and fixing processing of the color photographic sensitive material contg. at least one kind of the compds. expressed by formula I is executed with the single-bath processing after the color development processing and the processing time is confined to <=125 seconds. In the formula I, R denotes a hydrogenatom or alkyl group. The alkyl group may be further substd. R1, R2 may be respectively the same or different and denote an alkyl group or ally group; the alkyl group may be further substd. X and Y may be respectively the same or different and denote a hydrogen atom, halogen atom, etc.; Z1 denotes anion; (n) denotes 1 or 2; n=1 when the dye forms an intramolecular salt. The generation of a desilvering defect is obviated even if the bleaching processing and the fixing processing are executed by the single- bath processing and are rapidly executed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing color photographic materials with excellent desilvering properties.

It may also represent an alkyl group or an allyl group.

(Prior Art) Color photographic materials are usually developed after imagewise exposure. The development process includes various steps, but includes at least a color development process, followed by a bleaching process and a fixing process.

In the color development step, the silver halide grains are imagewise reduced to silver, and at the same time a color reaction occurs to form a dye image. At this time, the generated silver is oxidized and converted into silver salt in the next bleaching process. Furthermore, in the subsequent fixing process, it is converted into a soluble silver salt and exits from the system of the photosensitive material.

Silver halide grains that were not reduced in the color development process are also
In this fixing process, it is simultaneously solubilized and released from the system. The ease with which this silver compound leaves the system is called desilvering property.

In recent years, processing steps have been simplified and shortened, and it has become possible to perform bleaching and fixing in one bath. This is a bleach-fixing process, generally called a Brix process.

Although this Brix treatment is preferable in terms of the number of treatments and shortening of treatment time, its bleaching and fixing abilities are generally inferior to those in which bleaching and fixing are performed in separate baths.

(Problem R to be solved by the invention) When the bleaching and fixing ability of Brix treatment is insufficient,
Silver may remain in the photographic material after processing. This development is generally referred to as desilvering failure.

When this phenomenon occurs, silver remains in the color image, which significantly deteriorates the reproducibility of the zero image. The most effective way to prevent this phenomenon is to reduce the amount of silver used, but means to further improve this are generally known.

Conventionally, therefore, measures have been taken to add various desilvering accelerators to light-sensitive materials.

For example, U.S. Patent No. 3,893,858, West German Patent No. 1
, No. 290,812, No. 2.059.988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-65732, No. 53-726
No. 23, No. 53-95630, No. 53-95631, No. 53-104232, No. 53-124424,
No. 53141623, No. 53-28426, Research Disclosure Hiroshi No. 17129 (July 1978)
Compounds having a mercapto group or disulfide group such as those described in Japanese Patent Publication No. 1987-140129; Thiazolidine derivatives such as those described in Japanese Patent Publication No. 140129/1983;
Thiourea derivatives described in JP-A-52-20832, JP-A-53-32735 and US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-581
Iodide described in No. 6235; West German Patent No. 966°410
Polyethylene oxides described in Japanese Patent Publication No. 2.748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836;
No. 9644, No. 53-94927, No. 54-3572
No. 7, No. 55-26506 and No. 58-16394
Examples include the compound described in No. 0 and iodine and bromine ions.

However, when these compounds are included in photosensitive materials,
This had the disadvantage of deterioration in stability over time, especially an increase in fog.

Furthermore, it is also known that compounds adsorbed to silver halide grains in the light-sensitive material have a large effect on desilvering properties.

However, even with the above technology, the desilvering performance is not sufficient, and the development of further improved technology has been desired.

Therefore, an object of the present invention is to provide a technique for improving the desilvering properties of color photographic materials in which bleaching and fixing are performed in one bath. Furthermore,
An object of the present invention is to provide a technique that does not cause desilvering defects even when bleaching and fixing are performed in one bath and rapidly.

(Means for Solving the Problems) The object of the present invention is to have at least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one blue-sensitive silver halide emulsion layer on a support, and the following general formula (
After color development of a color photographic light-sensitive material containing at least one of the compounds represented by I), bleaching and fixing are performed in a bath treatment, and the processing time is 125 seconds or less. A method of processing color photographic materials.

-Form (I) 11h (L)--t (wherein R represents a hydrogen atom or an alkyl group, and the alkyl group may be further substituted.

R+ and Rt may be the same or different and represent an alkyl group or an allyl group, and the alkyl group may be further substituted. However, at least one of R1 and R2 is an alkyl group having an acid substituent (eg, sulfo group, carboxyl group, etc.).

X and Y may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups, hydroxy groups, alkoxy groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, carbamoyl groups, sulfamoyl groups, cyano groups, carboxyl groups , a sulfo group, a trifluoromethyl group, a phenyl group or a benzo-fused ring, and the carbamoyl group and sulfamoyl group may be further directly substituted.

However, at least one of X or Y represents a hydroxy group, an alkoxy group, an alkoxycarbonyl group or a carboxyl group.

zI represents an anion, n represents 1 or 2, and when the dye forms an inner salt, n=1. ) Next, the − format (H will be explained in detail.

In the general formula (1) used in the present invention, the following substituents are preferably used for each substituent.

That is, R is a hydrogen atom, an unsubstituted alkyl group having 6 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
pentyl group, hexyl group, etc.) or substituted alkyl group (
Examples of substituents include halogen atoms, alkoxy groups, hydroxy groups, carboxyl groups, phenyl groups, etc.) R+ and Rx may be the same or different, and include unsubstituted alkyl groups having 12 or less carbon atoms (for example, methyl groups, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, etc.) or substituted alkyl group (substituents include, for example, carboxyl group, sulfo group, hydroxy group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.) alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, hensyloxy group, phenethyloxy group, etc.) alkoxycarbonyl groups having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxy aryloxy group (carminyl group, benzyloxycarbonyl group, etc.) having less than 10 carbon atoms (carminyl group, benzyloxycarbonyl group, etc.)
For example, phenoxy group, p-)'J-ruoxy group, etc.) Acyl group with carbon number r or less (e.g. acetyl group, propionyl group, (zoyl group, etc.)) Substituted or unsubstituted carbamoyl group with carbon number less than r, (e.g. carbamoy/+4 .N.

A sulfamoyl group (such as a sulfamoyl group, N,N-dimethylcarbamoyl group, morpholinosulfonyl group, piperidinosulfonyl group) with the number of carbon atoms below It represents a 7-aryl group of up to several tens (for example, a phenyl group, a goomethylphenyl group, a φ-70lophenyl group, a gooseulfophenyl group, a ψ-carboxylphenyl group, an α-su7tyl group, etc.). However, R
1. At least 7 of R2 have a sulfo group or a carboxyl group.

Xi? and Y may be the same or different,
Hydrogen atom, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl group having 6 or less carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) hydroxy group, alkoxycarbonyl having less than r carbon atoms groups (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), acyl groups (for example, acetyl group, propionyl group, benzoyl group, etc.) having less than 1 carbon atoms, and nacyloxy groups (for example, acetoxy group, propionyloxy group) having less than 1 carbon atoms. group, benzoyloxy group, etc.) Alkoxy having up to r carbon atoms (e.g., methoxy group, ethoxy group, propyloxy group, butyloxy group, benzyloxy group, etc.) Carbamoyl group or substituted carbamoyl group having up to 6 carbon atoms (e.g., carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, etc.) sulfamoyl group or substituted sulfamoyl group having 6 or less carbon atoms (e.g. sulfamoyl group, N1N-dimethylsulfamoyl group, morpholinosulfamoyl group, etc.) cyano group, carboxyl group, It represents a sulfo group, a trifluoromethyl group, a phenyl group, or a benzo-fused ring. However, at least one of X and Y represents a hydroxy group, an alkoxy group, an alkoxycarbonyl group, or a carboxyl group.

Specific examples of the dye represented by the general formula (r) of the present invention are illustrated below. However, it is not limited to this only.

■-/ ■-2 -J -t I-φ -7 -r ■-2 [-10 I-// i-/1! 1-77)-/J-131-/ψ-it The compound represented by the general formula (I) of the present invention is also known and can be easily synthesized by conventionally known methods. Specifically, it is described in US Pat. No. 2,701t, 7/1, US Pat.

- The amount of the compound of form (I) to be added is not particularly limited, but
When used in a silver halide emulsion layer, l×IOA-2×
10 mol 1 mol Ag is preferred.

Compound having repeating unit of general formula (I), format (L)
The compound represented by can be incorporated into a photographic emulsion by a conventional method. Usually, it is dissolved in a solvent such as methanol, ethanol, water, methyl cellulose, or water-soluble ketones and added to the emulsion. It may be added at any stage in the emulsion manufacturing process.

The sensitizing dye represented by general formula (I) can be used with other sensitizing dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes,
It may be used in combination with complex merocyanine dyes, holo, N-largeanine dyes, hemicyanine dyes, styryl dyes, hemioquinol dyes, and the like. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

- As a sensitizing dye used in combination with the sensitizing dye of format (I), there is a dye represented by the following general formula (Ir).

(II) R13Ra 4 (Here, Y5 represents an oxygen atom or a sulfur atom, and %
X3 and X4 represent a sulfur atom or a selenium atom, Z3 and Z4 represent a group of nonmetallic atoms necessary to form a benzene ring or a naphthalene ring,
12 is an alkyl group having 6 or less carbon atoms or a carbon number/~≠
represents an alkyl group having 6 or less carbon atoms substituted with an alkoxy group, chlorine atom, fluorine atom or phenyl group, and R13 and R14 are an alkyl group having 10 or less carbon atoms, a sulfo group, a hydroxy group, a carboxy group, a carbamoyl group , a sulfoalkyl group, a carboxyphenyl group, or an alkyl group having 6 or less carbon atoms substituted with a rogen atom.

Next, preferred compounds represented by the -form (ff) are represented by the general formulas (ff-A) and (I[-B).

(II-A) 27 or ([-B) 7 Here, Y6 button and Y7 are oxygen atoms or sulfur atoms, preferably oxygen atoms.

R22/R23% R28 and R29 represent a lower alkyl group having 1 to 2 carbon atoms, which may be substituted with a lower alkoxy group having 1 to 5 carbon atoms, a chlorine atom, a fluorine atom, or a phenyl group. (preferably an alkyl group substituted with an alkoxy group) R24\R25% R3
0 and R31 are sulfoalkyl groups having 2 to q carbon atoms,
Starting from 2 carbons! represents a carboxyalkyl group having 2 to 2 carbon atoms, a hydroxyalkyl group having 2 to 2 carbon atoms, an alkyl group having an unsubstituted carbamoyl group having 2 to 2 carbon atoms, and a lower alkyl group having 6 or less carbon atoms, and the lower alkyl group is a fluorine atom,
It may be substituted with a chloro atom, an alkoxy group with a carbon number/number of carbon atoms, a phenyl group, or a sulfophenyl group.

R2s, R27, R32 and R33 are hydrogen atoms,
Chlorine atom, bromine atom, lower alkyl group having 1 to 7 carbon atoms, lower alkoxy group having 1 to 6 carbon atoms, carboxy group,
Hydroxy group, total number of carbons starts from 2! The number of carbon atoms in the alkoxycarbonyl group and acyl group part is from 2! represents an acylamino group, a phenyl group, and a phenyl group is a chlorine atom,
It may be substituted with a bromine atom, an alkyl group having ψ or less carbon atoms, or an alkoxy group having ψ or less carbon atoms. R22, R23
, R2s> and R29 may be the same or different.

Further, R26, R27, R32 and R33 may be the same or different.

%R2, 4 R25, R30 buttons and R3 are particularly preferably groups selected from methyl, ethyl, and sulfopropyl groups! Yes.

X7, X8, X9> and XIO are sulfur atoms or selenium atoms and may be the same or different.

- Specific examples of the dye represented by the format (If) include, but are not limited to, the following.

I[-1 If -,2 CH2CH2C)T3 しR3 I-J [-1 ■-ψ 1[-7 [-3 [-J' [-4 [-10] [-// ■-/yo11-/ J ■-77 [-/j ■-i3 [-/ ψ [-1g [-15' ■ Ko O ■-27 ■-22 ■-23 ■-27 , [-21 11-usu ■-uψ [- +21 OsH O3H ■-26 The sensitizing dye represented by general formula (II) is preferably used in a molar ratio of 115 to 1/200 of the compound represented by general formula (1), preferably 1/10 to 1/100. More preferably.

A technique for using the compound represented by the general formula (I) in order to control the progress of development was published in JP-A-60-'1.
Although it is disclosed in No. 72039, there is no description regarding desilvering properties and it is irrelevant to the present invention.

Next, the silver halide emulsion used in the present invention will be explained. These silver halide grains include those with regular crystals such as cubes, octahedrons, and dodecahedrons, those with irregular crystals such as spherical and plate shapes, and those with crystal defects such as twin planes. or a combination thereof.

The grain size of this silver halide may be fine grains of about 0.2 microns or less or large grains with a projected area diameter of about 1 p micron, and may be a polydisperse emulsion or a monodisperse emulsion, preferably with a coefficient of variation. It is a monodisperse emulsion of 20% or less.

The halogen composition of the silver halide grains may be any of silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloride. When silver bromide is used, it is preferable because the effects of the present invention are remarkable. In particular, silver iodobromide having a silver iodide content of 0 to 30 mol% is preferable, and 10 mol% or less is more preferable.

Such silver halide photographic emulsions are used, for example, in research and
Disclosure (RD), 17643 (1978
), pp. 22-23, “I.

Emulsion preparation
and types)' and on the same floor 18716 (1
(November 979), 648 pages, "Physics and Chemistry of Photography" by Glafkide, published by Beaumontel (P, Glafki
des, Chemic etPhjsique Ph
otographique Paul Montel,
1967) "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F. Duffin, Phot
graphic Emulsion Chemistry
y (Focal Press, 1966))
, “Production and Coating of Photographic Emulsions” by ZeHkman et al., published by Focal Press (ν, L. ZeHkman et a.
l, Makjng and Coating Photo
graphic emulsion, Focal
Press.

(1964) and others.

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

The silver halide emulsion used in the light-sensitive material of the present invention is usually one that has been subjected to physical ripening, chemical sensitization, and spectral sensitization.

The emulsion grains mentioned above may be of the so-called surface latent image type, which mainly forms a latent image on the surface, or may be of the internal latent image type, which mainly forms a latent image inside the grains. The agent is Research Disclosure N.
It is described in ch17643 and ch18716, and the relevant parts are summarized in the table below.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a phase structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, known photographic additives that can be used in the present invention, in which a mixture of particles of various crystalline forms may be used, are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below. .

Additive type RD17643 RD187
161 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649, right column 4 Brightening agent
Page 24 5 Antifogging agent Pages 24-25 Page 649 right column ~ and Stabilizer 6 Light absorber Page 25-26 Page 649 right column ~
Filter dye F4 650 pages left UV absorber 7 Su5i, r inhibitor 25 pages right 1ift
Page 650 left to right column 8 Dye image stabilizer page 25 9 Hardener page 26 Page 651 left column 1O
Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 12 Coating aid, Pages 26-27 Same as above Surface agent 13 Static Page 27 Same as above Inhibitor Also, in addition to phenol, preservatives include phenoxyethanols. Alternatively, meccins, proxel, salicylic acid sodium salt, etc. can be used.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) 17643, ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4.022.620, 4.3
No. 26,024, No. 4,401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425,020,
No. 1,476.760, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,067, Research Disclosure No. 81124220 (June 1984) ), Japanese Patent Application Publication No. 1986
-33552, Research Disclosure 24
230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630, U.S. Pat. No. 4,540.
Particularly preferred are those described in No. 654 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4.228,23
No. 3, No. 4.296,200, No. 2,369,92
No. 9, No. 2,801゜171, No. 2,772,16
No. 2, No. 2゜895.826, No. 3,772.0
No. 02, No. 3,758.308, No. 4,334.
No. 011, No. 4,327.173, West German Patent Publication No. 3,329.729, European Patent No. 121365A,
U.S. Patent No. 3,446.622, U.S. Patent No. 4,333,9
No. 99, No. 4,451,559, No. 4,427,
Preferred are those described in No. 767, European Patent No. 161.626A, and the like.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2125.
570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat. No. 4,080,211, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2.131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , multi-equivalent couplers described in JP-A No. 4,310.618, etc., DIR redox compound releasing couplers described in JP-A-60-185950, etc., and dyes that recolor after separation described in European Patent No. 173,302A. Examples include couplers that emit .

Couplers for non-inventive use can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. It is written in the number etc.

The photosensitive material of the present invention also contains hydroquinones that release development-inhibiting compounds described in U.S. Pat. Nos. 3,379,529 and 3,639,417, and research materials.
Disclosure N (L1B264 (June 1979)
Naphthohydroquinones that release the development-inhibiting compounds described in (1) and the like can be preferably used.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Na17643, and pages 647, right column to page 648, left column of Douben 18716.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclo + - (Research Disclo
sure) No. 176, pages 28-30 (RD-17643
) Any of the known methods and known treatment liquids can be applied. The processing temperature is usually selected between 18°C and 50°C, but it may also be below 18°C or above 50°C.

When forming a dye image, conventional methods can be applied.

For example, negative-positive method (e.g. Journal of
theSociety of Motion Pict
ure and Television Engineering
rs, 61 @ (1953), 667-701
): development with a developer containing a black and white developing agent to produce a negative silver image, followed by at least one -like exposure or other suitable capri treatment, followed by color development. A color reversal method is used to obtain a dye-positive image.A silver dye bleaching method is used in which a photographic emulsion layer containing two dyes is exposed and developed to form a silver imprint, and this is used as a bleaching catalyst to bleach the dye.

The color developing agent is generally prepared from an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer, such as phenylene diamine [(e.g. 4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3 -Methyl-4-amino-N-ethyl-N-
β-methanesulfamide ethylaniline, 4-amino-
3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition to this, Photog by F. A. Mason
rapicProcessing Chesist
ry (Focal Press, 1966)
pages 226-229 of U.S. Patent No. 2,193°015,
Those described in JP-A No. 2,592,364, JP-A-4864933, etc. may be used.

The color developer may also contain a pHI buffer, a development inhibitor or an antifoggant.

Also, if necessary, add water softener, preservative, etc. solvent,
It may also contain development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, tackifying agents, polycarboxylic acid chelating agents, antioxidants, and the like.

Specific examples of these additives include Research Disclosure (RD-17643) and U.S. Patent No. 4.083,7.
No. 23, West German Publication (○LS) No. 2622.950, etc.

The photographic emulsion layer after color development is usually bleached.9 In the present invention, the bleaching treatment is carried out simultaneously with the fixing treatment (Brix treatment).

Bleach agents include compounds of polyvalent metals such as iron (■), cobalt (I [[), chromium (■), copper (II)], peracids,
Quinones, nitrone compounds, etc. are used.

The bleach-fix solution (printer solution) is disclosed in US Pat. No. 3,042.
No. 520, No. 3,241,966, Special Publication No. 1973-1985
In addition to the bleaching accelerators described in Japanese Patent Publication No. 06 and Japanese Patent Publication No. 45-8836, and the thiol compounds described in Japanese Patent Application Laid-open No. 53-65732, various additives can also be added.

This Brix treatment is efficient for short periods of time, and has significant effects when the preferred Brix treatment time of the present invention is 125 seconds or less.

Example-1 Preparation of Emulsion A-1 A silver nitrate aqueous solution and an aqueous solution containing KBr and Kl were added by double jet to an aqueous gelatin solution kept at 60"C while keeping the pBr at 4.5 to change the (100) crystal habit. A monodisperse emulsion (width: 0.3 μm) containing 4 mol % of silver iodide and an average grain size of 0.3 μm was prepared. , chemical sensitization was carried out.Furthermore, red sensitizing dye Eχ
S-1, 10-3 mol-1 mol-Ag, and 1l-17
was added at a ratio of 4×10 −S mol 1 mol−Ag and adsorbed onto the grains to prepare red-sensitive silver iodobromide emulsion A-1.

Preparation of Emulsion B-1 A surface-low iodide type silver iodobromide emulsion was prepared by the double jet method containing iodine ions in the following manner.

In a reaction tank kept at 60° C., 1000 cc of water, 25 g of inert gelatin, 4 g of potassium iodide, and 10 g of potassium bromide were placed and continuously stirred.

A silver nitrate solution and a potassium bromide aqueous solution are added to this reaction tank using a double jet. This emulsion contains 116 mol% iodide.
It had a tabular shape (aspect ratio 5) with an average particle size of 0.75μ, and was chemically sensitized by adding sodium thiosulfate and potassium chloroaurate.

Furthermore, 5×10−4 of the sensitizing dye represented by ExS-1 was added.
Red-sensitive silver iodobromide emulsion B-1 was prepared by adding a compound represented by 1 mol-Ag and 2×10-'mol 1 mol-Ag of a compound represented by I[-17 to be adsorbed onto the grains. did.

Furthermore, samples were prepared by the following method.

A color photographic material was prepared by coating a paper support laminated on both sides with polyethylene and two layers of laminated glass starting from the next layer. The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/rrT are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin...1.30 2nd layer
Layer (antihalation layer) Black colloid layer...0.10 Gelatin...0.70 Third layer (low sensitivity red sensitive layer) Emulsion A-1...0.10 Gelatin...1.00 Cyan Coupler (ExC-1) = -0,14 Cyan coupler (ExC-2) = -0,07 Antifading agent (Cpd-2,3,4゜9 equivalent)...0.12 Power puller dispersion medium ( Cpd-5)...0.03 Coupler solvent (Solv-1, 2°3 equivalent)...0.06 4th layer (high sensitivity red sensitive layer) Emulsion B-1...0.15 Gelatin ...1.00 cyan coupler (ExC-1) -0,20 cyan coupler (ExC-2) ...0.10 antifading agent (Cpd-2,3,4゜9 equivalent) ...0 .15 Power puller dispersion medium (Cpd-5)...0.03 Coupler solvent (Solv-1,2 3)...0.10 5th layer (intermediate layer) Black colloidal silver...0.02 Gelatin ...1.00 Color mixing prevention agent (Cpd-6,7) ...0.08 Color mixing prevention agent solvent (Solv-4,5) ...0.16 Polymer latex (Cpd-8) ...0 .10 6th
Layer (Low sensitivity green sensitive layer) Silver iodobromide EM4 spectrally sensitized with green sensitizing dye (ExS-4) (silver iodide 2.5 mol%, average grain size 0.2
8 μ, grain size distribution 12%, cubic, core density type (core shell))...0.04 Silver iodobromide EM5 spectrally sensitized with green sensitizing dye (ExS-4) (silver iodide 2.8 mol) %, average particle size 0.4
5μ, particle size distribution 12%, flat plate (aspect ratio -5
))...0.06 gelatin
...0.80 magenta coupler (ExM-1)
-0, IO anti-fading agent (Cpd-9) -0
,10 stain inhibitor (Cpd-10) -0,01
4 Nine inhibitor (Cpd-11) -0,001 Stain inhibitor (Cpd-12) ・0.01 force puller dispersion medium (Cpd-5) = -0,05 coupler melt medium (S
olv-4,6)-0,15 7th layer (high sensitivity green sensitive layer) Silver iodobromide EM6 spectrally sensitized with green sensitizing dye (ExS-4) (3.5 mol% silver iodide, Average particle size 0.9
μ, particle size distribution 23%, flat plate (aspect ratio = 9,
0.10 Gelatin 0.80 Magenta coupler (ExM-1) 0.10 Anti-fading agent (Cpd-9) 0.10 Anti-stain agent (Cpd -10)...0.01 stain inhibitor (Cpd-11)...0.001 stain inhibitor (
Cpd-12) ...0.01 force puller dispersion medium (C
pd-5)...0.05 coupler solvent (S o
I v-4,6) ・=0.15 8th layer (yellow filter layer) Yellow colloid)'silver) ・0.20 Gelatin ・1.00 Color mixture prevention agent (Cpd-7) ・0. 06 Color mixing inhibitor solvent (Solv-4, 5)...0.15 Polymer latex (Cpd-8)...0.10 No. 9
Layer (low sensitivity blue sensitive layer) Spectrally sensitized with blue sensitizing dye (ExS-5) w
&EM7 (silver iodide 2.5 mol%, average grain size 0.
35μ, grain size distribution 8%, cubic, core density type (core shell))...0.07 Silver iodobromide EM8 spectrally sensitized with blue sensitizing dye (ExS-5) (silver iodobromide 265 mol%) , average particle size 0.
45μ, grain size distribution 16%, flat plate (aspect ratio =
6))...0.10 Gelatin...0.50 Yellow coupler (ExY-1) -0,20 Stain inhibitor (Cpd-11L=0.001 Anti-fading agent (Cpd)
-6) ・0.10 coupler dispersion medium (Cpd
-5) ・=0.05 coupler solvent (Solv-2
) -0,05 1st O layer (high sensitivity blue sensitive layer) Silver iodobromide EM9 spectrally sensitized with blue sensitizing dye (ExS-5) (iodide*2.5 mol%, average grain size 1. 2
μ, particle size distribution 21%, flat plate (aspect ratio = 14
) ) ...0.25 gelatin
...1.00 yellow coupler (ExY-1)
...0.40 Stain inhibitor (Cpd-11) Anti-fading agent (Cpd-6) Coupler dispersion medium (Cpd-5) Coupler solvent (Solv-2) 11th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber ( Cpd-1,3゜13 equivalent) ...0.002 ...0.10 ...0.15 ...0.10 ...1.50 ...1.00 Color mixing prevention agent ( Cpd-6,14 equivalent) ...0゜6 Dispersion medium (Cpd-5) Ultraviolet absorber solvent (Solv-1 2) ...0.15 Irajesitan prevention dye (Cpd-15,16 equivalent) ) ...0.02 anti-irradiation dye (Cpd-17, 18 equivalent) ...0.02 No. 12
Layer (protective layer) Fine particle chlorobromide 1! (Silver chloride 97 mol%, average size 0.
2μ) ...0.07 modified poval
...0.02 gelatin
...1.50 gelatin hardening agent (H-1
)...0.17 Further, in each layer, Alkanol IagefacF −
120 (manufactured by Dainippon Ink Co., Ltd.) was used. In the silver halide or colloidal silver containing layer, (Cpd
-1920, 21) was used. The compounds used in the examples are shown below.

ExS-1 (CM, 5O2 (CHz)ssO:+H xS 2 pd xS-4 xS-5 p d-4 SO,lI pd pd +CHt CH), C0NHCaHqCt) (n=100-1000) pd 0 CH3 C, H, 0 1 p d-7 H H pd-11 H pd polyethyl acrylate Cpd-13 Cpd-14 H Cpd-18 CH.

Ht Pd-19 Cpd-20 Cpd 1 N = N Cpd-15 Cpd-16 Cpd-17 osK xC xM-1 SO, to xY 1 1+O olv-1 Di(2-ethylhexyl) phthalate o1v-2 trinonyl phosphate olv-3 Di(3-methylhexyl) phthalate olv-4 tricresyl phosphate olv-5 dibutyl phthalate olv-6 trioctyl phosphate olv-7 1,2-bis(vinylsulfonylacetamido)ethane The sample prepared in this manner will be referred to as sample 101.

Next, in emulsion A-1, emulsions A-1 and 1-1.2 and 3.5 of the present invention were used instead of ExS-1.
2, 3, 4, 5.

Furthermore, in emulsion B-1, emulsions B-1 and I-1, 2, 3, and 5 of the present invention were used instead of ExS-1.
-2, 3, 4, 5.

Sample 10 was prepared by using emulsions A-2 to 5 and B-2 to 5 in place of emulsions A-1 and B-1 in sample 101, respectively.
2 to 105.

In emulsions A-2 and E-2, instead of 1l-17, E
Emulsions using xS-2 are designated as A-6 and B-6, respectively. Sample 106 is obtained by using emulsions A-6 and B-6 instead of emulsions A-1 and B-1 in sample 101, respectively.

Sample 107 is obtained by using emulsions A-7 and B-7 made of pure AgBr instead of emulsions A-1 and B-1 in sample 101.

Sample 10B is obtained by using emulsions A-8 and B-8 made of pure AgBr instead of emulsions A-2 and B-2 in sample 102.

Next, these samples were sufficiently exposed to white light, and then processed using the samples shown below.

[Processing process]

First development (black and white development) 38°C 1'15'' water
Wash at 38°C 1'30'1'30'
100 Lux or more 12 or more color development
38℃ 2'15' water washing
38°C 45' bleach fixing 38°C3
0' and 60'' water washing 38°C2
'15' [Treatment liquid composition] Xing Erli Yinglan Nitrilo-N, N, N-)rimethylenephosphonic acid, pentasodium salt 0.6g Diethylenetriaminepentaacetic acid, pentasodium salt Potassium sulfite Potassium thiocyanate Potassium carbonate Hydroquinone monosulfonate・Potassium salt diethylene glycol 1-phenyl-4-hydroxymethyl-4-methyl-3 = pyrazolidone Potassium bromide Potassium iodide Add water (pH 4゜30゜1゜35゜25.0g 15.0d 2,0g 0 , 5g 5, 0 ■ ff1 9, 70) Inner j: □ Side plate benzyl alcohol diethylene glycol 3.6-cythia 1.8-octanediol 15, (1wd 12.0m 0, 2g Nitrilo-N, N, N- Trimethylenephosphonic acid/pentasodium salt Diethylenetriaminepentaacetic acid/pentasodium salt Sodium sulfite Potassium carbonate Hydroxylamine sulfate N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate Bromide Add potassium potassium iodide water 5.0 g 0.5 g 1.0 mg 1 (pH 10.40) 0.5 g Appearance α 4 liquid 2-mercapto-1,3,4 triazoleethylenediaminetetraacetic acid 1.0 g Sodium trihydrate 5.Og ethylenediaminetetraacetic acid/Fe(I[[) ・Ammonium hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700 g/l liquid) 160.Oj glacial acetic acid
Add 5.0Wl water
11 (pH 6, 50,) After treatment, the amount of silver remaining in the sample was determined by optical density measurement using yellow light.

The results are shown in Table 1. The smaller the value, the less residual silver and the smaller the degree of desilvering failure.

Procedural amendment

Claims (1)

[Scope of Claims] A silver halide emulsion layer having at least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one blue-sensitive silver halide emulsion layer on a support, and represented by the following general formula (I). 1. A color photographic light-sensitive material, which is characterized in that, after color development, a color photographic light-sensitive material containing at least one compound selected from the group consisting of: processing method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom or an alkyl group.R
_1 and R_2 may be the same or different,
Represents an alkyl group or an allyl group. However, at least one of R_1 and R_2 is an alkyl group having an acid substituent. X and Y may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups, hydroxy groups, alkoxy groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, carbamoyl groups, sulfamoyl groups, cyano groups, carboxyl groups , a sulfo group, a trifluoromethyl group, a phenyl group or a benzo-fused ring. However, X
Alternatively, at least one of Y represents a hydroxy group, an alkoxy group, an alkoxycarbonyl group or a carboxyl group. Z represents an anion, n represents 1 or 2, and when the dye forms an inner salt, n=1. )