JPH01952A - Processing method for silver halide color photographic materials with excellent processing stability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and in particular, a method for processing silver halide color photographic materials, which improves processing stability and color staining, and reduces variation in the maximum density of cyan dye. The present invention relates to a method for processing silver halide color photographic materials.

[Background of the Invention] Usually, in color developing solutions, sulfites or sulfites are used as preservatives to prevent oxidation of aromatic primary amine color developing agents, such as p-phenylenediamine type developing agents. and a water-soluble salt of hydroxylamine.

It is already known that adding hydroxylamine as a water-soluble salt can provide effective preservability since adding these sulfites alone to the developer does not necessarily provide sufficient preservability. There is.

However, hydroxylamine salts decompose under the catalytic action of trace amounts of coexisting metal ions, especially iron ions, which not only reduces the preservative effect but also generates ammonia upon decomposition, which can be used in color photographic light-sensitive materials. It is known that this can cause fog and stains to form on the surface of the film, as well as abnormalities in photographic properties, especially hard contrast in the shoulder areas, resulting in a decrease in processing stability.

Metal ions, especially iron ions, are mixed into the color developing solution in automatic processors by splashing, conveyance leaders, belts, hangers for hanging the film, etc. This is caused by lightning back contamination that brings in bleach and bleach-fix solutions.

To prevent these undesirable effects of metal ions,
Techniques for incorporating various metal chelating agents have been proposed and put into practical use. For example, the technique of using a human Oxyalkylidene-diphosphonic acid sequestrant in combination with a lithium salt described in U.S. Pat. No. 3,839,045; techniques that use a polyhydroxy compound and an aminopolycarboxylic acid sequestrant in combination; techniques that use a polyhydroxy compound and an aminopolyphosphonic acid sequestrant in combination as described in U.S. Patent No. 4,264,716; However, the current situation is that even these techniques have not been able to solve the problems described above.

In this case, the decrease in processing stability caused by droxylamine salt is further amplified in low-replenishment processing that has been used in recent years due to pollution and economic problems. That is, in low replenishment processing, not only the amount of accumulated metal ions increases, but also the renewal rate of the developer decreases, so that the residence time of the developer in the processing tank increases significantly. For this reason, the above-mentioned problems of fogging and dark contrast caused by the decomposition of the hydroxylamine salt become even more pronounced. Furthermore, under these circumstances, it has become clear that, for example, trace metals contained in the reagent, especially copper ions, accelerate the decomposition of hydroxylamine salts, whereas conventional multiple replenishment treatments had little effect. Furthermore, it has been found that it is difficult to render these copper ions harmless by using conventional chelating agents.

From the above-mentioned viewpoints, various preservatives have been studied and developed that do not have the disadvantage of reduced processing stability of hydroxylamine salts and have high preservative ability.

Additionally, when certain preservatives are used for the above purpose, the maximum concentration of the cyan dye becomes susceptible to fluctuations in the concentration of the color developing agent in the color developer, especially the color developing agent in the color developer. When the density of cyan dye decreases, a problem arises in that the maximum density of the cyan dye tends to decrease, and a solution to this problem has also been desired.

[Object of the Invention] Therefore, the first object of the present invention is to develop a halogenated color developer which has excellent stability over time and has excellent processing stability with less variation in photographic performance such as increased fog and increased contrast in shoulders. An object of the present invention is to provide a method for processing silver color photographic materials.

A second object of the present invention is to provide a method for processing a silver halide color photographic material in which the maximum density of cyan dye is less likely to fluctuate.

[Structure of the Invention] The above object of the present invention is to provide an imagewise exposed silver halide color having on a support at least one silver halide emulsion layer containing a compound represented by the following general formula [C]. Achieved by a method for processing a silver halide color photographic material, which is characterized in that the photographic material is processed in a processing step that includes at least a step of using a color developing solution containing a compound represented by the following general formula [I]. be done.

General formula [C] (wherein, R+ is -CONR4R5, -NHCOR+,
-NHCOORs, -NH3O2Rs, NHCONR
4R5 or -NH3O2NR4R5, R2 is a monovalent group, R3 is a substituent, X is a hydrogen atom or a group that is eliminated by +m by reaction with an oxidized aromatic primary amine developer, l is O or 1 , ■ is an integer of 0 to 3, R4 and R5 are each a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group,
R6 represents an aromatic group, an aliphatic group or a heterocyclic group, and I
is 2 or 3, R3's are the same, different, and bonded to each other to form a ring, and R4
and Rs , R2 and R3, and R2 and X combine to form a ring. However, when evening is O, G, 1 is o, R+
Bar CON HR7 (F) R7 represents an aromatic group. ) General formula [I] (In the formula, R11 and R+2 each represent an alkyl group or a hydrogen atom. However, it does not include those in which both R++ and R+2 are hydrogen atoms at the same time. Also, R1+ and R12
Also includes those in which the ring forms a ring. ) Further, according to a preferred embodiment of the present invention, the color developing solution has the following general formula [II
] and [III].

General formula [II] General formula [1 [1] In general formula [II] and [I [[], is an alkylene group, a cycloalkylene group, a phenylene group, -L a-0
-L a-0-L a- or -19-Z-Ls-. Here, 2 represents an alkylene group, and each of 1 to Ln represents an alkylene group.

R21 to R3+ each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts). However, at least two of R21 to R24 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and a small number of R25 to R27 (both two are carboxylic acid groups) (including its salts) or phosphonic acid N (including its salts). [Specific constitution of the invention] The color developing solution used in the processing method of the present invention includes a compound represented by the general formula [I]. (hereinafter referred to as the compound of the present invention) is used as a preservative.

In the general formula [E], R1 and R12 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom, but the alkyl groups represented by R11 and R12 may be the same or different, and each has 1 to 3 carbon atoms. The alkyl group is preferred. The alkyl groups of R1+ and R+2 include those having substituents, and Rzt and R12 may be combined to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.

Specific examples of the hydroxyamine compound represented by [Ichifunen CI] are disclosed in U.S. Patent No. 3,287,125 and @
No. 3,293,034, No. 3,287.124, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention are usually free amines, hydrochlorides,
It is used in the form of sulfate, o-1-luenesulfonate, oxalate, phosphate, acetate, etc.

The concentration of the compound represented by the general formula [I] of the present invention in the color developing solution is usually 0.1J/ffi to 50a/2, preferably 11)/j! ~30(1/j!), more preferably 3g/2~20Q/l.

The compound represented by the general formula [I] of the present invention can be used in place of hydroxylamine sulfate, which has been widely used as a preservative in color developing solutions for conventional silver halide color photographic light-sensitive materials. However, among the compounds of the present invention, for example, N,N-diethylhydroxylamine is known to be used as a preservative for a black and white developing agent in a color developer containing a black and white developing agent. In the so-called external color development method, in which a color photographic material is developed by a reversal method using a color developing solution containing a coupler, there is a technique in which it is used together with phenidone. (Tokuko Showa 4
5-22198).

Further, as another example of using the compound of the present invention such as N,N-diethylhydroxylamine as a preservative for a black and white developing agent added to a color developing solution, in an internal color developing solution, A technique for preserving phenidone derivatives added thereto (see JP-A No. 53-32035) and a technique for preserving phenidone derivatives together with hydroquinones (see JP-A-52-153437). Can be done.

However, by using the compounds of the present invention in color developing solutions, they not only act as good preservatives;
It was completely unknown that hydroxylamine sulfate, which has been widely used as a preservative, hardly undergoes decomposition reactions catalyzed by metal ions.

Furthermore, compared to N,N-dialkylhydroxylamines with similar structures, such as N,N-diethylhydroxylamine; N,N-dimethylhydroxylamine, the compounds of the present invention - It has the advantage of almost no unpleasant amine odor inherent to dialkylhydroxylamines, and has great practical advantages. Furthermore, N
, N-dialkylhydroxylamines have the drawback of coloring a color developing solution yellow and staining light-sensitive materials, etc., whereas the compounds of the present invention have no problems in this respect.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the compound of the present invention is contained in a color developing Ω solution, and at least one layer of the silver halide emulsion layer of the silver halide photographic light-sensitive material has the general formula [C]. It is characterized by the fact that it is treated by containing a cyan coupler shown in
Not only does the color developer have excellent stability over time, but it also prevents the maximum concentration of cyan dye from decreasing even when the concentration of the color developing agent in the color developer decreases.

Next, the cyan coupler used in the present invention will be explained.

The cyan coupler of the present invention can be represented by the above general formula [C], and the general formula [C] will be further explained.

Each group represented by R8-R2 includes those having a substituent.

R, is an aliphatic group having 1 to 30 carbon atoms, and 6-carbon atoms;
30 aromatic groups and heterocyclic groups having 1 to 30 carbon atoms are preferred; as R4 and R1, hydrogen atoms and the groups listed as preferred for R are preferred ~1°; as R2, directly or , hydrogen atom bonded to NH via -NH-1-CO- or -802-, carbon number 1
-30 aliphatic group, C6-30 aromatic group, C1-30 heterocyclic group, -OR,, -CO2R16, -
8olRIDmal! -8OzOR,.

(Re, R* and V RIo are respectively the above R<, Ft
is the same as that pronounced in s and R6,
R6 and R1 may be combined to form a heterocycle) is preferred.

R is preferably an aromatic group having a carbon WL of 6 to 30, and representative examples of the substituent represented by Rt include a halogen atom, a hydroxy group, an amide group, a carboxyl group, a sulfonic acid group, a cyano group, and an aromatic group. group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic Examples include a group sulfonyl group, an aromatic sulfonyl group, a sulfonylamide group, a nitro group, an imide group, an aliphatic group, an aliphatic oxycarbonyl group, and the like.

When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, such as a dioxymethylene group.

Typical examples of the group represented by R5 include a halogen atom, a hydroxy group, an amide group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group,
Sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group,
Examples include an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamide group, a nitro group, an imide group, and the number of carbon atoms contained in R1 is preferably θ to 30. When m = 2, a cyclic Examples of R5 include dioxymethylene group and the like.

! is 1 and 1L is particularly preferably -coNR,Rs, R2 is preferably O, and R2 is directly IIN) (6-CO bonded to
R,, -COOR,, -8O,R1,, -CONRI
Rs, -5ozNRIR, is particularly preferred*, and even more preferred is C OOR+ o, C which directly binds to NH.
ORa, SOz R+ e, -COOR,
. is most preferred.

Also included in the present invention are those that form dimers or more multimers via R1-R2.

A specific example of a coupler represented by the general formula [CI is JP-A No. 6]
No. 0-237448, No. 61-153640, No. 61
-145557, 62-85242, 48-1
No. 5529, No. 50-117422, No. 52-183
No. 15, No. 52-90932, No. 53-52423, No. 54-48237, No. 54-68129, No. 5
No. 5-32071, No. 55-65957, No. 55-1
No. 052213, No. 56-1938, No. 5B-126
No. 43, No. 5B-27147, No. 56-128832
No. 58-95346 and U.S. Pat. No. 3.488.
No. 193, etc., and can be synthesized by the methods described therein.

In order to add the coupler of the present invention to a photosensitive material, depending on the physical properties (e.g. solubility) of the coupler, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent or an alkaline dispersion method in which the coupler is added as an alkaline solution can be used. Various methods can be used, such as a latex dispersion method, a solid dispersion method in which fine solids are added directly.

The amount of the coupler of the present invention added is usually in the range of 1.0XIO-' mol to 1.0 mol, preferably 5.0XIO-' mol to s.oxto-' mol, per 1 mol of silver halide.

Typical specific examples of couplers represented by the general formula [CI] are shown below, but the present invention is not limited thereto.

-I C-5 C-20 ! t l'l s (J (,;suN1-1+1 C,! )(,S C,,Hl.

／−１−−−−−＼ i CHlCH,SCH,CH,C0IH ■ CH, CH, NH30, CH.

This-38 /'IT υ CHtCH2SCHC+zH2s CO,H m43 m44 C-45 謬C,,)I□ C1@H! + OOH Summer OOH OOH OOH OOH CO. H It is preferable that the color developing solution used in the present invention further contains at least one compound selected from the compounds represented by the following general formulas [1[] and [I[[], respectively.

General formula [I] General formula [III] (In general formula [II] and [■], L is an alkylene group,
Cycloalkylene group, phenylene group, -L a-0-L
a-0-L a- or -Lq-Z-L9 @ table waste. Here z is L12 - R29 Ll2 - R2
9 zF%31 R%I Ll-Ll3 each represent an alkylene group.

R21 to R31 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphonic acid S<including its salts). However, at least two of R21 to R24 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least two of R25 to R27 are carboxylic acid groups (including salts thereof). (including its salt)
or a phosphonic acid group (including its salts). ) Alkylene groups, cycloalkylene groups and phenylene groups represented by formulas [I[] and [II[],
The alkylene groups represented by L1 to L13 also include those having substituents.

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

[Example Compound] [I[-1] Ethylenediaminetetraacetic acid [1[-2]
Diethylenetriaminepentaacetic acid [I[-31ethylenediamine-N-(β-hydroxyethyl)-N,N'
, N'-triacetic acid [n-41 propylene diamine tetraacetic acid [ll-5]
triethylenetetraminehexaacetic acid [1r-6]cyclohexanediaminetetraacetic acid [l-711,2-diaminopropanetetraacetic acid [ll-811,3-diaminopropan-2-ol-tetraacetic acid][l-91 ethyl etherdiaminetetraacetic acid] [11-
10] Glycol ether diamine tetraacetic acid [I [11] Ethylenediamine tetrabrobionic acid [I
F-12] phenylenediaminetetraacetic acid [I[-1
31 Ethylenediaminetetraacetic acid disodium salt [I[-14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [ll-151 Ethylenediaminetetraacetic acid tetrasodium salt [I[-16] Diethylenetriaminepentaacetic acid pentasodium salt [I[-17] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt [n-18] Propylenediamine tetraacetic acid sodium salt [[-19] Ethylenediamine tetramethylene phosphonic acid [1-201 Cyclohexanediamine Tetraacetic acid sodium salt [ll-21] Diethylenetriaminepentamethylenephosphonic acid [ll-221 Cyclohexanediaminetetramethylenephosphonic acid [1[[-1] Nitrilotriacetic acid [II[-21 Iminodiacetic acid [11[-31 Nitrilotripropionic acid] [[-4
] Nitrilotrimethylenephosphonic acid [m-5] Iminodimethylenephosphonic acid [111-6] Nitrilotriacetic acid trisodium salt [1[[-7] [11-81 [11[-91 [DI-10]] These general formulas [ Among the chelating agents represented by [II] or [11], compounds that are particularly preferably used from the viewpoint of the desired effects of the present invention include (I[-1), (I-2),
(1-5), (II-8), (n-19), (I-1)
and (1-4).

The amount m of the chelating agent represented by the general formula [1F or [I]] is preferably used in the range of 0.1 to 20 g per color developer 11, and particularly from the viewpoint of the purpose of the present invention, the amount m is in the range of 0.3 to 20 g. A range of 10 g is particularly preferably used.

The color developing solution used in the present invention further includes the following general formula [■], general formula [Vl], general formula [Vl], general mariner ■
It is preferable to use at least one compound selected from the compounds represented by the general formula [■] and the general formula [■].

General formula [IV] General formula [V] In the formula, R4+, R42, R43, R44, R45 and R46 are each a hydrogen atom, halogen atom, and Rso are each a hydrogen atom or a carbon atom number of 1 to 18
represents an alkyl group. However, when R44 and R42 represent -OH or a hydrogen atom, R43 is a halogen atom, a sulfonic acid group, or
, R43, R44, R45 and R46 include, for example, methyl group, ethyl group, 1so-propyl group, n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, Examples include methylcarboxylic acid group, benzyl group, and R47.
The alkyl group represented by R481R49 and Rso has the same meaning as above, and further includes an octyl group.

Furthermore, the phenyl group represented by R41, R42, R4ae R44, R45 and R46 includes phenyl group, 2-
Examples include hydroxyphenyl group and 4-aminophenyl group.

Representative specific examples of the compounds represented by the general formulas [IVl and [V] are listed below, but the invention is not limited thereto.

(IV-1>4-isopropyl-1,2-dihydroxybenzene (IV-2) 1,2-dihydroxybenzene-3゜5-
Disulfonic acid (IV-3) 1.2.3-trihydroxybenzene-5
-carboxylic acid, (rV-4)1.2.3-trihydroxybenzene-
5-carboxymethyl ester (IV-5>1.2.3-trihydroxybenzene-5
-Carboxy-〇-butyl ester (IV-6) 5-t-butyl-1,2,3-trihydroxybenzene (rV-7) 1,2-dihydroxybenzene-3゜4.
5-trisulfonic acid (rV-8) 1.2-dihydroxybenzene-3゜5.
6-trisulfonic acid (V-1”) 2.3-dihydroxynaphthalene-6-sulfonic acid (V-2) 2.3.8-trihydroxynaphthalene-6
-Sulfonic acid (V-3) 2.3-dihydroxynaphthalene-6-carboxylic acid (V-4) 2.3-dihydroxy-8-isopropyl-
Naphthalene (V-5) 2,3-dihydroxy-8-chloro-naphthalene-6-sulfonic acid Among the above compounds, compounds particularly preferably used in the present invention include 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 compounds represented by the general formulas [IVl and [V] can be used in an amount of 5 sc+ to 20 degrees per developer, preferably 10 g to 10 g, more preferably 20 g to 20 g. Good results are obtained by adding 3 g.

General formula [VI] (In the above general formula [VI], subtracted by 1, R5□ and R9
゜represents a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphoric acid group (including its salts), respectively. However, R5+ * At least one of R52 and RsB is a hydroxyl group, and only one of R51, R52 and R11 is a carboxylic acid group (including a salt thereof) or phosphorus V*<including a salt thereof).

nl, R2 and R3 each represent an integer of 1 to 3. ) In the general formula [VI], RT;t, Rtt and R51 are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including a salt thereof), or phosphorus? l [(including its salts), but as salts of carboxylic acid groups and phosphoric acid groups,
Examples include salts of alkali metal atoms, salts of alkaline earth metal atoms, etc., and salts of alkali metal atoms such as sodium and potassium are preferable. Also, R1;t+R5z
and at least one of R53 is a hydroxyl group, and only one of Rt+, Rs2 and R53 is a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof).

R51, R5Z and RS3 are each preferably selected from a hydroxyl group, a carboxylic acid group (including its salts), or a phosphoric acid group (including its salts).

n4. n2 and n3 each represent an integer from 1 to 3.

Typical specific examples of the compound represented by the general formula [VI] are listed below, but are not limited to these. General formula [■] In the general formula [■], R is hydroxyalkyl having 2 to 6 carbon atoms. Group, RI; 5 and R54 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a pencil group or an integer of 2 to 6, X' and 2- are each a hydrogen atom, a carbon It represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.

R54 is preferably a hydroxyalkyl group having 2 to 4 carbon atoms, and Rdada and Rwa6 are each preferably an alkyl group having 1 to 4 carbon atoms or a hydroxyfurkyl group having 2 to 4 carbon atoms.

Preferred specific examples of the compound represented by the general formula [■] are as follows.

Ethanolamine, jetanolamine, triethanolamine, di-isopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1-propatur, 3-dimethylamino-
1-Propertool, Isopro and Luamine Ethanol, 3
-Amino-1-propatol, 2-amino-2-methyl-1,3-propanediol, ethylenediaminetetraisopropanol, benzyljetanolamine, 2-
Amino-2-(hydroxymethyl)-1,3-propanediol.

These compounds represented by the general formulas [VI] and [VI] are preferably used in an amount of 3 to 100 g per color developer 11, more preferably in a range of 6 to 50a, from the viewpoint of the desired effect of the present invention. (In the formula, R5 represents an alkylene group having 1 to 6 carbon atoms, R'J represents an alkyl group, and n is 500 to 20
．． (representing an integer of 000) The alkylene group having 1 to 6 carbon atoms represented by the R back may be linear or branched,
Preferred are alkylene groups having 2 to 4 carbon atoms, such as ethylene, propylene, butene, isobutyne, dimethylethylene, and ethylethylene.

The alkyl group represented by R5F is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc., and also includes those having a substituent (for example, a hydroxyl group). n represents the number of repeating units in the polymer chain, and represents an integer of 500 to 20,000, preferably an integer of 500 to 2.000. Poly(ethyleneimine) in which aR11'7 is an ethylene group is the main Most preferred for purposes of the invention.

Specific examples of poly(alkyleneimine) represented by the general formula [■] are shown below, but the present invention is not limited thereto.

Exemplary Compounds PAI-1 Poly(ethyleneimine) PAI-2 Poly(propyleneimine) PAI-3 Poly(buteneimine) PAI-4 Poly(isobutyneimine) PAL-5 Poly(N-methylethyleneimine) FAI-
6 poly(N-β-hydroxyethylethyleneimine) PAI-7 poly(2,2-dimethylethyleneimine) PAI-8 poly(2-ethylethyleneimine) PAI-
9 Poly(2-methylethyleneimine) poly(alkyleneimine) can be used in the color developer in any amount that achieves the objectives of the present invention, but generally from 0.1 to 1/12 in the color developer. 50013 is preferred, and more preferably used in a range of 0.5 g to 300 g.

The compound of the present invention represented by the general formula [I] may be used in combination with other preservatives, and examples of preservatives that can be used in combination include sodium sulfite, potassium sulfite, sodium bisulfite, and bisulfite. Examples include sulfites such as potassium, and bisulfite adducts of aldehydes or ketones, such as formaldehyde bisulfite liquid additives and glutaraldehyde bisulfite adducts.

As the color developing agent used in the color developer of the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used.

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-phenylenediamine,
Not only does it have the advantage of not causing contamination of the photosensitive material and does not cause skin irritation, but especially in the present invention, by combining it with the compound represented by the general formula [I], the object of the present invention can be efficiently achieved. can be achieved.

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

-(CH2)l NH3O2-(CH2)n CH3,
-(CH2)I O-(CH2)n-CH3, -(CI
-120H20) n C11-121+1 (l and n each represent an integer of 0 or more), -COOH
Preferred examples include a -3O3H group and a -3O3H group.

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

Exemplary color development agent (A-1) H, C2C, H, NH30, CH3 \/ (A-2) H* Cs C2H40H \/ (A-3) H* Cz C2H40H \/ (A-4> HsC2C2H4OHs \/ (A-5) (A-8) HOH4C2C2H4OH\/ (A-7) Hs Cx Cz H4N HS Oz CHa\/ White Among the color developing agents exemplified above, used in the present invention,
Particularly preferred is (A-1).

The color developing agents mentioned above are usually used in the form of salts such as hydrochloride, sulfate, p-1-luenesulfonate and the like.

The color developing agent having a water-soluble group used in the present invention is
IX 10-2 to 2X10 per 12 ordinary color developer
It is preferable to use the amount in the range of −1 mol, but from the viewpoint of rapid processing, it is 1.5×10 −2 to 2
A range of X10' moles is more preferred.

The color developing agent may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
- May be used in combination with pyrazolidone, metol, etc.

Further, instead of using the above-mentioned color developing agent in the color developing solution, a color developing agent can be added to the light-sensitive material, and the color developing agent used in this case includes a dye precursor. A typical dye precursor is JP-A No. 5
Those described in No. 8-65429, No. 58-24137, etc. are used.

According to J3 of the present invention, when a triazylstilbene fluorescent brightener represented by the following general formula [IXl is used in the color developer according to the present invention, the gamma of the cyan dye is stabilized,
This is preferable because it causes less color staining.

General formula [IXl, where x1. ×2. Yl and Y2 each represent a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholim L alkoxy group, an aryloxy group, an alkyl group, an aryl group, an amino group, or an alkylamino group. M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

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

＝ ＝ ト
αko1! These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 69 g per 11 of the color developer used in the present invention, particularly preferably in a range of 0.4 to 3 g.

In addition to the above-mentioned components, the color developing solution of the present invention includes commonly used alkaline agents, various salts for increasing ionic strength,
Developer components such as inorganic and organic antifoggants and development accelerators can be included.

In particular, as a development accelerator, U.S. Patent No. 2,304,925
Regarding organic solvents that are poorly soluble in water, such as benzyl alcohol, which is described in the above issue, tar is likely to be generated, and due to the poor dissolution rate, there is a limit to the development promotion effect, and furthermore, the waste liquid treatment is difficult. However, it is desirable to reduce or eliminate its usage as much as possible, since it requires a great deal of labor and expense.

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

Furthermore, auxiliary developers can also be used with the developing agents. In addition, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor-releasing coupler (so-called DIR coupler), a development inhibitor-releasing compound, etc. may be added as required.

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

Each component of the above-mentioned color developing solution can be prepared by sequentially adding and stirring a certain amount of water.

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
~13.0.

In the present invention, the processing temperature for color development is 30°C.
As mentioned above, the higher the temperature is 50°C or less, the more preferable it is because it enables rapid processing in a short time, but from the viewpoint of image storage stability, it is better not to be too high, and it is preferable to process at a temperature of 33°C or higher and 45°C or lower.

The color development time has conventionally been generally about 3 minutes and 30 seconds, but from the viewpoint of speeding up, it is preferably within 2 minutes, and more preferably within a range of 30 seconds to 1 minute and 30 seconds.

The present invention can be applied to any system as long as it uses a color developing solution containing the compound of the present invention represented by the general formula [I]. Spray type that sprays liquid,
Alternatively, various processing methods such as a web method involving contact with a carrier impregnated with a processing solution, or a development method using a viscous processing solution can be used, but the processing steps are essentially color development, bleach-fixing, washing with water, or an alternative thereof. It consists of steps such as stabilization treatment.

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, copper, etc. is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. Such an acidic gold, Ii! ! The most preferred carboxylic acids used to form complex salts include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal 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] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10] ] 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'-Triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexane diamine tetraacetic acid sodium salt These bleaching agents are 5 to 4 SOQ/l , more preferably 2
Use at 0 to 250 g/fL. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetic acid iron (III) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halogen such as ammonium bromide may be used. Bleach-fix solutions with a composition containing a large amount of halides such as ammonium bromide, and even special bleach-fix solutions containing a combination of ethylenediaminetetraacetic acid iron (III) complex salt bleach and a large amount of halides such as ammonium bromide are also used. be able to.

The silver halide fixing agent contained in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as thiosulfur 1, which is used in ordinary fixing processing.
Typical examples include 1ti, thiocyanine salt, thiourea, and thioether.

These fixatives are 5G/j! Although it is used in an amount within a range that can dissolve it, it is generally used in an amount of 70a to 2SOQ/(l).

The bleach-fix solution may contain various 118Iiii agents singly or in combination of two or more.

Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. Further, various preservatives, organic chelating agents or stabilizers, organic solvents, etc. can be included as appropriate.

Various bleach accelerators can be added to the bleach-fix solution used in the present invention.

The I)H of the bleach-fix solution is used at 4.0 or more, but generally it is used at pH s, o or more and pH 9.5 or less, preferably at pi-16.0 or more and pHa, s or less. The most preferable 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 washing substitute stabilizing liquid that can be applied to the present invention will be explained.

I)H of the water washing alternative stabilizer that can be applied to the present invention is preferably in the range of 565 to 10.0, more preferably l
) 86.3 to 9.5, particularly preferably pH
It ranges from 7.0 to 9.0. 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, it is preferable that the processing time be as short as possible, but it is usually 20 seconds or more.
The treatment time is 10 minutes, most preferably 1 to 3 minutes, and in the case of a multi-species stabilization treatment, it is preferable that the treatment time be shorter in the first stage tank and longer in the second stage tank. Especially 20% of the anterior 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.

As described above, in the present invention, the treatment with a water-washing substitute stabilizing solution refers to a stabilization treatment that is performed immediately after the treatment with a bleach-fixing solution and does not substantially require a water-washing treatment. The treatment liquid used for this is called a washing alternative stabilizer, and the treatment tank is called a stabilization bath or stabilization tank.

The number of stabilization tanks in the stabilization treatment that can be applied to the present invention is 1 to 5.
The effect of the present invention is great when the tank is a tank, and it is particularly preferable to
-3 tanks, preferably 9 tanks or less at most.

The crystal structure of the silver halide grains used in the present invention 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.

In addition, tabular silver halide grains (JP-A-58-1139
No. 34 and Japanese Patent Application No. 170070/1983) may also be used.

The silver halide emulsion used in the present invention may be chemically sensitized with activated gelatin, a sulfur sensitizer, a selenium sensitizer, a reduction sensitizer, a noble metal sensitizer, etc. alone or in combination as appropriate. good.

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.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 x 10-8 to 3
Optical sensitization may be achieved by adding 3 moles.

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.

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

The silver halide emulsion layer may contain a coupler other than the cyan coupler of the present invention, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

Yellow couplers and magenta couplers that can be used in the present invention can be used without particular limitations. These couplers may be of the so-called 2-equivalent type,
A 4-equivalent coupler may be used, and a diffusible dye-releasing coupler or the like may be used in combination with these couplers.

As magenta couplers for photography, compounds such as pyrazolone, pyrazolinobenzimidazole, and indasilone are used, but the magenta coupler represented by the following general formula [M-II] improves processing stability and color reproducibility of images. It is preferable from the aspect.

General formula [M-i] (In the formula, 2' represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2' may have a substituent.

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

Moreover, R represents a hydrogen atom or a substituent. ) general formula [M-I
There are no particular restrictions on the substituent represented by R in I, but
Typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Six groups include alkenyl, cycloalkyl, etc.
In addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoylcyano, alkoxy, aryloxy, heterocyclicoxy,
Six groups: siloxy, acyloxy, carbamoyloxy, amine, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl heterocyclic thio, spiro compound residues, bridged hydrocarbon compounds Also included are residues and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by Xo include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthiosulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino, aryloxy 6 such as carbonylamino, carboxyl, (R' has the same meaning as R, 2' has the same meaning as 2', and R2 and R3 represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group). Among these groups, a halogen atom, particularly a chlorine atom is preferable.

Examples of the nitrogen-containing heterocycle formed by 2' or 2'' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those mentioned above for R. Things can be mentioned.

More specifically, what is represented by the general formula [M-II] is represented by, for example, the following general formulas [M-If] to [M-■].

CM-II] [M-11[] [M-IV] [M-Ml-Throwing coins [M-Vl] 1 in the above-mentioned-Throwing coins [M-II] to [M-Vl]
71' to R81 and Xa have the same meanings as R and X above.

Particularly preferable ones among the above-mentioned coins [M-III to Magenta Kabra represented by [M-V[]] are those represented by the general formula [M-
1] is a magenta coupler.

- The substituent that the ring formed by Z' in M-IF may have, and - The money [M-11 to [M-V
R2' to R81 to be placed in [M-
■Those represented by C are preferred.

-Token [M-■J -R4-3O2-R5 In the formula, R4 represents an alkylene group, and R5 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R4 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and does not matter if the straight chain has 9 branches.

The cycloalkyl group represented by R5 is preferably a 5- to 6-membered one.

In addition, when used for positive image formation, the substituent R on the heterocycle
The most preferable one for R1′ and R1′ is the following:
-IXI.

- Throwing money [M-IXI R,/R+o'-C- R11' In the formula, Rs', Rho' and R11' each have the same meaning as R above.

Also, two of the above R9' + Rho' and R11', for example R9' and Rho', are bonded to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle).
may be formed, and R11' may further be bonded to the ring to form a bridged hydrocarbon compound residue.

Among the general formulas [M-IXI, (i) R
When at least two of s' to R11' are alkyl groups, (ii> one of Rs' to R11', for example, R
11' is a hydrogen atom, and the other two are Rs' and R+o
' is combined with the root carbon atom to form a cycloalkyl.

Furthermore, among (i), R9' to R11' are preferable.
Two of them are alkyl groups, and the other one is a hydrogen atom or an alkyl group.

In addition, when used for negative image formation, the substituent R on the heterocycle
And the most preferable as R1' is the following - coin CM -
X].

- Throwing coins [M-X] R+2'-CH2- In the formula, R12' has the same meaning as R above.

Preferred as R12' is a hydrogen atom or an alkyl group.

Typical specific examples of the compounds according to the present invention are shown below.

In addition to the representative examples of the compounds represented by the general formula [M-II] according to the present invention, specific examples of the compounds according to the present invention include Japanese Patent Application No. 61-9791 Mei Ill. Among the compounds described on pages 66 to 122 of
4, 6.8~17.19~24°26~43.45~5
9. ．． 61-104. 106-121, 123-1
62. Compounds represented by 164 to 223 can be mentioned. Furthermore, Japanese Patent Application No. 61-288370,
Compounds described on pages 20 to 32 and pages 16 to 30 of Japanese Patent Application No. 62-65314 may also be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal of the Chem)
ical 5ociety), Perki
n) I (1977), 2047-2052, U.S. Patent No. 3.725.067, JP-A-59-99437
No. 58-42045, No. 59-162548,
No. 59-171956, No. 60-33552, No. 6
No. 0-43659, No. 60-172982 and No. 60
It can be synthesized by referring to No.-190779 and the like.

The above couplers are usually 1X10- per mole of silver halide.
3 mol to 1 mol, preferably 1X10-2 mol to Bxi
It can be used in a range of o-' moles.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

Furthermore, colored magenta couplers of the type described in U.S. Pat.

As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers can be used. Furthermore, the carbon atom at the coupling position f! during the coupling reaction! Diary yellow couplers substituted with substituents capable of being jilB2 are also advantageously used.

The use of the above-mentioned diffusion-resistant coupler in the present invention (2) is generally 0.5% per mole of silver in the light-sensitive silver halide emulsion layer.
05 to 2.0 mol.

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

In addition to DIR compounds, the present invention also includes compounds that release a development inhibitor during development.

Furthermore, JP-A No. 54-145135, 5G-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Alternatively, a so-called timing DIR compound, which is a compound that releases a development inhibitor through an elimination reaction, is also included in the present invention.

Also, JP-A No. 58-160-54, 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 upon reaction 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.times.10@-3 moles to 10.times.10@-3 moles per mole of silver.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives. For example, Research Disclosure Magazine 17643
Antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, and wetting agents listed in the No. etc. can be used.

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

As the support for the silver halide color photographic light-sensitive material used in the present invention, all commonly used supports can be used depending on the purpose. The installation location can be determined arbitrarily.

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 contains a coupler in the light-sensitive material and is processed by a so-called internal development method, color It can be applied to any silver halide color photographic material such as vapor, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color paper.

[Effects of the Invention] As explained above, according to the present invention, the color developing solution has excellent stability over time such as preservation, and there is little variation in photographic performance such as fogging or hard contrast in the shoulder area in dye images. Furthermore, it is possible to provide a method for processing a silver halide color photographic light-sensitive material, which has excellent processing stability and has a small variation in the maximum density of cyan dye.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.Example 1 Color developing solution No. 1 to 1 with the following compositions 6 was prepared.

(Color developer) The above color developer contains 4 ppn+ ferric ions and 2 copper ions.
E) 11m (FeC23, CuSO4・6H2 respectively)
0 was dissolved and added), and the opening ratio was 150 at 33°C.
The concentration of the color developing agent in the color developer was analyzed using the 1111m cerium method while the color developer was stored in a glass container of C1'/ffi (air contact area is 150C1' for a color developer of 1ffi). The number of days until the concentration of i-developing agent reached O was determined as the lifespan of the color developer.

As is clear from the results in Table 1, the life of the color developer using hydroxylamine sulfate, which is one of the conventional preservatives, is short when metal ions are mixed. In contrast, all of the color pA image solutions using the compounds of the present invention have significantly extended lifespans.

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 (1/n' gelatin, o,
A blue-sensitive silver halide emulsion (A!l Br :A(It Cff1-0.
5:99.5) and 1.0 x 10-3 mol g/12 of the following yellow coupler (Y-R) dissolved in 0.55 g/f of diocdylphthalate.

Layer 2: Intermediate layer consisting of gelatin of 0.70+J/i2.

Layer 3 ----1,20 o/v gelatin, 0.
220/f green-sensitive silver halide emulsion (AgSr:A
! I Gl=0.5: 99.5) and 0.30 (1
/f(7) 1,OX dissolved in dioctyl phthalate
The following magenta coupler (M-R
).

Layer 4: Intermediate layer consisting of gelatin of 0.70 (1/f).

Layer 5...1.20 (1/u' gelatin, 0.
28 (1/l' red-sensitive silver halide emulsion (A!J B
r:8gCffi=0.5:99.5) and 0.
1,90 dissolved in 309/u” dibutyl phthalate
X 10-3 mol (J/f of an exemplary cyan coupler (
C-29).

Layer 6...1.0q/f gelatin and 0.25
0,3 dissolved in dioctyl phthalate of fJ/f
A layer containing 2 g/f of Tinuvin 328 (UV absorber manufactured by Ciba Geigy).

Layer 7: A layer containing 0,648 g/f of gelatin.

In addition, 2,4-dichloro-6-hydroxy-5-t-lyazine sodium was added as a hardening agent in layers 2.4 and 7.
Each was added in an amount of 0.0171 J per 1 g of gelatin.

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

Processing process 3! ! Temperature Processing time (1) For color development @ 35℃ 45 seconds (2) Bleaching window @
35℃ 45 seconds (3) Wash with water 30℃
90 seconds (4) Drying 60-80℃ 60 seconds The color developing solution used had the following composition: N 0.7-
13.

(color developer) The bleach-fix solution used had the following composition.

[Bleach-fix solution] is adjusted to pH 5.5 with glacial acetic acid.

After processing, the sample was measured for the reflection density of the cyan dye using an optical densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.), a sensitometric curve was created, and the minimum reflection density of the cyan dye was measured. . Next, the slope (gamma value) from the 1!1 degree point with a reflection density of 0.8 of the cyan dye to the density point with a reflection density of 1.8 was calculated.

The same amount of the same metal ion as in Example 1 was added to the color developing solution after the treatment, and the solution was stored at 35° C. for one week.

Repeat the process after storage to remove the lowest amount of cyan dye! )
111 degrees was measured and the cyan gamma value was calculated.

The difference in the minimum reflection si and the cyan gamma value of the cyan dyes of the pre-preserved samples are shown in Table 2.

From Table 2, it is clear that J: Sea urchin, hydroxylamine IXt l, one of the conventional preservatives! 2 J? , the increase in cyan fog and cyan gamma after storage was significant.

On the other hand, it can be seen that all the images treated with the color developing Jr2 image solution using the compound of the present invention as a preservative are good.

Example 3 The sample used in Example 2 and a sample in which the cyan coupler used in this sample was replaced with the cyan coupler shown in Table 3 were treated in the same processing steps as the actual JMIIA2.

However, here, the preservative and the amount added in the color development liquid are as follows:
As described in Section 3a.

Location L! [! Table 3 shows the maximum concentration of cyan dye.

Comparative cyan coupler (1) Comparative cyan coupler (2) As is clear from Table 3, by using the preservative of the present invention and the cyan coupler of the present invention, the maximum concentration of cyan can be stably obtained, and the minimum concentration is also lower. It can be seen that when a preservative other than the one according to the invention is used, the maximum density decreases greatly, and even when a coupler other than the one according to the invention is used, the maximum density and the minimum cyan density are affected, resulting in unfavorable results.

Example 4 From the support side, a black colloidal silver antihalation layer, a red-sensitive silver halide emulsion layer, an i-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer were formed, and the blue-sensitive silver halide emulsion layer was A monodisperse highly sensitive silver halide emulsion layer was disposed on the outermost side of the silver emulsion layer to prepare a silver halide photosensitive material sample.

However, the amount of coated silver was 55 rna/100 cf, and the dry film thickness was 23 μm.

Mll...A dispersion of 0.8 g of black colloidal silver, which exhibits high absorbency to light in the wavelength range of 400 to 700 nm by reducing silver nitrate with hydroquinone as a reducing agent, is made with 3 g of gelatin, and an antihalation layer is applied. °

Layer 2: Middle layer made of gelatin.

Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion <A
1.6 g of gelatin and o, as
g of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy[δ-(2,4-di[-amylphenoxy)butyl]
-2-naphthamide (hereinafter referred to as cyan coupler (C-0)
), 0. 030 g of 1-hydroxy-4- [
4- <1-hydroxy-8-acetamido-3,6-
disulfo-2-naphthylazo)phenoxy]-N-[δ
-(2,4-di-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CG-1)) is dissolved in 0.4σ tricresyl phosphate (hereinafter referred to as TCP). A low-sensitivity red-sensitive silver halide emulsion layer containing

Layer 4...1.1g of highly sensitive red-sensitive silver iodobromide emulsion (A
gI: 6 mol%), 1.2 g of gelatin and 0. 2
50 cyan coupler (C-0), 0. 0.020 colored cyan coupler (CG-1) dissolved. 1
7 (Highly sensitive red-sensitive silver halide emulsion layer containing TCP of J.

Layer 5...0. 07g of 2.5-di-t-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1))
0. 04 (J dibutyl phthalate (J,
4 below, referred to as DBP) and an intermediate layer containing 1.2 g of gelatin.

Layer 6: 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (A
al: 6 mol%), 1.1 g of gelatin and 0.1 g of gelatin. 3
2g of 1-(2,4.6-dolichlorophenyl)-3
- [3-(2.4-di-t-amylphenoxyaletamidonebenzenamide]-5-pyrazolone (hereinafter referred to as
Magenta coupler (M-1)), 0. 209 4,4-methylenebis-1 1- (2,4,6-dolychlorophenyl)-3- [3- (2,4-di-monoamylphenoxyacetamide)benzenamide]-5
-pyrazolone (hereinafter referred to as magenta coupler (M-2)), 0.066 g of 1-(2,4,6-dolichlorophenyl)-4-(1-naphthylazo)-3-(
2-chloro-5-octadecenylsuccinimide anilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)).
．． Low-speed green-sensitive silver halide emulsion layer containing 3 g of TCP.

! ii7...- 1.5 g of high-sensitivity green-sensitive silver iodobromide emulsion (A!JI; 8 mol %), 1.9 g of gelatin and o. io g magenta coupler (M-1), 0, 0
98 (J magenta coupler (M-2), -〇.
049111 colored magenta coupler (CM-1)
0. A highly sensitive green-sensitive silver halide emulsion layer containing 129 TCP.

1! i8...0.2g yellow colloidal silver, 0. 2g
of antifouling agent (HQ-1) and tcO. 11(J
(7) Yellow filter layer containing D B P and 2.1 g gelatin.

Layer 9 - 0.95 g of low-speed blue-sensitive silver iodobromide emulsion (AgI; 7 mol %), 1.9 g of gelatin and 1.
84 g of α-[4-(1-benzyl-2-]]nyl-3,5-dioxo-1,24-triaziridinyl)]-
] Contains 0.93 g of DBP in which α-pivaloyl-2-chloro5[γ-(2,4-di[-amylphe”noxy)butanamide]acetanilide (hereinafter referred to as yellow coupler (Y-1)) is dissolved. Low-speed blue-sensitive silver halide emulsion layer.

Layer 10...1.2 g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (A (Jl; 6 mol%)), 2.0 g of gelatin and 0.460 of yellow coupler (Y-1) were dissolved. A highly sensitive blue-sensitive silver halide emulsion layer containing DBP of 0.23(l).

Layer 11: Second protective layer made of gelatin.

Layer 12: first protective layer containing 2.3 g of gelatin.

In the above sample, cyan coupler (C
-0) of the present invention as shown in Table 4.
The experiment was conducted in the same manner except that -20, C-35, and C-46 (equimolar amounts) were used.

These samples were cut into pieces, subjected to horizontal exposure according to a conventional method, and processed using a piece processing device according to the following steps (hereinafter referred to as manual processing).

Processing process Processing temperature ('C) Tank Processing time 1, color development 37.8 1 3 minutes 15 seconds 2,
Bleach 38 1 3 minutes 15 seconds 3,
Fixed @ 35~38 1 3 minutes 15 seconds 4, alternative water bath
30-3422 minutes 5, stable 30-34 1 1 minute 5 seconds 6,
Drying 1 2 minutes 10 seconds The following color developing solution, bleaching solution, fixing solution, washing alternative bath solution, and stabilizing solution were used.

[Color developer] [Bleach solution] [Fixer] [Water washing alternative stabilizer J [Stabilizer] Optical i1B! Courage 1) Using D△-65 (manufactured by Konishiroku Photo Industry Co., Ltd.),
The A density was measured 1, and a Melly curve from Range 1 to 1 was created, and the minimum transmission density of the cyan dye was measured. Next, the slope (
gamma value) was calculated by a1.

The same amount of the same metal ion as in Example 1 was added to the color developing solution after the treatment, and the sample was temporarily stored in an INN at 38°C.

After storage, the treatment was repeated, the lowest concentration of cyan dye was measured, and the cyan gamma value was calculated.

The difference in minimum transmission density and cyan gamma value of the cyan dye before and after storage were determined and are listed in Table 4.

As is clear from Table 4, when preservatives or cyan couplers other than those of the present invention were used, a marked increase in cyan fog density and gamma of 4 were observed, whereas hydroxylamine of the present invention Derivative (I-1, l-18, l-
21) and the coupler of the present invention (C-20, C-35,0-
It is clear that when 46) is combined, both fog and gamma increase are suppressed and good results are obtained by 1q.

Example 5 The magenta coupler (M-1) used in Example 4 was
Samples similar to those in Example 4 were prepared and processed, except that C-20 was used as the cyan coupler as shown in the table. However, as is clear from Table 5 for magenta in addition to cyan fog density fluctuations and cyan gamma value fluctuations, exemplified compound (1) is used as a magenta coupler in the preservative of the present invention.
, (3), (7) and (14), the stability of the magenta dye image has been improved, and in addition to this, it has also decreased by 0.04 to 0.05 against cyan gamma fluctuations. We also obtained a surprising improvement effect.

Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (2)

[Claims] (1) At least one layer of the following general formula [C] on the support
At least the step of using a color developing solution containing a compound represented by the following general formula [I] to provide an imagewise exposed silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a compound represented by the formula [I] below. 1. A method for processing a silver halide color photographic material, which comprises performing the processing in a processing step. General formula [C] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is -CONR_4R_5, -NHCOR
_4-NHCOOR_6, -NHSO_2R_6, -N
HCONR_4R_5 or -NHSO_2NR_4R_
5, R_2 is a monovalent group, R_3 is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developer, l is 0 or 1, m is An integer from 0 to 3, R_4 and R_5 are each a hydrogen atom, an aromatic group,
an aliphatic group or a heterocyclic group, R_6 represents an aromatic group, an aliphatic group, or a heterocyclic group, and when m is 2 or 3, R_
It includes those in which 3 are the same, different, and those in which R_4 and R_5, R_2 and R_3, and R_2 and X combine to form a ring. However, when l is 0, m is O, and R_1 is -CONHR.
_7, and R_7 represents an aromatic group. ) General formula [I] (In the formula, R_1_1 and R_1_2 each represent an alkyl group or a hydrogen atom. However, R_1_1 and R_1_
It does not include cases where both of 2 are hydrogen atoms at the same time. It also includes those in which R_1_1 and R_1_2 form a ring. ) (2) The color developing solution has the following general formulas [II] and [III]
The method for processing a silver halide color photographic light-sensitive material according to claim (1), which comprises at least one compound selected from compounds represented by the following. 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
Represents _8-O-L_8- or -L_9-Z-L_9-. Here, Z is ▲mathematical formula, chemical formula, table, etc.▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. L_1 to L_1_3 each represent an alkylene group. R_2_1 to R_3_1 are hydrogen atoms, hydroxyl groups,
Represents a carboxylic acid group (including its salts) or a phosphonic acid group (including its salts). However, R_2_1 to R_2_4
at least two of the R
At least two of _2_5 to R_2_7 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof). )