JPS62249149A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent occurrence of fog and deterioration of color development density by processing a color photographic material having an emulsion layer composed substantially of silver chloride grains with a liquid color-developer specified in sulfite concentration containing a preservative. CONSTITUTION:The photographic sensitive material has an emulsion layer composed of silver halide grains containing >=80mol% silver chloride, and an emulsion layer containing the magenta coupler represented by formula I in which Z is a nonmetallic atomic group necessary to form an N-containing hetero ring; X is H or a group to be released by the coupling reaction with the oxidation product of a color developing agent; and R is H or a substituent. The photographic sensitive material is processed with the liquid color-developer containing the sulfite in an amount of <=4X10<-3>mol per l of the developer and the preservative represented by formula II in which each of R<1> and R<2> being 1-3C alkyl, thus permitting the developer superior in storage stability to be obtained and deterioration of dye density due to rapid processing and occurrence of fog to be restrained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, it relates to a method for processing a silver halide color photographic light-sensitive material. The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains consisting of:

[Background of the Invention] Usually, in a method of forming a dye image by processing a silver halide color photographic light-sensitive material, after imagewise exposure, an oxidized p-phenylenediamine color developing agent and a dye image-forming coupler are used. A dye image is formed by reacting with the dye. In this method, a subtractive color reproduction method is usually applied, and cyan, magenta and yellow dye images corresponding to red, green and blue are formed on respective photosensitive layers. In recent years, in forming such dye images, high-temperature development processing and processing steps have generally been omitted in order to shorten the processing time. In particular, in order to shorten the development time, it is extremely important to increase the development speed in color development. The development speed in color development is influenced by two directions. One is a silver halide color photographic material and the other is a color developer. In the former case, the composition of the grains of the silver halide emulsion used has a great influence on the development speed, and in the latter case, the conditions and composition of the color developing solution have a great influence on the development speed.

A silver halide color photographic light-sensitive material (hereinafter referred to as a silver chloride color photographic light-sensitive material) in which a light-sensitive silver halide emulsion consists essentially of silver chloride is a silver halide color photographic light-sensitive material (hereinafter referred to as a silver chloride color photographic light-sensitive material), which contains conventional silver chloride bromide, silver chloroiodobromide, silver iodine. Color photographic light-sensitive materials made of halide emulsions containing silver bromide and silver iodide, such as silver bromide emulsions, are rapidly developed, and bromide and iodide ions, which inhibit the development reaction, are used for color development. Since it does not accumulate in the solution, it is extremely useful as a light-sensitive material for rapid processing.The inventor of the present invention conducted various studies using a silver chloride color photographic light-sensitive material suitable for rapid processing, and found that it has the following drawbacks. I understand.

That is, firstly, hydroxylamine, which is conventionally used as a preservative, acts as a developer for silver chloride, causing silver development to proceed and the color density of the final dye image to be obtained to be reduced. .

Second, sulfite, which is used as another conventional preservative, acts as a dissolving agent for silver chloride, and physical development with a color developing agent proceeds rapidly, resulting in a silver development reaction and a coupling reaction. The color density was reduced because the balance was lost, that is, silver development was too advanced and the coupling reaction was delayed.

The present inventors conducted various studies in order to solve the first and second problems mentioned above. As a result, the first problem was solved by using a specific compound in place of hydroxylamine. It was possible to obtain a color developing solution without developing, thus suppressing a decrease in dye density, and having a good preservative.

In addition, as a result of various studies to solve the second problem,
It has been found that by using a specific coupler, a decrease in color density can be prevented without disrupting the balance between the coupling reaction and the silver development reaction.

In other words, by combining the above two techniques, the present inventors have discovered that, for the first time, they have developed a material that is substantially free from silver chloride, which does not reduce dye density and has good storage stability even when the sulfite concentration in the color developing solution is low. Although it was possible to obtain a color developing solution for silver halide color photographic light-sensitive materials, as a result of further investigation, it was found that fogging is likely to occur particularly when heavy metal ions are mixed.

These heavy metal ions pose a particular problem when a large amount of photosensitive material is processed continuously.

In addition, in development processing methods in which silver halide photographic light-sensitive materials are continuously processed using an automatic processor, etc., the components of the color developer are kept within a constant concentration range in order to avoid changes in development finish characteristics due to changes in component concentration. means are necessary. As such a method, a method of replenishing a replenisher is usually used to supplement the missing components and dilute the unnecessary increased components.

The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow liquid, a low fall thickness replenishment system has been widely used in which these replenishers are concentrated and refilled in small amounts. The generation of capri due to heavy metal ions is a problem and its solution is strongly desired.

[Object of the Invention] Accordingly, the object of the present invention is to provide a silver halide color photographic light-sensitive material that uses a color developing solution with excellent storage stability, has excellent photographic properties such as fog and maximum color density, and enables rapid processing. The objective is to provide a processing method for

[Structure of the invention]

The above-mentioned object of the present invention is to process a silver halide color photographic light-sensitive material, which comprises imagewise exposing a silver halide color photographic light-sensitive material containing at least one silver halide emulsion layer, and then subjecting it to a process including at least a color development step. In the method, the silver halide emulsion layer is a silver halide emulsion layer containing silver halide grains consisting of 80 mol% or more of silver chloride, and at least one layer of the silver halide emulsion layer has the following general formula: The color developer having a magenta coupler represented by [M] and used in the color development step contains a compound represented by the following general formula [I], and contains a sulfurous acid 1!
This is achieved by a method for processing a silver halide color photographic material, which is characterized in that the salt concentration is 4.times.10@-3 mol or less per color developer.

General formula [I] (In the formula, R1 and R2 each represent an alkyl group having 1 to 3 carbon atoms.) General formula [M] (Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle. The ring formed by 2 may have a substituent.

X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent.

In addition, R represents a hydrogen atom or a substituent.) [Specific constitution of the invention] In the color developing solution used in the present invention, instead of hydroxylamine conventionally used as a preservative, the general formula [I]
A compound represented by (hereinafter referred to as the preservative of the present invention) is used.

In the general formula [I], R1 and R2 each represent an alkyl group having 1 to 3 carbon atoms, but the alkyl groups having 1 to 3 carbon atoms represented by R1 and R2 may be the same or different, for example, a methyl group. , ethyl group, n-propyl group, 1so-propyl group, etc.

R1 and R2 are preferably both ethyl groups.

Specific examples of the compound of the present invention represented by the general formula [I] are shown below, but the present invention is not limited thereto.

(I-2) (I-3) (i-4) (I-4) These compounds of the present invention are usually hydrochloride, sulfur M salt, p-1
It is used in the form of salts such as luenesulfonate, oxalate, phosphate, and acetate.

The concentration of the compound of the present invention in the color developing solution is preferably the same as that of human 0xylamine commonly used as a preservative, for example, 0.11 J/ffi to 50 a/ffi, more preferably 0.5 g. //! ~30g/
/! It is.

Among the compounds represented by the general formula [I] of the present invention, for example, N,N-diethylhydroxylamine can be used as a preservative for a black and white developing agent in a color developer containing a black and white developing agent. Are known.

Normal black and white developing agents such as hydroquinone, hydroquinone monosulfonic acid, phenidone, and rose 7 minophenol are relatively stable when used as black and white developing agents in black and white developers, and sulfites are used as preservatives. However, it is known that when added to color developing solution i, a cross-oxidation reaction occurs with the color developing agent, resulting in extremely poor storage stability. To preserve the black and white developing agent added to these color developing solutions,
Hydroxylamine has little effect.

N as a preservative for the black and white developing agent added to the color developer.
As an example of using N-diethylhydroxylamine, it is known that it is used together with phenidone in the so-called external color development method, in which color photographic materials are developed by a reversal method using a color developing solution containing a coupler. There is. The role of 7-enidone in this case is to increase the development rate of external type light-sensitive materials with poor developability and to increase the density of dye images.

Furthermore, in magenta color developing solutions that do not contain phenidone, for example, N,N-diethylhydroxylamine is known to have a rather negative effect on the storage stability of external color developing solutions by destroying couplers. (Refer to Japanese Patent Publication No. 45-22198).

Another example of using a compound of the present invention, such as N,N-diethylhydroxylamine, as a preservative for a black and white developing agent added to a color developer is as follows: Techniques for preserving added phenidone derivatives (see JP-A No. 53-32035) and techniques for preserving phenidone derivatives together with hydroquinones (see JP-A-52-153437) can be mentioned. .

As mentioned above, the compound of the present invention is conventionally known to be used as a preservative for black and white developing agents added to color developing solutions; It is not known as such.

As described above, some of the compounds of the present invention are already known as preservatives for black and white developing agents added to color developing solutions, but in the present invention, the following sulfite concentration is 4. X 10-3 mol/below not only acts effectively as a preservative for ordinary color developing solutions, but also acts as a chelating agent represented by the general formula [II] and/or [I[] described in detail below. As expected, when used in combination, the generation of capri due to the contamination of heavy metal ions was well prevented, and furthermore, a color developer with excellent stability was obtained without a drop in pH, generation of tar, etc. There was no surprising effect.

The color developing solution used in the present invention has a sulfite concentration of not more than 4.times.10@-3 mol per 12 of the color developing solution, preferably from 2.times.10@-4 to 0 mol.

In conventional color developing solutions, sulfite is added as one of the preservatives, usually at a concentration of 8X10-3 to 4X1 per 1/L of color developer.
Although an amount of about 0-2 mol was used, when the conventional system was applied to the present invention, a decrease in color density occurred, which was thought to be caused by dissolution of silver chloride. The present invention solves the above problem by lowering the sulfite concentration to a specific range, and further by using a specific combination of the above-described compound of the present invention as a preservative. This was solved by combining it with a coupler.

Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

As described above, some of the compounds of the present invention are already known as preservatives for black and white developing agents added to color developing solutions, but in the present invention, the compounds described below are used as preservatives for black and white developing agents.
! ! A chelating agent with an acid salt concentration of 4 x 10-3 mol/C or less, which not only acts as a preservative for ordinary color developing solutions, but also has the general formula % formula % detailed below. As expected, when used in combination, the occurrence of fog caused by the contamination of heavy metal ions was well prevented, and furthermore, a color developer with excellent stability was obtained without a decrease in DH and the generation of tar. It was an amazing effect.

The color developing solution used in the present invention contains the general formula [I
It is preferable to contain a chelating agent selected from [], [I[], [V], [VI] and [■1].

General formula [II] General formula [I [I] Ls -Ra R7-Ls N L7 Rs (In the general formulas [II] and [I [[], is an alkylene group, a cycloalkylene group, a phenylene group, -La - 0
-La -0-La- or Ls -Z Ls-. Here, 2 represents L12-R11L12-Rn, and each of 1 to L+3 represents an alkylene group.

R3 to R+s are hydrogen atoms, hydroxyl groups, and carboxylic acids, respectively! l! (including its salts) or phosphone Mll (including its salts). However, at least two of R3-R6 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least two of R7-R9 are carboxylic acid groups (including salts thereof). General formula [V] General formula [V[I (In the above general formulas [V] and [VI], R1, R2, R
3 and R4 each represent a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -0Rs, -COORs, -CON or a phenyl group. Further, Rs, Rs, R7 and R8 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R2 represents 10H or a hydrogen atom, R1 is a halogen atom, a sulfonic acid group, or a carbon atom number of 1
~7 alkyl group, R7 10Rs, -COOR6, =C0N, or a phenyl group. ) General formula [VI] (In the above general formula [■], R1, R2, and R3 are each a hydrogen atom, a hydroxyl group, and a carboxylic acid group (including salts thereof)
Or represents a phosphate group (including its salts). However, R1,
At least one of R2 and R3 is a hydroxyl group, and at least one of R1, R2 and R3 is a carboxylic acid group (including a salt thereof) or a phosphorus group (including a salt thereof). nl, R2 and 03 each represent an integer of 1 to 3) general formulas [II and [1! ! The alkylene group, cycloalkylene group, and phenylene group represented by L in ], and the alkylene group represented by L1 to L13 include those having a substituent.

Next, preferred specific examples of the compounds represented by the general formulas [I[] and [II[] are listed below.

[Exemplary compounds] [I[-11 ethylenediaminetetraacetic acid [ll-2]
diethylenetriaminepentaacetic acid [ll-3]ethylenediamine-N-(β- and droxyethyl)-N,N'
, N'-triacetic acid [n-41 propylene diamine tetraacetic acid [I[-5]
Triethylenetetraminehexaacetic acid [11-61 cyclohexanediaminetetraacetic acid [n-711,2-diaminopropanetetraacetic acid [n-811,3-diaminopropan-2-ol-tetraacetic acid [I[-9]ethyl ether diamine tetraacetic acid] Acetic acid [ll
-101 glycol ether diamine tetraacetic acid
゛[I[-11]ethylenediaminetetrabrobion wave [
II-12] phenylenediaminetetraacetic acid [I[-
13] Ethylenediaminetetraacetic acid disodium salt [I[-14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [ll-151 Ethylenediaminetetraacetic acid tetrasodium salt [ll-16] Diethylenetriaminepentaacetic acid pentasodium salt [I-17] ] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt [ll-181 Propylenediaminetetraacetic acid sodium salt [If -191 Ethylenediaminetetramethylenephosphonic acid [ll-201 Cyclohexanediaminetetra Sodium acetate salt [ll-211 diethylenetriaminepentamethylenephosphonic acid [ll-22] cyclohexanediaminetetramethylenephosphonic acid [1-1] nitrilotriacetic acid [11[-2] iminodiacetic acid [11-31 nitrilotrib O pionic acid [111-] 41
Nitri-O trimethylenephosphonic acid [11[-5] iminodimethylenephosphonic acid [I [[-61 nitrilotriacetic acid trisodium salt] Among these chelating agents of the present invention, from the viewpoint of the desired effect of the present invention, it is particularly preferably used. Examples of the compounds include [1-11, [ll-21, [ll-51,
[ll-81, Cl-191, [111-11 and [I
Examples include [[-4].

The amount of the chelating agent represented by the general formula [1 [] or [III] added is 0.1 to 20 g per 12 color developing solutions.
It is preferably used in the range of 0.3 to 5 g from the viewpoint of the purpose of the present invention.
In and [VI], the alkyl group represented by R1, R2, R3 and R+ includes, for example, a methyl group, an ethyl group, a 1so-propyl group, a rhopropyl group, a t-butyl group, an n-butyl group, a hydroxymethyl group, Examples include hydroxymethyl group, methylcarboxylic acid group, benzyl group, etc.
Further, the alkyl group represented by R5, R6, R7 and R8 has the same meaning as above, and further includes an octyl group and the like.

Furthermore, the phenyl group represented by R+, R2, R3 and R4 is a phenyl group, 2-hydroxyphenyl group, 4-
Examples include aminophenyl group.

Typical specific examples of the compounds represented by the general formula [VI] and/or [VI] are listed below, but the invention is not limited thereto.

(V-1) 4-isopropyl-1,2-dihydroxybenzene (V-2> 1,2-dihydroxybenzene-3゜5
-Disulfonic acid (V-3> 1.2.3-1-dihydroxybenzene-5-carboxylic acid (V-4) 1,2.3-trihydroxybenzene-
5-carboxymethyl ester (V-5) 1.2.3-trihydroxybenzene-
5-carboxy-rope tyl ester (V-6) 5-t-butyl-1,2,31-dihydroxybenzene (■-1) 2,3-dihydroxynaphthalene-6-
Sulfonic acid (VI-2) 2.3.8-trihydroxynaphthalene-6-sulfonic acid (VI-3) 2.3-dihydroxynaphthalene-6
-Carboxylic acid (Vl-4) 2.3-dihydroxy-8-isopropyl-naphthalene (VI-5) 2.3-dihydroxy-8-chloro-
Naphthalene-6-sulfonic acid Among the above compounds, 1,2-dihydroxybenzene-3.
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salt and potassium salt.

In the present invention, the above compound is 5!1g per 12 developer solution.
It can be used in the range of ~20g, preferably 10g.
111! It~10g, more preferably 20II1g
Good results are obtained by adding ~3g.

The compounds of the present invention may be used alone or in combination. Furthermore, aminotri(methylenephosphonic m> or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane-1.2
．． Other chelating agents such as phosphonocarboxylic acids such as 4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

In the general formula [■] below, R+, R2 and R3 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts) or a phosphorus It group (including its salts). Examples of the salts of carboxylic acid groups and phosphorus WiM include salts of alkali metal atoms, salts of alkaline earth gold II atoms, and salts of alkali metal atoms such as sodium and potassium are preferred. Further, at least one of R1, R2, and R3 is a hydroxyl group, and at least one of R+, R2, and R3 is a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof). .

R+, R2 and R3 preferably each have a hydroxyl group,
This is the case when it is selected from a carboxylic acid group (including its salts) or a phosphoric acid group (including its salts).

nl, R2 and R3 each represent an integer of 1 to 3.

Typical specific examples of the compound represented by the general formula [■] are listed below, but the invention is not limited thereto.

The following margin> ≧ 2 2 The adding device for the compound shown in [V], [VI], and [VI] above can be used in the range of 0.1 to 100 (J) per 11 color developing solutions, preferably 1 to It is in the range of 50g.

As the color developing agent used in the color developer used in the present invention, a p-phenylenediamine compound having a water-soluble group is preferable because it suppresses the occurrence of fogging.

A p-phenylenediamine compound having a water-soluble group is
Compared to phenylenediamine-based compounds that do not have water-soluble groups such as N,N-diethyl-p-7enylenediamine,
Not only does it have the advantage of not causing contamination of the photosensitive material and does not cause skin irritation, but it also has the advantage that the object of the present invention can be efficiently achieved by combining it with a compound represented by the general formula [II]. can do.

Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine compound, and a specific example of the water-soluble group is -(CH2)n -CH20H.

-(CH2)II -NH8O2-(CH2)n -C
H5, -(CH2)III 0-(CH2)n-CHa, (C
H2CH20)n CI H21+1 (l and n each represent an integer of 0 or more), -COOH group, -
Preferred examples include 50s H group.

Specific examples of color developing agents preferably used in the present invention are shown below.

Below, 'margin' t, i+-,,,'- Exemplary color development agent (A-1) HsC2C2H, NH30zCH- 85C2C2H,OH (A-3) H,C2C,H,OH (A-4) H, C2C2H, ○CH.

H,C2C,ILSO,H H, CC2H, OH (Δ-7) HOH4C, C2H40H (A-8) H* C4C< Ha S Os H (A-9) Hs　C4C3E(g　S　O,H (A-10) HC82COOH \N/ (A-11) H-kai) CH2CH20 piece CH.

(A-12) H-kai) CH2CH20CH.

(A-13) (A-14) (A-15) H2 (A-16) H5C2C2H,OH Below margin Among the color developing agents exemplified above, example No. 1 is preferred for use in the present invention because it causes less fogging. , (A-
1) (A-2), (A-3>, (A-4), (A-
6), (A-7) and (A-15), and particularly preferably No. and (A-1).

The color developing agents mentioned above are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent having a water-soluble group used in the present invention is
IX 10-2 to 2X10 per 1 color developer
It is preferable to use a molar range of 1.5 x 10' to 2 molar per 12 color developing solution from the viewpoint of rapid processing.
A range of X10'' moles is more preferred.

In the present invention, when a triazylstilbene-based optical brightener represented by the following general formula [■] is used in the color developing solution according to the present invention, the general formula [2] which better achieves the desired effect of the present invention is used. ■] In the formula, Xl, X2, Yl and Y2 are tsuretsure water 8!
halogen atoms such as chlorine or bromine, morpholino groups, alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g. phenoxy, p-
sulfophenoxy, etc.), alkyl groups (e.g. methyl, ethyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, etc.), amino groups, alkylamino groups (e.g. methylamino, ethylamino, propylamino, dimethylamino, Schiff O hexylamino) , β-hydroxyethylamino, di(β-hydroxyethyl)amino, β-sulfoethylamino, N-(β-sulfoethyl)-N'-methylamino, N-(β-hydroxyethyl-N'-methylamine, etc. ), arylamino groups (e.g. anilino, 0-1
l-1p-sulfoanilino, 0-1m-1p-chloroanilino, 0-1m-1p-toluidino, O-1shin-1p
-carboxyanilino, 0-1l-1p-hydroxyanilino, sulfonaphthylamino, 0-1m-1p-aminoanilino, 0-1I-1p-anilino, etc.).

M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds may be mentioned, but the invention is not limited thereto.

Margin, white, t, ↓ Eng Q A A -C+
ω general formula [■]
The l-lyadylsdirbene-based brightener represented by can be synthesized, for example, by the usual method described in "Fluorescent Brightening - 1" (Published in August 1976) by the Japan Chemical Industry Association, page 8. Can be done.

These triadylstilbene-based brighteners are
It is preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per 1 fl of a color developing solution used for brightness.

The color developing solution of the present invention can contain the following developer components in addition to the above components.

Examples of alkaline agents other than the above carbon'Pli salts include sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. alone or in combination. Therefore, they can be used together as long as the above-mentioned effects of the present invention, that is, no precipitation occurs and the pH stabilizing effect is maintained. In addition, due to pharmaceutical needs or for the purpose of increasing ionic strength, dibasic sodium phosphate, dihydrogen phosphate, etc.
Various salts can be used, such as potassium, sodium bicarbonate, potassium bicarbonate, borates, and the like.

Additionally, inorganic and organic antifoggants can be added as necessary.

Furthermore, a development accelerator can also be used if necessary.

Development accelerators (I include various pyridinium compounds typified by U.S. Pat. No. 2,648,604, U.S. Pat. No. 3,671,247, and Japanese Patent Publication No. 44-9503, and other cationic compounds, Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.
No. 533.990, No. 2.531.832, No. 2
．． 950.970, 2.577, 127, and Japanese Patent Publication No. 44-9504, nonionic compounds such as polyethylene glycol, derivatives thereof, and polythioethers are included. Also, U.S. Patent No. 2.304.9
In addition to benzyl alcohol and phenethyl alcohol described in No. 25, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines can be mentioned.

In the above, when using a poorly soluble organic solvent such as benzyl alcohol, tar is likely to be generated due to long-term use of the color developing solution, especially during running processing in a low replenishment system. Depending on the proximity of the paper sensitive material to be processed, it may even cause serious malfunctions that significantly impair its commercial value.

In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome that a W1 stirring device is required to adjust the temperature of the color developing solution itself, but even the use of such a stirring device does not improve the dissolution rate. Due to the poor quality, there is a limit to the development promotion effect.

In addition, poorly soluble organic solvents reduce the biochemical oxygen demand (
800), etc., and it is impossible to dispose of it in sewers or rivers, etc., and treatment of the waste liquid requires a great deal of labor and cost. It is preferred to reduce or eliminate its usage.

Furthermore, the color developing solution of the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other ingredients as required.
The compounds described in the specification can be used as organic solvents to increase the solubility of developing agents.

Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol).
, phenidone, N,N'-diethyl-p-7 minophenol hydrochloride, N,N.

N',N'-tetramethyl-p-phenylenediamine hydrochloride is known, and the amount added is usually 0.
．． 01o to 1.0 (lzl is preferred. In addition, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor-releasing coupler (so-called DIR coupler), or a development inhibitor-releasing compound, etc., may be used as necessary. It can also be added.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used.

Each component of the above color developing solution is added sequentially to a certain amount of water.
! ! It can be prepared with itching. In this case, the component with low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a plurality of components, each of which can stably coexist, is prepared in advance in a small container as a floating aqueous solution or in a solid state, and then added to water and stirred to prepare the color developer of the present invention. can be obtained as

In the present invention, the above color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
is preferable, more preferably p)-19,8
~13. Used in O.

In the present invention, the processing temperature for color development is 30
C. or more and 50.degree. C. or less, the higher the temperature, the faster the processing can be performed in a short time, which is preferable.However, from the viewpoint of image storage stability, it is better not to be too high, and it is preferable to process at 33.degree. C. or more and 45.degree. C. or less.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 2 minutes.
Furthermore, it is also possible to carry out the test within a range of 30 seconds to 1 minute and 30 seconds.

In the present invention, the compound represented by the general formula [I] is contained, and the sulfite concentration is 4. It can be applied to any system as long as it uses a color developing solution of OX 10' mol/liter or less, such as bath treatment and various other methods, such as a spray set in which the treatment solution is atomized, or treatment. Various processing methods can be used, such as a web method involving contact with a carrier impregnated with a solution, or a development method using a viscous processing solution, but the processing steps essentially involve color development, bleach-fixing, washing with water, or stabilization as an alternative. Consists of processes such as processing.

The bleach-fixing step may be a bleaching step and a fixing step provided separately, or may be a bleach-fixing bath that processes bleaching and fixing in one bath.

Bleaching agents that can be used in the bleach-fix solution used in the present invention are metal complex salts of organic acids. The complex salt is one in which a metal ion such as iron, cobalt or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferred m'ra used to form such metal salts of organic acids include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali gold riA salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [4] BuO pyrene diamine tetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediamine tetraacetic acid [7] Iminodiacetic acid [81 Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [ 101 Glycol ether diamine tetraacetic acid [11] Ethylenediamine tetrabrobionic acid [12]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N -(β-oxyethyl)
-N, N', N' -t-Triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [191 Nitriloacetic acid sodium salt [20] Cyclohexane diamine tetraacetic acid sodium salt These bleaches have a concentration of 5 to 450 (]/ l!, more preferably 20 to 25 G1J/J!.The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent,
If necessary, a solution containing sulfite is applied as a preservative. In addition, iron ethylenediaminetetraacetate (II
[) A bleach-fix solution consisting of a complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixer mentioned above, or conversely, a composition containing a large amount of a halide such as ammonium bromide. Further, a special bleach-fix solution having a composition consisting of a combination of an ethylenediaminetetraacetate iron (m) SR salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The silver halide fixing agents contained in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples thereof include thiosulfate such as ammonium 1jA acid, thiocyanic acid 1= such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and dioether. These fixing agents are used in the range of 5 (1/e or higher) and can be dissolved, but generally 70 g to 25
Use at 0g/11.

In addition, various pH buffers such as TM acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide are used alone in the bleach-fix solution. Alternatively, two or more kinds can be contained in combination.

Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic A solvent and the like can be contained as appropriate.

The bleach-fix solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fix solution is used at 4.0 or more, but generally it is used at pH 5.0 or more and pH 9.5 or less, preferably pH 6.0 or more and 1) H8.5 or less, and more preferably, it is used at pH 8.5 or more. The pH is 6.5 or more and 8.5 or less. The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation.

In the present invention, following the color development and bleach-fixing steps, washing with water or a stabilizing treatment as an alternative to washing with water is performed.

Hereinafter, a stabilizing ground solution that can be used as an alternative to washing with water will be explained.

The pH of the water washing alternative stabilizer that can be applied to the present invention is 5.5 to
It is in the range of 10.0. As the pH adjusting agent that can be contained in the water washing substitute stabilizing solution applicable to the present invention, any commonly known alkaline agents or acid agents can be used.

The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 20 seconds to 10 minutes, most preferably 1 minute to 3 minutes, and in the case of multiple tank stabilization treatment, how long should the first stage tank be used? It is preferable that the treatment time is longer in the latter tank.Especially, 20% of the front tank
It is desirable to process sequentially with ~50% more processing time.

After the stabilization treatment applicable to the present invention, no water washing treatment is required at all, but rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary.

As for the method of supplying the water-washing substitute stabilizing solution in the stabilization treatment step that can be applied to the present invention, when a multi-tank countercurrent system is used, it is preferable to supply it to the after bath and overflow from the front bath. Of course, it can also be treated in a single tank. The above compounds can be added as a concentrated solution to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and then added to the washing alternative stabilizing replenishment solution. Although there are various methods such as using it as a supply liquid, it may be added by any method.

In this way, in the present invention, treatment with a stabilizing solution as an alternative to water washing refers to treatment with a processing solution having bleach-fixing ability, which immediately performs stabilization treatment and does not substantially involve washing with water. The treatment liquid used in the stabilization treatment is called a water-washing alternative stabilizer, and the treatment layer is called a stabilization bath or a stabilization tank.

The number of stabilization tanks in the stabilization treatment that can be applied to the present invention is 1 to 5.
The number of tanks is preferably 4ff, particularly preferably 1 to 3 tanks, and preferably 9 tanks or less at most.

The method for processing a silver halide color photographic light-sensitive material of the present invention uses the color developer used in the present invention, that is, the color developer containing the compound of the present invention and the chelating agent of the present invention as a preservative. , having a silver halide emulsion layer containing silver halide grains consisting of 80 mol% or more of silver chloride,
and at least one of the silver halide emulsion layers has the general formula [
A silver halide color photographic light-sensitive material containing at least one cyan coupler selected from [C-1] to [C-3] is processed.

The silver halide grains used in the silver halide color photographic light-sensitive material applied to the present invention contain at least 80% silver chloride.
Silver halide grains containing 0 mol % or more, preferably 90 mol % or more, more preferably 95 mol % or more.

The silver halide emulsion containing silver halide grains consisting of 80 mol% or more of silver chloride may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride,
In this case, silver bromide is at most 20 mol%, preferably at most 10 mol%, more preferably at most 5 mol%, and when silver iodide is present, it is at most 1 mol%, preferably 0.5 mol%. It is as follows. Such silver halide grains substantially consisting of silver chloride according to the present invention contain 80% or more by weight of all the silver halide grains in the silver halide emulsion layer containing the silver halide grains. It is preferable that the ratio is 100%, and more preferably 100%.

The crystals of the silver halide grains used in the present invention may be normal crystals, twin crystals, or other crystals, and have [1001 planes and [111
] Any aspect ratio can be used.

Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Further, tabular silver halide grains (JP-A-58-
No. 113934 and Japanese Patent Application No. 170070/1983) may also be used.

The silver halide grains used in the present invention may be obtained by any of the acidic method, neutral method, and ammonia method.

Further, for example, when growing silver halide grains, the pH in the reaction vessel may be determined by forming seed grains using an acidic method and then growing them using an ammonia method, which has a high growth rate, to grow them to a predetermined size.

1) Control Ag etc., for example, JP-A-54-48
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in No. 521.

Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to as a silver halide emulsion in Honkawa M's book.

These silver halide emulsions are composed of activated gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc.: selenium sensitizers: reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.: Noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-
Sensitizers with water-soluble groups such as methylbenzothiazolium chloride or ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chlorobratinate and sodium chloroparadate (consisting of these These types act as sensitizers, fog suppressants, etc. depending on the size of the film. It may also be chemically sensitized by using a combination of agents, etc.).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

To each silver halide used in the present invention, an appropriate sensitizing dye is added in an amount of 5 x 10-3 to 3 x 10-3 mol per 1 mol of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. It may also be optically sensitized. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat.
Same No. 2.503.776, Same No. 2,519,001, Same No. 2,912゜329, Same No. 3.656.959
No. 3,672,897, No. 3,694,21
No. 7, No. 4.025.349, No. 4.046.5
No. 72, British Patent No. 1,242,588, Special Publication No. 1972
Examples include those described in No. 14030, No. 52-24844, and the like. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat. .763,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 505,979. Furthermore, the sensitizing dyes used in red-sensitive silver halide emulsions are disclosed in, for example, U.S. Pat. .454. [No. 729, 2.776, 280
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 4 and the like.

Furthermore, U.S. Patent Nos. 2,213,995 and 2,4
No. 93,748, No. 2,519,001, West German Patent No. 929,080, etc., cyanine dyes, merocyanine dyes or composite cyanine dyes are used as green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. It can be advantageously used in emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 4
No. 9-6209, No. 53-12375, Japanese Unexamined Patent Publication No. 1983-
'23931, '52-51932, '54-8
No. 0118, No. 58-153926, No. 59-116
Examples include methods described in No. 646 and No. 59-116647.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-
No. 115820, No. 51-135528, No. 52-1
No. 04916, No. 52-104917, and the like.

Regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-406624, JP-A No. 56-25128, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication Nos. 43-4932, 43-4933, 45-26470, 4
No. 6-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 114533, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 5G-40659, etc. is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that can be decolorized with a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful.

Examples of AI dyes that can be used include British Patent No. 584.6
No. 09, No. 1,277.429, Japanese Unexamined Patent Publication No. 1985-85
No. 130, No. 49-99620, No. 49-114
No. 420, No. 49-129537, No. 52-10
No. 8115, No. 59-25845, No. 59-11
No. 1640, No. 59-111641, U.S. Patent No. 2
．． 274,782, 2,533,472, 2,956,019, 3,125,448, 3.148.187, 3,177.078,
3,247.127, 3,260.601, 3,540,887, 3,575,704
No. 3,653,905, No. 3.718.47
No. 2, No. 4,071.312, No. 4,070,3
Examples include those described in No. 52.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 10-3 to 5X10-1 mol, more preferably IX 10-2 to 1x10-1 mol.

In the method for processing a silver halide color photographic material of the present invention, a magenta coupler represented by the general formula [M] is used in at least one of the silver halide emulsion layers.

Next, the magenta coupler represented by the general formula [M] according to the present invention will be specifically explained.

In the magenta coupler represented by the general formula [Ro] in the margin below, Z represents a group of nonmetallic atoms necessary to form a containing heterocycle, and the ring formed by Z is It may have a substituent.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group,
Spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, anluoquine group, carbamoyloquine group, amino group, acylamino group, sulfonamide group, imide group, ureido group group, sulfamoylamino group, alkoxycarbonylamino group, aryloquinecarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and peterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The alkyl group represented by R has 1 to 732 carbon atoms, and the alkenyl group and alkynyl group have 2 to 732 carbon atoms.
32 carbon atoms, cycloalkyl groups, and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms,
The alkyl group, alkenyl group, and alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atom, petero ring, cycloalkyl, cycloalkenyl, spiro compound residue, Yoibashi hydrocarbon compound In addition to residues, those substituted via a carbonyl group such as anol, carboquine, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom (specifically, hydroquino, alkokene, aryl thione, heterocyclic ochine,
Those substituted via an oxygen atom such as carbonyloxy, acyloxy, carbamoyloxy, nitro, amino (including noalkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, anora-amino, sulfonamide, imide, Those substituted through a nitrogen atom such as ureido, alkylthio, arylthio, peterocyclic thio, sulfonyl, sulfinyl,
(such as those substituted via a sulfur atom such as sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl).

Specifically, for example, methyl (, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group,!
-Ditoxytridenyl group, 1-methquine isopropyl group, methanesulfonylethyl group, 2.4-not-t-amylphenoquinemethyl group, anilino group, l-buenylisopropyl group, 3-m-butanesulfonaminophenoquine Probyl group, 3-4.-(α-[4..(p-hydroxybenzenesulfonyl)phenoquine]dodecanoylamino)phenylpropyl group, 3-(4.-[α-(2..)
Examples include 4...-not-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(0~chlorphenoquine)tetradecanamidophenoquine]propyl group, allyl group, nclobentyl group, nclohequinyl group, and the like.

The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di-amylphenyl group, 4-tetradecanamidophenyl group, hexadenoroxyphenyl group, 4.
-[α-(4...=shi-butylphenoquino)tetradecanamidophenyl group and the like.

The heterocyclic group represented by R is preferably a 5- to 7-membered heterocyclic group, which may be substituted or fused.

Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, alkylcarbonyl group such as α-2,4-di-amylphenoxybutanoyl group, benzoyl group, and 3-bentadenyl group. Examples include arylcarbonyl groups such as a luoquinbenzoyl group and a p-chlorobenzoyl group.

The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include an ethylsulfinyl group, an octylsulfinyl group, an alkylsulfinyl group such as a 3-phenoquibutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group, and a m-pentadenulfenylsulfinyl group. can be mentioned.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoquinephosphonyl group, and a phenylphosphonyl group. Base.

Examples include arylphosphonyl groups such as.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4-di-t) -amylph, enoxy)propyl)carbamoyl group, and the like.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-(2-pentadecyl oquinethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group, Examples include moyl group.

Examples of spiro compound residues represented by R include spiro [
3,3]hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[3
, 3,1,1'''']decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group, a pentadecyl oquine group, Examples include 2-dodecyloxyethoxy group and phenethyloxyethoxy group.

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group,
For example, phenoxy group, p- is -butylphenoxy group, l
-pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by R preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3. .

4.5.6-tetrahydropyranyl-2-oxy group, 1
-phenyltetrazole-5-oxy group.

The siloxy group represented by R can be further represented by an alkyl group, etc.
LFIA may be used, and examples thereof include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, and the like.

Examples of the acyloxy group represented by R include an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., which may further have a substituent, and specifically, an acyloquine group, an α-chloroacetyloxy group, etc. group, benzoyloxy group, and the like.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. It will be done.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc. (for example, ethylamino group, anilino group, m-chloroanilino group,
Examples include 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamide anilino group, and the like.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α- Ethylpropanamide group, N-phenylacetamide group,
Examples thereof include a dodecanamide group, a 2,4-amylphenoquinoacetamide group, and an α-3-t-butyl 4-hydroquinophenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, and further substituents may be added.

Specifically, methylsulfonylamino group, bentadenorsulfonylamino group, benzenesulfonamide group,! 3-
Examples include toluenesulfonamide group and 2-methquine-5-4-amylbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutaric acid group. Examples include imide groups.

The ureido group represented by R is an alkyl group, an aryl group (
Preferred examples include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, and Np-tolylureido group.

The sulfamoylamino group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. .

The alkoxycarbonylamino group represented by R is
It may further have a substituent, for example, a methoxycarbonylamino group, a methquinethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxinecarbonyl group, an octadecyloxycarbonyl group, an ethquinmethoxycarbonyloquine group, Examples include pennoroxene, carbonyl group, and the like.

The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chlorophenoxycarbonyl group and m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, a dove-silthio group,
Examples include octadecylthio group, phenethylthio group, and 3-phenoquinopropylthio group.

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-acetaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5 to 7 heterocyclic thio group, which may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine, bromine, fluorine, etc.), as well as substituents that and substituent groups.

In addition to the carfoquinol group, examples of the group substituted via a carbon atom include the general formula (R1. is the same as the above R, Z. is the same as the above Z, R2. and R1. are hydrogen atoms, aryl groups, , representing an alkyl group or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, peterocyclic okyne groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. can be mentioned.

The alkoxy group may further have a substituent, for example,
Examples thereof include an ethquin group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group, and a p-chlorobenzyloxy group.

The aryloxy group is preferably a fenoquine group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-
Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-[α-(3-pentadecylphenoxy)butanamide]phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, ! -naphthyloxy group, p-
Examples include metoquinofenoquine group.

The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-phenyltetrazolyluoquine group and 2-benzothiazolyloxy group.

The acyloxy group includes, for example, an acetoxy group, an alkylcarbonyloxy group such as a butanolokino group, an alkenylcarbonyloxy group such as a cinnamoylokino group,
Examples include arylcarbonyloxy groups such as penzoyluoquine.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a penzyloxycarbonyloxy group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group, a benzylthio group, and the like.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropencunamidophenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t- Examples include butylphenylthio group.

Examples of the heterocyclic thio group include 1-phenyl-1,
Examples include 2,3,4-tetrazo6lyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

Examples include those represented by the general formula -N. Here, R4 and R, are hydrogen atoms, alkyl groups,
Represents an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R4 and R
s. may be combined to form a heterocycle. However, R4・
and R6. are never both hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, such as an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
L-lylthio group, alkylamino group, arylamino group, anrylamino group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, ryolsulfonyl group,
Examples include carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxinecarbonylamino group, aryloxycarbonylamino group, hydroquinol group, carbonyl group, cyano group, and halogen atom.

Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexynyl group, and 2-chloroethyl group.

The aryl group represented by R4 or R1 has 6 to 32 carbon atoms, and is particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent such as those mentioned above. Examples of substituents for the alkyl group represented by R4. or R, . include those listed above and an alkyl group. Specific examples of the aryl group include phenyl group, -naphthyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4 or R1 is 5 to 6
It is preferable that the ring is a membered ring, and it may be a condensed ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-hylinol group.

Examples of the sulfamoyl group represented by R4 or R2 include N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-arylsulfamoyl group,
, N-diarylsulfamoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group and N-p-tolylsulfamoyl group.

The carbamoyl group represented by R4 or R6 is,
Examples include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups can be substituted with the substituents listed above for the alkyl group and aryl group. It may have a group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodenylcarbamoyl group, N-p-noanophenylcarbamoyl group, and N-p-blylcarbamoyl group. Can be mentioned.

Examples of the acyl group represented by R4' or R6 include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. It's okay. Specific examples of the acyl group include hexafluorobutanoyl group, 2°3.4.5. ．． Examples include 6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, and 2-furylcarbonyl group.

Examples of the sulfonyl group represented by R4 or R3 include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, such as an ethanesulfonyl group. , a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, and the like.

The aryloxycarbonyl group represented by R4 or Rs' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like.

The alkoxycarbonyl group represented by R4 or Rs may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. Can be mentioned.

The heterocycle formed by combining R4 and R3 is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity. or,
It may be a condensed ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolidinyl group, 2- N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
! -pyrrolyl group, l-pyrrolidinyl group, 1-pyrazolyl group, ■-pyrazolidinyl group,! -piveridinyl group, 1-
Pyrrolinyl group, ■-imidazolyl group, ■-imidazolinyl group, 1-indolyl group, l-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, l-benzotriazolyl group, l-benzimidazolyl group, l
-(1,2,4-triazolyl) group, l L(1,2,
3-) riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2.3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2 -IH-pyridone group, phthaladione group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl group, aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkyl group, etc. Amino group, arylamino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imide group,
It may be substituted with a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like.

Examples of the nitrogen-containing heterocycle formed by Z or Z include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

In addition, the general formula [Yu] and the general formula CM-1) to (M-
substituent on the heterocycle in 'I) (for example, RlRI-
R8) is! When a moiety (R..., X, and 2... have the same meanings as R, X, and Z in the general formula [C]) exists, it forms a so-called screw-type coupler, but is of course included in the present invention. .

In addition, the ring formed by 2.2', 2... and Zl described below can further be a pond ring (for example, a 5- to 7-membered cycloalkene).
may be condensed. For example, in the general formula [Iris-Go], R2 and R1 are R7 and R1 in the general formula CM().
1 may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene).

Izecha 1 Sh.

More specifically, what is represented by general formula (1) is represented by, for example, the following general formulas (M-1) to (M-6).

General formula CM-1) General formula [Bar-2] N N -N General formula [Yu-3] N N NH General formula [Iris-hour] General formula [Bar f] N N -1f) l General formula [Bar ] N-1+-1 In the general formulas CM-2) to CM-(,,), RI-
R8 and X are synonymous with R and X described above.

In addition, the following general formula [Iris] is more preferable than the general formula [Iris].
M-'l).

General formula [:M-'I) N-N,,' In the formula, R, , x and Z have the same meanings as RlX and Z in the general formula [C].

Among the magenta couplers represented by the general formulas [Bar 1] to [C], particularly preferred are those represented by the general formula CM-1)
It is a magenta coupler represented by .

Regarding the substituents on the heterocycles in general formulas [M], [M-1] to [M-7], in general formulas [iris], R or general formulas CM-1) to [Ryo -7], it is preferable that R1 satisfies the following condition 1, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1.2 and 3 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituents R and Ro on the search ring are those represented by the following general formula [Iris-g].

General formula [color-3] R.

Io-C-(2) may be formed, and RIl may be further bonded to the ring to form a bridged hydrocarbon compound residue.

The group represented by R9-R1 may have a substituent,
Specific examples of the groups represented by R8 to R+t and substituents that the groups may include include specific examples of the groups and substituents represented by R in the aforementioned general formula [c].

Also, for example, a ring formed by combining Rs and R8°, and R,
The specific list of the bridged hydrocarbon compound residues formed by ~R11 and the substituents thereof may include the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the above general formula [Yu]. Specific examples of hydrocarbon compound residues and their substituents are listed.

General formula CM-1? ) is preferable among (i) Re
- When two of R11 are alkyl groups, (ii) Rs
~ One of R11, for example R11, is a hydrogen atom,
When the other two R1 and R10 combine to form a cycloalkyl together with the root carbon atom, the following is true.

Further preferred in (1) is the case where two of R and -R11 are alkyl groups and one of the atoms is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substitution represented by R in the general formula [c] above. Specific examples of the group are listed below.

Pa1 The following is life y-t 1'l1- 1C2H )'l-4 CI21125 tm ? 'l-9 C.I.

CII.

Previous-11 -t　2 ■-13 Cll.

1-r 4 i-ts lh -t6 C21t.

r'l-17 C2H5 Oki 18 C2H.

1'l-2s C, lI.

Mon-26 Cll, CM.

h・27 C.H.

Member-28 ctolltt l2b5 4H1 Portrait-31 c+211ts Hm 1-3s )'I-aa ゝ゛Ctslht bar 40 ■ H1 C1゜ Front-43 1i-44 □, C, Ho(L) L Reward-47 Jls Gate-52 Ro-53 C, Il.

1'55 C, 11° CH.

1-s9 C1l.

C.I.

lll C.H.

h-64 C,H.

Ima Tohaku i? Lp inside 4 Mon-66 C1l.

NO: ■ ■ C.I.H.

Js C, H number C.B.

Ro-76 M-77 Member-79 OCR, C0IIHOI, CM20CH.

C2chi C, H Gate-82 C21I C, lI.

C, lI custom C11゜ f'1l-C7 C,H.

Distance 88 C,H.

Dairy-90 t'l-92 C,H.

The following is poisonous 1-t7 CI+! M-ra.

C, Hff R-s　　　1 C4H times Ro-102 ah M(03 j-tu CI21125 M-105 C1oth 1'1-toe C,H.

-to7 tJts Front-109 C6H+3 Below is “margin” 11-υ礪 Moon-110 Member-111 -tt3 Gate-114 ll1 t4-t15 lli -xts 'OC, H.

N-N"' (C1lt)* -<'ffNH30t
-<Two juices OC, J.

M-its NllSO2C+5Hii -1t9 )'%-121 CiHo(LI heat C1l.

C1H++(tl C[I! C1l.

year 127 C.I.

tj-t 2 g CH1CaH+ t(Ll tl-129 M-t 30 C1l, ・ 1-t3t t'l-t 32 h-133 ■ C1l.

C2H 'C? HI3 1-+.

Gate-138 ? -1-t 39 11ic CR.

i-t 40 Mr-r　4　t C,H.

M-t 42 and above, ¥ white tp7. ,, ■-143 -x44 M-t 4 a M-147 t'1-r4a ■-15O N -N N C,
,H,.

N -N N (41゜-tss N -N -N 1-tst N N Ml -162 M -163 N N 8B L:J9 (H, N N NH
N N HH C,ll.

M-+as C1h j’l-169 ■ Gate-179 M-133 HN NO N HH N Nll +1-ts.

1':M.

N N NH N -8-11 -zsz N -N□niI Jti tl -tss Mae-199 Ida Toshiro Gohi 41 Also, the synthesis of the coupler is described in the Journal of th
eChemical 5ociety, Perkin
Synthesis was carried out with reference to I (1977), 2047-2052, US Pat.

The couplers of the invention typically have lX per mole of silver halide.
10-3'E to 5 x 10'' moles, preferably 1
It can be used in a range of X10-2 mol to 5X10-1 mol.

In addition to the magenta coupler of the present invention, photographic couplers used in the present invention are preferably cyan couplers such as phenolic compounds and naphthol compounds, such as U.S. Pat. No. 2,369.929 and U.S. Pat.
No. 72, No. 2,474,293, No. 2,895.
No. 826, No. 3,253,924, No. 3.034
．． No. 892, No. 3,311,476, No. 3.38
6.301, 3.419.390, 3.4
58,315, 3.476, 563, 3.
You can choose from those listed in No. 531,383, etc.
Methods for synthesizing these compounds are also described in the same publication.

As the photographic magenta coupler, in addition to the magenta coupler represented by the general formula [M] according to the present invention, compounds such as pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type and indacylon type are used. Examples of pyrazolone magenta couplers include U.S. Patent Nos. 2,600,788, 3.062.653, 3.127.269, and 3,311,476.
No. 3,419,391, No. 3.519.42
No. 9, No. 3,558,318, No. 3,684,51
No. 4, No. 3,888,680, JP-A-49-296
3'1 No. 49-111631, No. 49-1295
No. 38, No. 50-13041, Special Publication No. 53-4716
7, No. 54-10491, and No. 55-30615, compounds in which the coupling position of a colorless magenta coupler is substituted with arylazo are generally used as diffusion-resistant colored magenta couplers. , for example, U.S. Pat. No. 2,801,171;
, No. 983,608, No. 3,005.712, No. 3
．． 684,514, British Patent No. 937,621, and JP-A-49-123625 and JP-A-49-31448.

Furthermore, a colored magenta coupler of the type in which the dye flows out into the processing solution by the reaction of the oxidized product of the developing agent as described in US Pat. No. 3,419,391 can also be used.

As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and hibaloylacetanilide type yellow couplers can be used. Furthermore, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction are also advantageously used.

Examples of these are U.S. Pat.
, No. 265.506, No. 3,664,841, No. 3
, No. 408.194, No. 3,277.155, No. 3
．． No. 447.928, No. 3,415゜652, Japanese Patent Publication No. 13576-1976, Japanese Patent Application Publication No. 29432-1974, 1
1i 4B-68834, 49-10736, 49-122335, 5G-28834, 5
It is described in G-132926 etc. together with the synthesis method.

The amount of the diffusion-resistant coupler used in the present invention is generally 0.0 per mole of silver in the light-sensitive silver halide emulsion layer.
It is 5 to 2.0 moles.

In the present invention, DIR compounds are preferably used in addition to the above-mentioned diffusion-resistant couplers.

Furthermore, in addition to DIR compounds, the present invention also includes compounds that release development inhibitors during development; for example, U.S. Pat. No. 3.297.445, U.S. Pat.
West German Patent Application (OLS) No. 2,417,914, JP-A No. 52-15271, JP-A No. 53-9116,
Examples include those described in No. 59-123838 and No. 59-121038.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized form of a color developing agent to release a development inhibitor.

A typical example of such [)IR compounds is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the coupler active site. No. 935.454, U.S. Patent No. 3,227,554, U.S. Patent No. 4.095,98
No. 4, No. 4,149,886, etc.

When the above DIR coupler undergoes a coupling reaction with an oxidized color developing agent, the coupler core forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Further, in the present invention, US Pat. No. 3,652,345 and US Pat.
, No. 041, No. 3,958,993, No. 3, 96
No. 1.959, No. 4,052,213, Japanese Unexamined Patent Publication No. 1973
-110529, 54-13333, 55-1
Also included are compounds that release a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 61237, but do not form a dye.

Furthermore, JP-A-54-145135 and JP-A-56-1
14946 and 57-154234, the core forms a dye or colorless compound, while It! tlA
The present invention also includes so-called timing DIR compounds, which are compounds in which the L timing group releases a development inhibitor through an intramolecular nucleophilic substitution reaction or an elimination reaction.

Also, JP-A No. 58-160954, No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
It also includes R compounds.

The amount of the DIR compound contained in the photosensitive material is preferably in the range of 1×10 → mol to 10×IO−1 mol per mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives, such as antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure No. 17643. Agents, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, and proteins such as albumin and casein. , cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Examples of the support for the silver halide color photographic light-sensitive material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, Examples include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and other usual transparent supports may be used. These supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2,76
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 1,791 and No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. . Each of these photosensitive silver halide emulsion layers may consist of two or more layers.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, if the silver halide color photographic light-sensitive material is a light-sensitive material that is processed by a so-called internal development method containing a coupler in the light-sensitive material, color paper can be used. The present invention can be applied to any silver halide color photographic material such as color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color vapor.

[Specific Effects of the Invention] As explained above, the present invention provides a silver halide color photographic light-sensitive material which has excellent storage stability of a color developing solution and excellent photographic properties such as maximum color density of the obtained dye image. We were able to provide a processing method.

The following is a margin 1, white "' and IIS. [Specific Examples of the Invention] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited to these.

[Example 1] Color developing solutions Nos. 1 to 14 having the following compositions were prepared.

(Color developer) Potassium chloride 1.0g Potassium sulfite 0.2g Preservative (Table 1
) 10g Chelating agent (listed in Table 1) Color developing agent (Exemplary compound A-1) 5.5g Potassium carbonate Add 30g water and add 1
2, and adjust Hlo to 15 with potassium hydroxide and sulfuric acid.

Ferric ion 4ppm in the above color developer N081-14
, 2 ppm copper ions and 1100 ppm calcium ions
1) El (Fe C113, ' Cu S, respectively)
O+ 66H20 and ca Cf12 were dissolved and added) and stored at 40° C. for 2 weeks in a glass container with an aperture ratio of 30 cf/4 (air contact area is 30 cm 2 for 1ffi color developer). The appearance (degree of coloration) of the color developing solution after 1E was observed.

However, the appearance of the liquid was divided into the following four levels.

÷＋◆ A large amount of tar generated 1◆ Blackening + Whitening (considerable discoloration) 1° is hardly discolored and less than −゛ remainder −t・2, Table (1) As is clear from the results of Table (1) Hydroxylamine lil as a preservative! When an i acid salt is used, the appearance of the liquid changes somewhat depending on the presence or absence of a chelating agent, but it is discolored or blackened. This means that the color developing agent in the color developing solution is oxidized and tar formation has begun to occur.

- Preservability has been improved by using the preservative of Rikiki's invention, and furthermore, the preservability has been improved to that of chopsticks by combining it with a chelating agent.

[Example 2] A silver halide photosensitive material was prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer 1 - 1.20 Mr gelatin, 0.40 g/f (in terms of silver, the same applies hereinafter) blue-sensitive silver halide emulsion (AgBr
:Ao Cff1-4 :96) and 0.550/l"
i,ox i o− dissolved in dioctyl phthalate of
Layer 2 containing a mole O/f of yellow coupler (Y-1) - Intermediate layer 113 consisting of 0.70 a/v gelatin
...1.20! It/f gelatin, 0.22! J/
f green-sensitive silver halide emulsion (AgBr:AgCf
f1-3:97) and 0.30 g/f of dioctyl phthalate 1. OX 10-3 mol g/
A layer containing the following magenta coupler (M-1) of f.

14...Intermediate layer consisting of gelatin of 0.70Q/f.

li5...1.20 (If/m' gelatin, 0.2
8M f red-sensitive silver chlorobromide emulsion (AIJ Sr: A!
JCl! -4:96) and 0.25! 1,75 x 1Q-3 dissolved in dibutyl phthalate of It/i'
A layer containing the following cyan coupler (C-1) in molar (J/f).

Layer 6...1.0 (J/f gelatin and 0.25M
0,320/dissolved in dioctyl phthalate of f
A layer containing Tinuvin 328 (UV absorber manufactured by Ciba Geigy).

Layer 7: A layer containing gelatin of 0.48i11/f. In addition, as a hardening agent, use sodium 2,4-dichloro-6-hydrooxy-s-triazine! ! ! 2.4 and 7, respectively, in amounts of o and olra per 1 g of gelatin.

The silver halide composition in each silver halide emulsion is shown in the table (
2).

1h-First, these samples were subjected to wedge-shaped exposure using a conventional method, and then processed according to the following processing steps.

Processing process Processing temperature Processing time [11 Color development 35℃ - [2] Bleach fixing 3
5℃ 45 seconds [3] Wash with water 30℃
90 seconds [4] Drying 60-80℃
As the 60 second color developing solution, ONα6 of Example 1 was used. The composition of the bleach-fix solution is as follows.

The following is a white lieutenant...;! -J, ' [Bleach-fix solution] Ethylenediaminetetraacetate ferric ammonium 2 water points 60.0g Ethylenediaminetetraacetate M 3.0g Ammonium thiosulfate (70% solution) 100. OiN ammonium sulfite cum (40% solution) Add 27.5 d of water to make Kanayama 12 and prepare with potassium carbonate or glacial acetic acid E)H
Adjust to 7.1.

The maximum reflection density of the yellow dye was measured using an optical densitometer PDA-65 (Konishiroku Photo Industry K) when color development was carried out at 35°C for 10 minutes.
The maximum reflection density of the yellow dye at this time is 100, and the development time (development convergence time) required for the maximum reflection density of the yellow dye to reach 80 is shown in Table (2). Described. Since this result is the development convergence time of the blue-sensitive emulsion layer having the slowest development speed, it indicates the development completion time of the photosensitive material used.

Table (2) As is clear from Table (2), the content of silver chloride is 80%.
The above samples Nα3 to Nα10 have short convergence times, indicating that rapid processing is possible. In particular, it can be seen that rapid processing is possible for samples 5 to 10 in which the silver chloride content is 90% or more, especially samples NCL 6 to 10 in which the silver chloride content is 95% or more.

[Example 3] Using the color photosensitive material prepared in Example 2 (the silver halide composition is shown in Table (3)), NcL was used as a color developer.
Silver developability of Samples No. 2.4 and No. 11 (without color developing agent) was evaluated by performing the following treatment.

Standard processing steps (processing temperature and processing time) [1] Development 35℃ 45 seconds [2] Constant @
35℃ 45 seconds [3] Water washing treatment 30
℃ 90 seconds [4] Drying 68-80℃
60 seconds (fixer) Ammonium thiosulfate (70% solution) 150ti2 Ammonium sulfite (40% solution) Add 20mQ water and transfer the total amount to IJ2. Bind, pi with ammonium hydroxide or acetic acid
Adjusted to -17,00.

The spectral reflection density of [) 1 laX of the sample after the development treatment was measured using PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.) under orange light, and the spectral reflection density of [) WaX and D The difference between Iin and spectral inversion rJI of 11 degrees was taken as a representative characteristic with respect to silver concentration.

The results are shown in Table (3).

Table (3) As is clear from Table (3), samples Nos. 18 to 24 using hydroxylamine all had high silver concentrations and progressed in silver development. In particular, it can be seen that silver development is progressing for samples 19 to 24 with a silver chloride content of 80% or more.

However, in color developer No. 11 using Exemplified Compound I-1 of the present invention, almost no silver development occurred regardless of the silver chloride content.

[Example 4] Using the color paper sample used in Example 2, following the processing steps of Example 2, Example 10 color developer 11fi
A similar process was repeated using the bleach-fix solutions of Example 5 and Example 2. However, the silver halide composition of the color paper sample was AgSr:A! in the blue-sensitive emulsion layer. I CfL is Q:10G, if sensitive K agent 111- is 2:98, red-sensitive emulsion layer is 5:95, magenta coupler is table (
4) was used. The color development processing time was 45 seconds, the concentration of potassium sulfite in the color developer was as shown in Table (4), and the chelating agent was as shown in Table (4).
I used the one described in . In addition, the color developing solution contains ferric ion 41)l)l, copper ion 2EIDI, and calcium ion 10100pp, FeC23, Cu, respectively.
SO4.6H20 and CaCl2 were dissolved (added) and stored under the same conditions as in Example 1 for 10 days before use. The maximum color density and minimum color density of the magenta dye after treatment were measured and shown in Table (4).

As is clear from the results in table (4), when the couplers of Comparisons 1 and 2, which are couplers outside the present invention, are used, the concentration of potassium sulfite is 4. (An increase in the minimum color density is observed when IX i Q-3 mol/liter or less. - When the magenta coupler of Rikiki's invention is used, the increase in the minimum color density is significantly improved even when the concentration of potassium sulfite is low, and the chelate It can be seen that even better results can be obtained by combining with other agents.

In addition, in sample 55, M-
Similar results were obtained using 22 and M-109.

[Example 5] Exemplary compound (A'-2) was added to the color developer used in Example 4.
, (A'-4) and (A'-9) (all triadylstilbenzene optical brighteners) at 2o/(
When an experiment was carried out in the same manner as in Example 4, except for the addition of 1.5% of the total magenta concentration, the magenta minimum density was improved by 0.01 to 0.02 in all cases.

[Example 6] Color developing agent (A-1) in the color developer used in Example 4
When similar experiments were conducted by changing > to (B-1) or (B-2> below, the minimum magenta density in the unexposed area deteriorated by 0.02 in both cases.

Similarly, the color developing agent (A-1) of Example 4 was
When the same experiment as in Example 1 was carried out by changing the exemplified compounds (A-2), (A-4) and (8-15),
Similar results were obtained.

(B-1) (B-2) [Example 7] Using samples 1.3 and 6 used in Example 2 (however, the magenta coupler listed in Table (5) was used), color development was performed. The developer used in Example 1 was Nα6 (
However, potassium sulfite (shown in Table (5)) was used to examine the influence of silver halide composition and sulfite on magenta density (maximum and reflection density).

The processing and evaluation method for the enamel image was in accordance with Example 2.

The following margin, white', +; "', J- As is clear from Table (5), when silver chloride is outside the scope of the present invention as a silver halide composition (samples Nα59 to 62), the development time is short, so magenta Although the maximum concentration is low, it is not significantly affected by the concentration of potassium sulfite or the type of magenta coupler.

- The samples invented by Rikiki (NQ63-70) have a silver chloride content of 80 mol% or more and the development speed is fast, so the magenta maximum density is high even if the time is short, but the maximum dye density is significantly higher than that of potassium 1a nitrite. Depends on potassium sulfite 4. OX1
When it exceeds 0-3 mol/l, a remarkable concentration value is shown, but 4
．． Very good maximum concentrations are obtained below OX 10-3 mol/l. However, on the other hand, the minimum density of magenta is
If a coupler other than the present invention is used, the sulfite colorimu will be 4. Although it becomes particularly high at OX 10-3 mol %/fl or less, it can be seen that an extremely good minimum concentration can be obtained using the coupler of the present invention.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (procedural amendment) % formula % 1. Indication of the case 1985 Patent Application No. 92932 2. Name of the invention Processing method for silver halide color photographic light-sensitive materials 3. Amendment Relationship with the case of the person who filed the patent application Address of the patent applicant: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Gyōte 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 (Shipping date) June 24, 1988 6, Subject to amendment

Claims (1)

[Claims] (1) In a method for processing a silver halide color photographic material, which comprises imagewise exposing a silver halide color photographic material containing at least one silver halide emulsion layer, and then subjecting it to a process including at least a color development step, The silver halide emulsion layer is a silver halide emulsion layer containing silver halide grains consisting of 80 mol% or more of silver chloride, and at least one layer of the silver halide emulsion layer has the following general formula [M]
The color developer used in the color development step contains a compound represented by the following general formula [I], and has a sulfite concentration of 4 x 10^- per liter of color developer. A method for processing a silver halide color photographic material, characterized in that the amount of silver halide is 3 mol or less. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 each have a carbon atom number of 1 to
3 represents an alkyl group. ) General formula [M] ▲ Numerical formulas, chemical formulas, tables, etc. (X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Also, R represents a hydrogen atom or a substituent.) Formula [II], [III], [V]
2. The method for processing a silver halide color photographic material according to claim 1, which comprises at least one compound selected from , [VI] and [VII]. General formula [II] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (In general formulas [II] and [III], L is an alkylene group,
Cycloalkylene group, phenylene group, -L_8-O-L_8-O-L_8- or -L_9-
Represents Z-L_9-. Here Z is >N-L_1_0-
Represents R_1_0, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, >N-R_1_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. L_1 to L_1_3 each represent an alkylene group. R_3 to R_1_3 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt), or a phosphonic acid group (including its salt). However, at least two of R_3 to R_6 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least two of R_7 to R_9 are carboxylic acid groups (including salts thereof). ) or a phosphonic acid group (including its salts). ) General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above general formulas [V] and [VI], R_1, R_2,
R_3 and R_4 are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -O
R_5, -COOR_6, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Or, it represents a phenyl group. Also, R_5, R_6, R_7 and R_8
each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R_2 represents -OH or a hydrogen atom, R_1 is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR_5, -COOR
＿６、▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or, it represents a phenyl group. ) General formula [VII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above general formula [VII], R_1, R_2, and R_
3 each represents a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphoric acid group (including its salts). However, at least one of R_1, R_2 and R_3 is a hydroxyl group, and at least one of R_1, R_2 and R_3 is a carboxylic acid group (including its salt) or a phosphoric acid group (including its salt). n_1, n_2 and n_3
each represents an integer from 1 to 3) (3) The sulfite concentration in the color developer is 4 x 10^-^ per liter of color developer.
Claim 1 characterized in that the amount is 3 moles or less
A method for processing a silver halide color photographic light-sensitive material according to item 1 or 2.