JP2640229B2 - Processing method for silver halide color photographic light-sensitive materials having excellent processing stability - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, the processing stability and color contamination are improved, and the fluctuation of the maximum density of cyan dye is small. The present invention relates to a method for processing a silver halide color photographic light-sensitive material.

BACKGROUND OF THE INVENTION Generally, in a color developer, a sulfite or a sulfite is used as a preservative to prevent oxidation of an aromatic primary amine color developing agent represented by a p-phenylenediamine developing agent. And a water-soluble salt of hydroxylamine.

If these sulfites were added alone to the developer,
It is already known that effective preservation can be obtained by adding hydroxylamine as a water-soluble salt because the storage stability is not always sufficient.

However, hydroxylamine salts are decomposed by catalysis by trace amounts of coexisting metal ions, especially iron ions, and not only reduce the preservative effect, but also generate ammonia when decomposed. It is known that fogging and stains are formed on the surface, and abnormalities in photographic characteristics, particularly hardening of the shoulder portion, occur, thereby deteriorating the processing stability.

The mixing of metal ions, particularly iron ions, in the color developing solution in such an automatic developing machine is usually performed by adding a ferric salt of an organic acid to the color developing solution by using a splash, a transport leader, a hanger for suspending a belt or a film, or the like. This is caused by so-called back contamination, in which a bleaching solution or a bleach-fixing solution is introduced.

In order to prevent these undesired effects of metal ions, techniques for incorporating various metal chelators have been proposed and put to practical use. For example, a technique in which a lithium salt is used in combination with a hydroxyalkylidene-diphosphonic acid sequestering agent described in U.S. Patent No. 3,839,045, a polyhydroxy compound and a metal aminopolycarboxylate described in U.S. Patent No. 3,746,544 Techniques using ion sequestering agents in combination, such as techniques using polyhydroxy compounds and aminopolyphosphonic acid sequestering agents described in U.S. Pat.No.4,264,716, can also be mentioned. At present, such problems have not been solved.

Such a decrease in the processing stability caused by the hydroxylamine salt is further amplified in the low replenishment treatment used in recent years due to pollution and economic problems. That is, in the low replenishment process, not only the accumulated metal ions increase, but also the renewal rate of the developer decreases, so that the stagnation time of the developer in the processing tank significantly increases. For this reason, the above-mentioned problems of generation of fog due to the decomposition of the hydroxylamine salt and hardening of the shoulder portion become more remarkable. Under these circumstances, it was also found that the conventional multi-supplementation treatment had little effect, for example, the decomposition of hydroxylamine salts was accelerated by trace metals, particularly copper ions, contained in the reagent. Furthermore, it has been found that it is difficult to make this copper ion almost harmless by using a conventional chelating agent.

From the above-mentioned viewpoints, various preservatives which do not have the disadvantage of such a decrease in the processing stability of the hydroxylamine salt and have a high preservative ability have been studied and developed.

Also, when using certain preservatives for the above purpose,
It is said that the maximum concentration of the cyan dye is easily affected by the concentration fluctuation of the color developing agent in the color developing solution, and particularly when the concentration of the color developing agent in the color developing solution is reduced, the maximum concentration of the cyan dye is likely to decrease. A problem has arisen, and it has been desired to solve such a problem.

[Object of the Invention] Accordingly, a first object of the present invention is to provide a color developing solution which has excellent stability over time, has little fluctuation in photographic performance such as an increase in fog and a high contrast of a shoulder portion, and has an excellent processing stability. An object of the present invention is to provide a method for processing a silver color photographic light-sensitive material.

A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which the maximum density of a cyan dye does not vary much.

[Constitution of the Invention] The object of the present invention is to provide an image-wise exposure method having at least one silver halide emulsion layer containing a compound represented by the following general formula [C] on a support. A silver halide color photographic light-sensitive material other than a silver halide color photographic light-sensitive material having an emulsion layer containing a silver halide having a chlorine content of 50 mol% or more in halogen is represented by the lower general formula [I]. This is achieved by a method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed in a processing step including at least a step of using a color developer containing a compound.

General formula [C] (Wherein, R ₁ -CONR ₄ R ₅ , -NHCOR ₄ , -NHCOOR ₆ , -NHSO ₂ R
_6, the -NHCONR ₄ R ₅ or -NHSO ₂ NR ₄ R _5, the R ₂ is a monovalent radical,
R ₃ represents a substituent; X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized aromatic primary amine developer; l represents 0 or 1;
And m is an integer of 0 to 3, R ₄ and R ₅ each represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, and R ₆ represents an aromatic group, an aliphatic group or a heterocyclic group. , when m is 2 or 3, those R ₃ are each identical, also includes those different and bonded to each other to form a ring, and, R ₄ and R _5, R ₂ and R _3, R ₂
And X are combined to form a ring. Where l is 0
In the formula, m is 0, R ₁ is —CONHR ₇ , and R ₇ represents an aromatic group. ) General formula [I] (Wherein, R ₁₁ and R ₁₂ each represent an alkyl group or a hydrogen atom, provided that R ₁₁ and R ₁₂ are not both hydrogen atoms at the same time, and R ₁₁ and R ₁₂ form a ring Further, according to a preferred embodiment of the present invention, the color developer contains at least one compound selected from compounds represented by the following general formulas [II] and [III].

General formula [II] General formula [III] (In the general formulas [II] and [III], L is an alkylene group,
Cycloalkylene group, a phenylene group, -L ₈ -O-L ₈ -O
-L ₈ - or -L ₉ -X-L ₉ - represent. Wherein Z is, N-L ₁₀ -R _28, NR ₃₀ or Represents L _{1 to} L ₁₃ each represent an alkylene group. R
_{21 to} R ₃₁ are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt)
Represents However, at least two of R _{21 to} R ₂₄ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof), and at least two of R _{25 to} R ₂₇ are
One is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt). [Specific Configuration of the Invention] In the color developer used in the processing method of the present invention, 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 [I], R ₁₁ and R ₁₂ each independently represent an alkyl group or a hydrogen atom that is not a hydrogen atom, but the alkyl groups represented by R ₁₁ and R ₁₂ may be the same or different, and 1-3 alkyl groups are preferred. The alkyl group of R ₁₁ and R ₁₂ includes those having a substituent, and R ₁₁ and R ₁₂ may combine to form a ring,
For example, a heterocyclic ring such as piperidine or morpholine may be formed.

Specific examples of the hydroxyamine-based compound represented by the general formula [I] are described in US Pat. Nos. 3,287,125 and 3,293,095.
No. 34, No. 3,287,124, etc., and particularly preferred and specific exemplary compounds are shown below.

These compounds of the present invention usually contain free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate,
It is used in the form of 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 0.1 g / to 50 g /, preferably 1 g / g.
3030 g /, more preferably 3 g / 〜20 g /.

The compound represented by the general formula [I] of the present invention is used in a conventional color developing solution for a silver halide color photographic light-sensitive material in place of hydroxylamine sulfate which has been widely used as a preservative. However, among the compounds of the present invention, for example, N, N-diethylhydroxyamine is known to be used as a preservative for a black-and-white developing agent in a color developing machine to which a black-and-white developing agent is added. In a so-called external color developing method in which a color photographic light-sensitive material is developed by a reversal method using a color developing solution containing a coupler, there is a technique used together with phenidone. (Special Publication 45-
22198).

Another example of using the compound of the present invention such as N, N-diethylhydroxylamine as a preservative of a black-and-white developing agent added to a color developing solution is a color developing solution in an internal type color developing solution. A technique for preserving the phenidone derivative added therein (see JP-A-53-32035) and a technique for preserving the phenidone derivative together with hydroquinones (see JP-A-52-153437) Can be.

However, the use of the compounds of the present invention in color developers not only act as good preservatives, but also catalyze metal ions such as hydroxylamine sulfate, which has been widely used in the past as a preservative. The fact that the decomposition reaction hardly occurred was not known at all.

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 solution, and at least one of the silver halide emulsion layers of the silver halide photographic light-sensitive material has a general formula [C]. It is characterized by the fact that the processing is carried out by containing the cyan coupler shown, and thus, even when the concentration of the color developing agent in the color developing solution is lowered, not only is the color developing solution excellent in stability over time but also in the color developing solution. , Prevents a decrease in the maximum density of the cyan dye.

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

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

Each of the groups represented by R _{2 to} R ₇ includes those having a substituent.

As R ₆ , an aliphatic group having 1 to 30 carbon atoms, 6 to 30 carbon atoms
Aromatic group, a heterocyclic group having 1 to 30 carbon atoms is preferable,
As R ₄ and R ₅ , a hydrogen atom and the groups described as preferable as R ₆ are preferable.

R ₂ is directly or -NH-, -CO- or -SO
₂ - hydrogen atoms bonded to the NH via an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, -OR _8, -COR _8, −POOR ₁₀ ) ₂ , −POR ₁₀ ) ₂ , -CO ₂ R ₁₀ , -SO ₂ R ₁₀ or -SO ₂ OR ₁₀ (R ₈ , R ₉ and R ₁₀ are the same as defined above for R ₄ , R ₅ and R ₆ , and R ₈ And R ₉ may combine to form a heterocyclic ring.).

R ₇ is preferably an aromatic group having 6 to 30 carbon atoms, R ₇
Representative examples of the substituent represented by are a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carmoyl group, and a sulfamoyl group. , Ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide Groups, aliphatic groups, aliphatic oxycarbonyl groups, and the like. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, and examples thereof include a dioxomethylene group.

Representative examples of the group represented by R ₃ include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carboxamide group, a sulfonamide group, a carbomoyl group, and a sulfamoyl group. Group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, An imide group or the like can be mentioned, and the number of carbon atoms contained in R ₃ is preferably 0 to 30. When m = 2, examples of the cyclic R ₃ include a dioxymethylene group.

When 1 is 1, R ₁ is particularly preferably -CONR ₄ R ₅ and m is 0
Preferably, R ₂ is directly bonded to NH, -COR ₈ , -COOR ₁₀ ,
_{-SO 2 R 10, -CONR 8 R} 9, particularly preferably -SO ₂ NR ₈ R _9, more preferred, -COOR ₁₀ bond directly NH, -COR _8,
—SO ₂ R ₁₀ , with —COOR ₁₀ being most preferred.

Further, those forming multimers of dimers or more via R _{1 to} R ₃ are also included in the present invention.

Specific examples of the coupler represented by the general formula [C] are disclosed in
No. 60-237448, No. 61-153640, No. 61-145557, No. 62
-85242, 48-15529, 50-117422, 52-18
No. 315, No. 52-90932, No. 53-52423, No. 54-48237
No. 54-66129, No. 55-32071, No. 55-65957,
No. 55-105226, No. 56-1938, No. 56-12643, No. 56
No. 27147, No. 56-126632, No. 58-95346 and U.S. Pat. No. 3,488,193, and can be synthesized by the methods described therein.

In order to add the coupler of the present invention to a light-sensitive material, an oil-in-water emulsification dispersion method using a water-insoluble high-boiling organic solvent or an alkali dispersion method adding as an alkaline solution is used depending on the physical properties (eg, solubility) of the coupler. , Latex dispersion method,
Various methods such as a solid dispersion method of directly adding a fine solid can be used.

The amount of the coupler of the present invention is usually 1.0 × 10 ⁻³ mol to 1.0 mol, preferably 5.0 × 10 ⁻³ mol per mol of silver halide.
Mol to 8.0 × 10 ^-1 mol.

Next, typical specific examples of the coupler represented by the general formula [C] are shown, but the invention is not limited thereto.

The color developer used in the present invention preferably further contains at least one compound selected from the compounds represented by the following general formulas [II] and [III].

General formula [II] General formula [III] (In the general formulas [II] and [III], L is an alkylene group,
Cycloalkylene group, a phenylene group, -La-O-L ₈ -O
-L ₈ - or -L ₉ -Z-L ₉ - represent. Where Z is
N-L ₁₀ -R _28, NR ₃₀ or Represents L _{1 to} L ₁₃ each represent an alkylene group. R
_{21 to} R ₃₁ are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt)
Represents However, at least two of R _{21 to} R ₂₄ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof), and at least two of R _{25 to} R ₂₇ are
One is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt). In the general formulas [II] and [III], the alkylene group, cycloalkylene group and phenylene group represented by L, and the alkylene groups represented by L _{1 to} L ₁₃ include those having a substituent.

Next, preferred specific exemplary compounds of the compounds represented by the general formulas [II] and [III] are shown below.

[Example compound] [II-1] Ethylenediaminetetraacetic acid [II-2] Diethylenetriaminepentaacetic acid [II-3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid [II-4] ] Propylenediaminetetraacetic acid [II-5] triethylenetetraminehexaacetic acid [II-6] cyclohexanediaminetetraacetic acid [II-7] 1,2-diaminopropanetetraacetic acid [II-8] 1,3-diaminepropane-2 -All-tetraacetic acid [II-9] Ethyl etherdiaminetetraacetic acid [II-10] Glycoletherdiaminetetraacetic acid [II-11] Ethylenediaminetetrapropionic acid [II-12] Phenylenediaminetetraacetic acid [II-13] Ethylenediaminetetra Disodium acetate [II-14] Ethylenediaminetetraacetate tetra (trimethylammonium) [II-15] Tetrasodium salt of ethylenediaminetetraacetic acid [II-16] Pentasodium salt of diethylenetriaminepentaacetic acid [II-17] Sodium salt of ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetate [II-18] Propylenediaminetetraacetic acid sodium salt [II-19] Ethylenediaminetetramethylenephosphonic acid [II-20] Cyclohexanediaminetetraacetic acid sodium salt [II-21] Diethylenetriaminepentamethylenephosphonic acid [II-22] Cyclohexanediaminetetraacid Methylenephosphonic acid [III-1] nitrilotriacetic acid [III-2] iminodiacetic acid [III-3] nitrilotripropionic acid [III-4] nitrilotrimethylenephosphonic acid [III-5] iminodimethylenephosphonic acid [III-6] nitrilotri Trisodium acetate Among these chelating agents represented by the general formula [II] or [III], compounds particularly preferably used from the viewpoint of the effects of the present invention include (II-1), (II-2),
(II-5), (II-8), (II-19), (III-1) and (III-4).

The addition amount of the chelating agent represented by the general formula [II] or [III] is preferably used in the range of 0.1 to 20 g per color developing solution, and more preferably 0.3 to 20 g for the purpose of the present invention.
A range of 1010 g is particularly preferably used.

The color developing solution used in the present invention further includes the following general formulas [IV], [V], [VI], and [VI].
It is preferable to use at least one compound selected from the compounds represented by I] and the general formula [VII].

General formula [IV] General formula [V] In the formula, R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ and R ₄₆ each represent a hydrogen atom, a halogen atom, a sulfonic acid group, a carbon atom number of 1 to
An alkyl group of 7, -OR ₄₇ , -COOR ₄₈ , Or, it represents a phenyl group. R ₄₇ , R ₄₈ , R ₄₉ and R
₅₀ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, respectively. However, when R ₄₁ and R ₄₂ represent -OH or a hydrogen atom, R ₄₃ is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR ₄₇ , -COOR ₄₈ , Or, it represents a phenyl group.

Examples of the alkyl group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ and R ₄₆ include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a t-butyl group, and a A butyl group, a hydroxymethyl group, a hydroxyethyl group, a methylcarboxylic acid group, a benzyl group, etc., and R ₄₇ , R ₄₈ ,
The alkyl group represented by R ₄₉ and R ₅₀ has the same meaning as described above, and further includes an octyl group.

Further, as the phenyl group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ and R ₄₆ , a phenyl group, a 2-hydroxyphenyl group,
4-aminophenyl group and the like.

Representative specific examples of the compounds represented by the general formulas [IV] and [V] are shown below, but are 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 (IV-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (IV-5) 1,2,3-trihydroxybenzene-5-carboxy-n-butyl ester (IV-6) 5-t-butyl-1,2,3-trihydroxybenzene (IV-7) 1,2-dihydroxybenzene-3,4,5-trisulfonic acid (IV-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 - in-6-sulfonic acid above compounds, particularly preferred compounds used in the present invention include 1,2-dihydroxybenzene-3,5
And disulfonic acid, which can be used as an alkali metal salt such as a sodium salt and a potassium salt.

In the present invention, the compounds represented by the general formulas [IV] and [V] can be used in a range of 5 mg to 20 g, preferably 10 mg to 10 g, more preferably 2 mg per developer.
Good results are obtained with the addition of 0 mg to 3 g.

General formula [VI] (Represented in the general formula _{[VI], R 51, R} 52 and R ₅₃ are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphoric acid group (including salts thereof). However R _51, At least one of R ₅₂ and R ₅₃ is a hydroxyl group, and R ₅₁ , R ₅₂
And only one of _R53 is a carboxylic acid group (including its salt) or a phosphoric acid group (including its salt). n ₁ , n
₂ and n ₃ each represent an integer of 1 to 3; In the general formula [VI], R ₅₁ , R ₅₂ and R ₅₃ are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including a salt thereof).
Or a phosphate group (including a salt thereof), and examples of the salt of a carboxylic acid group and a phosphate group include salts of an alkali metal atom and salts of an alkaline earth metal atom, and preferably sodium, potassium, and the like. And the like. Further, at least one of R ₅₁ , R ₅₂ and R ₅₃ is a hydroxyl group and any one of R ₅₁ , R ₅₂ and R ₅₃
Only one is a carboxylic acid group (including its salt) or a phosphoric acid group (including its salt). R ₅₁ , R ₅₂ and R ₅₃ are each preferably selected from a hydroxyl group, a carboxylic acid group (including its salt) or a phosphoric acid group (including its salt).
n ₁ , n ₂ and ₃ each represent an integer of 1 to 3.

Hereinafter, typical specific examples of the compound represented by the general formula [VI] will be described, but the invention is not limited thereto.

General formula [VI] In the general formula [VII], R ₅₄ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₅₅ and R ₅₆ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, and a benzyl group, respectively. Or expression It is shown, n of the formula represents the integer of 1 to 6, X 'and Z ₀ are each a hydrogen atom, an alkyl group or hydroxyalkyl group having 2 to 6 carbon atoms having 1 to 6 carbon atoms.

R ₅₄ is preferably a hydroxyalkyl group having 2 to 4 carbon atoms, and R ₅₅ and R ₅₆ are each preferably an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms.

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

Ethanolamine, diethanolamine, triethanolamine, di-isopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-
Dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1-propanol, 3-dimethylamino-
1-propanol, isopropylaminoethanol, 3
-Amino-1-propanol, 2 amino-2-methyl-
1,3-propanediol, ethylenediaminetetraisopropanol, benzyldiethanolamine, 2-amino-2- (hydroxymethyl) -1,3-propanediol.

These compounds represented by the general formulas [VI] and [VII] are preferably used in the range of 3 g to 100 g, more preferably 6 g to 50 g per color developing solution in view of the effects of the present invention. Used in

General formula [VIII] (Wherein, R ₅₇ represents an alkylene group having 1 to 6 carbon atoms atoms, R ₅₈ represents an alkyl group, n. Represents an integer of 500 to 20,000) carbon atoms 1 represented by the above R ₅₇ The alkylene group of 6 may be linear or branched, and preferably has 2 to 2 carbon atoms.
4, alkylene groups such as ethylene group, propylene group,
Butene group, isobutene group, dimethylethylene group, ethylethylene group and the like. The alkyl group represented by R ₅₈ is preferably an alkyl group having 1 to 4 carbon atoms,
For example, methyl group, ethyl group, propyl group and the like,
Further, those having a substituent (for example, a hydroxyl group) are also included. n represents the number of repeating units in the polymer chain, and represents an integer of 500 to 20,000, preferably 500 to 2,
It is an integer of 000. Poly (ethylene imine) wherein R ₅₇ is an ethylene group is most preferred for the purposes of the present invention.

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

Exemplary compound PAI-1 poly (ethyleneimine) PAI-2 poly (propyleneimine) PAI-3 poly (butenimine) PAI-4 poly (isobutenimine) PAI-5 poly (N-methylethyleneimine) PAI-6 poly (N -Β-hydroxyethylethyleneimine) PAI-7 poly (2,2-dimethylethyleneimine) PAI-8 poly (2-ethylethyleneimine) PAI-9 poly (2-methylethyleneimine) poly (alkyleneimine) In the color developing solution, it can be used in any amount that can achieve the object of the present invention, but generally 0.1 to 500 g per color developing solution is preferred,
More preferably, it is used in the range of 0.5 g to 300 g.

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

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

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material and the skin as compared with a baraphenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage of being less susceptible to fogging, but in particular, the object of the present invention can be efficiently achieved by combining with the compound represented by the general formula [I] in the present invention.

Examples of the water-soluble group include those having at least one amino group on a p-phenylenediamine-based compound or a benzene nucleus. Specific examples of the water-soluble group include-(CH ₂ )
_{n -CH 2 OH, - (CH} 2) mNHSO 2 - (CH 2) nCH 3, - (CH 2)
_{mO- (CH 2) n-CH} 3, - (CH 2 CH 2 O) nCmH 2 m + 1 (m and n each represent an integer of 0 or more.), - COOH group,
—SO ₃ H groups and the like are preferred.

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

Illustrative color developing agents Among the color developing agents exemplified above, (A-1) is particularly preferred for use in the invention.

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

The color developing agent having a water-soluble group used in the present invention is usually preferably used in an amount of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developing solution, but from the viewpoint of rapid processing, the color developing agent is preferably used. The range is more preferably 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liquid.

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

Further, instead of using the above color developing agent in the color developing solution, a color developing agent can be added to the light-sensitive material. In this case, the color developing agent used is, for example, a dye precursor. A typical dye precursor is disclosed in
Those described in JP-A Nos. 58-65429 and 58-24137 are used.

In the present invention, when a triazylstilbene-based fluorescent whitening agent represented by the following general formula [IX] is used for the color developing solution according to the present invention, gamma of a cyan dye is stabilized, and color contamination is further reduced, which is preferable.

General formula [IX] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an amino group,
Represents an alkylamino group. M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specific examples include the following compounds, but are not limited thereto.

These triazylstilbene-based brighteners are preferably used in the range of 0.2 to 6 g, more preferably 0.4 to 3 g, per color developing solution used in the present invention.

The color developing solution of the present invention contains, in addition to the above components, commonly used developing agents such as alkali agents, various salts for increasing ionic strength, inorganic and organic antifoggants, and development accelerators. Can be.

In particular, as a development accelerator, poorly water-soluble organic solvents represented by benzyl alcohol described in U.S. Pat.No. 2,304,925 are apt to generate tar and have a poor dissolution rate. There is also a limit to the wastewater treatment, and the wastewater treatment has problems such as a great deal of labor and cost. Therefore, it is preferable to reduce or eliminate the amount of the wastewater as much as possible.

Further, the color developing solution of the present invention may contain, as necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, JP-B-44-9509. Can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. In addition, if necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (a so-called DIR coupler), a development inhibitor releasing compound, or the like can be added.

Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

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

In the present invention, the above color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably from 9.5 to 13.0, more preferably from 9.8 to 13.0.

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the faster the processing can be performed in a shorter time, which is preferable. However, it is preferable that the temperature is not so high from the viewpoint of image storage stability.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but it is preferably within 2 minutes for speeding up, and more preferably in the range of 30 seconds to 1 minute and 30 seconds.

In the present invention, any system using a color developing solution containing the compound of the present invention represented by the general formula [I] can be applied. For example, a single bath treatment and other various methods such as treatment Various processing methods such as a spray method in which the liquid is sprayed, a web method by contact with a carrier impregnated with the processing liquid, and a developing method using a viscous processing liquid can be used, but the processing step is substantially coloration. It consists of steps of development, bleach-fix, washing with water or a stabilization process instead of this.

In the bleach-fixing step, a bleaching step and a fixing step may be separately provided, or a bleach-fixing bath in which bleaching and fixing are performed in a single bath may be used.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is obtained by coordinating a metal ion such as iron, cobalt and copper with an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid. The most preferred organic acids used to form such metal complexes of organic acids 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 are as follows.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] silohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetra acetic acid [10] Glycol ether diamine tetra acetic acid [11] Ethylene diamine tetrapropionic acid [12] Phenylenediamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetic acid tetra (trimethyl ammonium) salt [15] ] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetate sodium salt [18] Propylenediaminetetraacetate sodium salt [19] Nitriloacetate sodium salt [20] Cyclohexanediaminetetraacetate sodium salt 20-2
Use at 50g /. To the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. A bleach-fixing solution comprising a composition in which a small amount of a halide such as ammonium bromide is added to the above-mentioned silver halide fixing agent, and an iron (III) complex salt of ethylenediaminetetraacetate;
Conversely, a bleach-fixing solution having a composition to which a large amount of a halide such as ammonium bromide is added, and a composition comprising a combination of an iron (III) complex salt of ethylenediaminetetraacetate and a large amount of a halide such as ammonium bromide. The special bleach-fixing solution may be used.

As the silver halide fixing agent contained in the bleach-fixing solution, a compound which reacts with silver halide to form a water-soluble complex salt such as thiosulfate, thiocyanate, thioic acid, etc. Urea, thioether and the like are typical examples. These fixing agents are used in an amount in a range that can dissolve 5 g / or more, but generally, 70 g to 250 g /
Used in.

The bleach-fixing solution may contain various pH buffers alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be added. In addition, various preservatives, organic chelating agents or stabilizers, organic solvents and the like can be appropriately contained.

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

The pH of the bleach-fix solution is used at 4.0 or higher.
Used at H5.0 or more and pH 9.5 or less, desirably pH 6.0 or more and pH
Used below 8.5, with a further preferred pH of 6.5
The processing is performed in the range from 8.5 to 8.5. The processing temperature is 80 ° C. or less and 3 ° C. or more, preferably 5 ° C., higher than the temperature of the processing solution in the color developing tank.
Although it is used at a lower temperature, it is desirably used at a temperature of 55 ° C. or less while suppressing evaporation and the like.

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

Hereinafter, the washing stabilizing solution applicable to the present invention will be described.

The pH of the washing alternative stabilizer applicable to the present invention is preferably in the range of 5.5 to 10.0, and more preferably pH 6.3 to 9.5.
And particularly preferably in the range of pH 7.0 to 9.0. As the pH adjuster that can be contained in the washing-substitute stable liquid applicable to the present invention, any commonly known alkali agent or acid agent can be used.

The treatment temperature of the stabilization treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ℃ to 45 ℃ is good. The processing time is also preferably shorter from the viewpoint of rapid processing, but usually 20 seconds to 10 minutes,
The time is most preferably 1 minute to 3 minutes. In the case of the multiple tank stabilization treatment, it is preferable that the treatment is performed in a shorter time in the former tank and the treatment time is longer in the latter tank. In particular, it is desirable to sequentially perform the treatment with a treatment time that is 20% to 50% longer than that of the preceding tank. No water washing treatment is required after the stabilization treatment applicable to the present invention, but rinsing by small amount of water washing and surface washing in an extremely short time can be arbitrarily performed as necessary.

In the case of using a multi-tank countercurrent method, it is preferable to supply a post-bath bath and overflow from a pre-bath, when a stabilizing treatment step applicable to the present invention is supplied in a stabilizing treatment step using a multi-tank countercurrent method. Of course, it can also be processed in a single tank. As a method for adding the above compound, the above compound and other additives are added to the stabilizing tank as a concentrated liquid, or the above-mentioned compound and other additives are added to the washing alternative stabilizing liquid supplied to the stabilizing tank. Although there are various methods such as a method of using the liquid as a supply liquid, the liquid may be added by any addition method.

As described above, in the present invention, the treatment with the stabilizing solution instead of the washing process refers to a stabilizing process in which the stabilizing process is performed immediately after the process with the bleach-fixing solution and the washing process is not substantially performed. The processing solution used for the washing is called a washing-substituting stabilizer, and the processing bath is called a stabilizing bath or a stabilizing bath.

The stabilization tank in the stabilization treatment applicable to the present invention is 1 to
When the number of tanks is five, the effect of the present invention is large, particularly preferably one to three tanks, and preferably at most nine tanks or less.

Crystal structure of the silver halide grains used in the present invention,
It may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and the outside are different. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (JP-A
No. 58-113934 and Japanese Patent Application No. 59-170070).

The silver halide emulsion used in the present invention is chemically sensitized with active gelatin, a sulfur sensitizer, a selenium sensitizer, a reduction sensitizer, a noble metal sensitizer, or the like alone or in combination with another as appropriate. Is also good.

The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and before, during or after the chemical ripening, a nitrogen-containing heteroatom having at least one hydroxytetrazaindene and a mercapto group. At least one kind of a ring compound may be contained.

The silver halide used in the present invention may contain an appropriate sensitizing dye in an amount of 5 × 10 ⁻⁸ 3 × 10 ⁻³ mol per mol of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. It may be added for optical sensitization.

To the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention, a dye (AI dye) capable of decolorizing with a water-soluble or color developing solution can be added. Examples of the AI dye include an oxonol dye and a hemioxonol. Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes,
Hemioxonol dyes and merocyanine dyes are useful.

These AI dyes are generally used in two moles per mole of silver in the emulsion layer.
It is preferable to use from 10 ^{-3 to} 5 x 10 ^-1 mol, more preferably from 1 x 10 ^-2 to 1 x 10 ^-1 mol.

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

The yellow coupler and the magenta coupler that can be used in the present invention can be used without any particular limitation. These couplers may be so-called two-equivalent type or four-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler in combination with these couplers.

As photographic magenta couplers, compounds such as pyrazolone-based compounds, pyrazolinobenzimidazole-based compounds and indazolone-based compounds are used. Magenta couplers represented by the following general formula [MI] improve processing stability and color reproducibility of images. It is preferable from the viewpoint of.

General formula [MI] (In the formula, Z ′ represents a group of nonmetal atoms necessary to form a nitrogen-containing heterocyclic ring, and the ring formed by Z ′ may have a substituent.

X ₀ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

R represents a hydrogen atom or a substituent. In the general formula [MI], the substituent represented by R is not particularly limited, but is typically a group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Other examples include a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues And the like.

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

As the aryl group represented by R, a phenyl group is preferable.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X ₀ include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom and the like), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alcoholoxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ¹ has the same meaning as R, Z ″ has the same meaning as Z ′, and R ² and R ³ each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) But preferably a halogen atom, especially a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z ′ or Z ″ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring, and the like. Things.

The compound represented by the general formula [MI] is more specifically represented by, for example, the following general formulas [M-II] to [M-VII].

General formula [M-VII] In the general formulas [M-II] to [M-VII], R ₁ ′ to R _1
8 'and X ₀ have the same meanings as R and X _0.

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], those particularly preferred are those represented by the general formula [MI]
I] is a magenta coupler.

Substituents which the ring formed by Z ′ in the general formula [MI] may have, and general formulas [M-II] to [M-
R ₂ ′ to R ₈ ′ in the formula [VI]
Those represented by I] are preferred.

The general formula ^{[M-VIII] -R 4 -SO} 2 -R ⁵ Formula R ⁴ is an alkylene group, R ⁵ represents an alkylene group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ⁴ preferably has at least 2 carbon atoms in the straight chain portion, more preferably 3 to 6, and may be straight chain or branched.

The cycloalkyl group represented by R ⁵ is preferably a 5- or 6-membered cycloalkyl group.

When used for positive image formation, the most preferred substituents R and R ₁ ′ on the heterocycle are those represented by the following general formula [M-
IX].

General formula [M-IX] In the formula, R ₉ ′, R ₁₀ ′ and R ₁₁ ′ have the same meanings as R described above.

Further, two of R ₉ ′, R ₁₀ ′ and R ₁₁ ′, for example, R ₉ ′
And R ₁₀ ′ may combine to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle),
Further, R ₁₁ ′ may be bonded to the ring to form an organic hydrocarbon compound residue.

Among the general formulas [M-IX], preferred are (i)
When at least two of R ₉ ′ to R ₁₁ ′ are an alkyl group, (ii) one of R ₉ ′ to R ₁₁ ′, for example, R ₁₁ ′ is a hydrogen atom, and the other two R ₉ ′ to R ₁₁ ′ are a hydrogen atom. And R ₁₀ 'combine to form a cycloalkyl with the root carbon atom.

Furthermore, a preferable case of (i) is a case where two of R ₉ ′ to R ₁₁ ′ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

When used for forming a negative image, the most preferable substituents R and R ₁ 'on the heterocyclic ring are those represented by the following general formula [M
-X].

General formula [MX] R ₁₂ '-CH _2- wherein R ₁₂ ' has the same meaning as R described above.

Preferred as R ₁₂ 'is a hydrogen atom or an alkyl group.

 Hereinafter, typical specific examples of the compound according to the present invention will be shown.

In addition to the typical specific examples of the compound represented by the general formula [MI] according to the present invention, specific examples of the compound according to the present invention are described in Japanese Patent Application No. 61-9791, pp. 66-122. Among the compounds described on the page, No. 1-4, 6, 8, 17, 19, 24, 2
Compounds represented by 6 to 43,45 to 59,61 to 104,106 to 121,123 to 162,164 to 223 can be exemplified. Further, Japanese Patent Application No. 61
No. 288370, pages 20 to 32 and Japanese Patent Application No. 62-6531
The compounds described in the specification of JP-A No. 4, page 16 to page 30 can also be mentioned.

In addition, the coupler is used in the Journal of the Chemical Societe
y), Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, and JP-A-58-42045.
Nos. 59-162548, 59-171956, 60-33552
Nos. 607-43659, 60-172,982 and 60-190779
No. can be synthesized with reference to the symbols.

The above coupler is usually used in an amount of 1 × 10 ^-3 per mol of silver halide.
It can be used in the range of 1 mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol.

Further, the coupler of the present invention can be used in combination with another type of magenta coupler.

Further, a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391 in which a dye flows out into a processing solution by reaction with an oxidized form of a developing agent can also be used.

As a photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide-type yellow coupler generally used widely,
A pivaloylacetanilide type yellow coupler can be used. Further, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction are also advantageously used.

The amount of the diffusion-resistant coupler used in the present invention is generally 0.05 to 0.05 mol per mol of silver in the photosensitive silver halide emulsion layer.
~ 2.0 mol.

In the present invention, a DIR compound is preferably used in addition to the above-mentioned diffusion-resistant coupler.

Further, in addition to the DIR compound, a compound that releases a development inhibitor upon development is also included in the present invention.

Further, when reacted with an oxidized form of a color developing agent as described in JP-A-54-145135, JP-A-56-114946 and JP-A-57-154234, the mother nucleus forms a dye or a colorless compound. On the other hand, a so-called timing DIR compound in which the released timing group releases a development inhibitor by an intramolecular nucleophilic substitution reaction or elimination reaction is also included in the present invention.

In addition, the timing group as described above is present in a coupler nucleus which forms a completely diffusible dye when reacted with an oxidized form of a color developing agent described in JP-A-58-160954 and JP-A-58-162949. Includes bound timing DIR compounds.

The amount of the DIR compound contained in the photosensitive material is preferably in the range of 1 × 10 ⁻⁴ mol to 10 × 10 ⁻³ mol per mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure No. 17643 , A plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, casein and the like. Proteins, hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any one such as a synthetic hydrophilic polymer of a single or copolymer such as polyacrylamide is included.

As the support of the silver halide color photographic light-sensitive material used in the present invention, any support generally used depending on the purpose is used, and it can be coated by a usual method.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer may be appropriately used as constituent layers. It can be used in combination. In these constituent layers, a hydrophilic colloid which can be used in the above-mentioned emulsion layer can be similarly used as a binder, and various layers which can be contained in the above-mentioned emulsion layer can be contained in the layer. Photographic additives.

In the method for processing a silver halide color photographic light-sensitive material of the present invention,
Color papers, color negative films, color positive films, color reversal films for slides, color reversal films for movies, color reversal films for TV, as long as the photosensitive material contains a coupler in the photosensitive material and is processed by the so-called internal development method And any silver halide color photographic light-sensitive material such as reversal color paper.

[Effects of the Invention] As described 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 in a dye image and hardening of a shoulder portion. Further, it is possible to provide a method for processing a silver halide color photographic light-sensitive material having a small maximum fluctuation of the cyan dye and excellent processing stability.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Color developing solutions Nos. 1 to 6 having the following compositions were prepared.

4 ppm of ferric ion and 2 ppm of copper ion in the above color developing solution
(Dissolve and add FeCl ₃ and CuSO ₄ .6H ₂ O, respectively) and store at 33 ° C. in a glass container with an opening ratio of 150 cm ² / (one color developing solution has an air contact area of 150 cm ² ) While the concentration of the color developing agent in the color developing solution was analyzed by the cerium sulfate method, the number of days until the concentration of the color developing agent became 0 was determined as the life of the color developing solution.

 The results are shown in Table 1.

As is clear from the results in Table 1, one of the conventional preservatives
In a color developer using hydroxylamine sulfate, the life of the color developer when metal ions are mixed is short. On the other hand, the life of each of the color developing solutions using the compound of the present invention is greatly extended.

Reference Example 1 On a paper support laminated with polyethylene, the following layers were sequentially applied from the support side to prepare a silver halide photosensitive material.

Layer 1 ...... 1.20g / m ² of gelatin, 0.40 g / m ² (in terms of silver, hereinafter the same) blue-sensitive silver halide emulsion (AgBr of: AgCl = 0.5: 99.
5) and 1.0 dissolved in 0.55 g / m ² dioctyl phthalate
A layer containing the following yellow coupler (YR) in an amount of × 10 ^-3 mol g / m ² .

Layer 2: an intermediate layer made of 0.70 g / m ² gelatin.

Layer 3 ...... 1.20g / m ² of gelatin, 0.22 g / m ² green-sensitive silver halide emulsion (AgBr: AgCl = 0.5: 99.5 ) 1.0 was dissolved in dioctyl phthalate and 0.30g / m ² × 10 ^-3 Layer containing the following magenta coupler (MR) in an amount of mol g / m ² .

Layer 4: an intermediate layer made of 0.70 g / m ² gelatin.

Layer 5 ...... 1.20g / m ² of gelatin, of 0.28 g / m ² red-sensitive silver halide emulsion (AgBr: AgCl = 0.5: 99.5 ) and 0.30 g / m ² of 1.90 × dissolved in dibutyl phthalate ^10-3 Layer containing mol g / m ² of the exemplary cyan coupler (C-29).

Layer 6: Layer containing 1.0 g / m ² of gelatin and 0.32 g / m ² of Tinuvin 328 (an ultraviolet absorber manufactured by Ciba Geigy) dissolved in 0.25 g / m ² of dioctyl phthalate.

Layer 7: Layer containing 0.48 g / m ² of gelatin. In addition, sodium 2,4-dichloro-6-hydroxy-s-triazine was used as a hardening agent in layers 2, 4 and 7, respectively.
It was added so as to be 0.017 g per g.

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

Processing step Processing temperature Processing time (1) Color development 35 ° C 45 seconds (2) Bleaching and fixing 35 ° C 45 seconds (3) Rinse 30 ° C 90 seconds (4) Dry 60-80 ° C 60 seconds No. 7 to 13 having the following composition
belongs to.

The bleach-fix solution used had the following composition.

Using the optical densitometer PDA-65 (manufactured by Konishi Roku Kogyo Co., Ltd.), the sample after the treatment was used to measure the reflection density of the cyan dye, to prepare a sensitometric curve and to measure the minimum reflection density of the cyan dye. . Next, the slope (gamma value) from the density point of the reflection density of the cyan dye of 0.8 to the density point of the reflection density of 1.8 was calculated.

The same metal ions as in Example 1 were added to the color developing solution after the processing, and stored at 35 ° C. for one week. After storage, the same processing was repeated, the lowest reflection density of the cyan dye was measured, and the cyan gamma value was calculated.

The difference between the minimum reflection density of the cyan dye before and after the storage and the difference between the cyan gamma values were determined and are shown in Table 2.

As is clear from Table 2, in the case of processing with a color developing solution using hydroxylamine sulfate which is one of the conventional preservatives, the fog density of cyan and the gamma of cyan after storage are significantly increased. . On the other hand, it can be seen that all the compounds treated with the color developer using the compound of Reference Example as a preservative are good.

Reference Example 2 The sample used in Reference Example 1 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 manner as in Reference Example 1.

However, here, the preservative and the amount of addition in the color developing solution were as described in Table 3.

 The maximum density of the cyan dye after the treatment is shown in Table 3.

As is clear from Table 3, the maximum concentration of cyan was obtained stably and the minimum concentration was low by using the preservative of the reference example and the cyan coupler of the present invention. It can be seen that the use of the preservatives of Reference Exception greatly reduces the maximum density, and the use of couplers of Reference Exception affects the maximum density and the minimum density of cyan, which results in undesirable results.

Example 2 From the support side, a black colloidal silver antihalation layer,
A red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity silver halide emulsion layer on the outermost side of the blue-sensitive silver halide emulsion layer To prepare a silver halide photosensitive material sample. However, the coated silver amount was 55 mg / 100 cm ² and the dry film thickness was 23 μm.

Layer 1: A dispersion of 0.8 g of black colloidal silver exhibiting high absorbency for light in the wavelength range of 400 to 700 nm by reducing with hydroquinone using silver nitrate as a reducing agent was prepared with 3 g of gelatin to form an antihalation layer.

Layer 2: Intermediate layer made of gelatin.

Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (Ag I; 7 mol%), 1.6 g of gelatin and 0.85 g of 1
-Hydroxy-4- (β-methoxyethylaminocarbonylmethoxy) -N- [δ- (2,4-di-t-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-
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter, referred to as TCP) in which naphthamide disodium (hereinafter, referred to as colored cyan coupler (CC-1)) is dissolved. .

Layer 4: 1.1 g of a high-sensitivity red-sensitive silver iodobromide emulsion (Ag I; 6 mol%), 1.2 g of gelatin, 0.25 g of a cyan coupler (C-0), and 0.020 g of a colored cyan coupler (CC- A high-sensitivity red-sensitive silver halide emulsion layer containing 0.17 g of TCP dissolved in 1).

Layer 5: 0.04 g of 0.07 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as a pollution inhibitor (HQ-1)) dissolved therein
An intermediate layer containing g of dibutyl phthalate (hereinafter referred to as DBP) and 1.2 g of gelatin.

Layer 6: 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (Ag I: 6 mol%), 1.7 g of gelatin and 0.32 g of 1
-(2,4,6-trichlorophenyl) -3- [3- (2,4-
Di-t-amylphenoxyacetamide) benzeneamide] -5-pyrazolone (hereinafter referred to as magenta coupler (M-
1)), 0.20 g of 4,4-methylenebis-11- (2,4,
6-trichlorophenyl) -3- [3- (2,4-di-t-
Amylphenoxyacetamide) benzeneamide] -5
-Pyrazolone (hereinafter referred to as magenta coupler (M-2)), 0.066 g of 1- (2,4,6-trichlorophenyl)-
Dissolves three types of couplers, 4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) Low-sensitivity green-sensitive silver halide emulsion layer containing 0.3 g of TCP.

Layer 7: 1.5 g of a high-sensitivity green photosensitive silver iodobromide emulsion (Ag I; 8 mol%), 1.9 g of gelatin, 0.10 g of a magenta coupler (M-1), and 0.098 g of a magenta coupler (M-2) ), 0.049g colored magenta coupler (CM-
A high-sensitivity green-sensitive silver halide emulsion layer containing 0.12 g of TCP dissolved in 1).

Layer 8: 0.2 g of yellow colloidal silver, 0.2 g of stain inhibitor (HQ-
Yellow filter layer containing 0.11 g of DBP dissolved in 1) and 2.1 g of gelatin.

Layer 9: 0.95 g of a low-sensitivity blue-sensitive silver iodobromide emulsion (Ag I; 7 mol%), 1.9 g of gelatin and 1.84 g of α
-[4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-
Low-sensitivity blue containing 0.93 g of DBP in which 2-chloro-5- [γ- (2,4-di-t-amylphenoxy) butanamide] acetanilide (hereinafter referred to as yellow coupler (Y-1)) is dissolved. Photosensitive silver halide emulsion layer.

Layer 10: 1.2 g of a high-sensitivity monodisperse blue-sensitive silver iodobromide emulsion (Ag
I; 6 mol%), a high-sensitivity blue-sensitive silver halide emulsion layer containing 2.0 g of gelatin and 0.23 g of DBP in which 0.46 g of a yellow coupler (Y-1) is dissolved.

Layer 11: Second protective layer made of gelatin.

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

In the above sample, the cyan couplers (C-0) of layers 3 and 4 were changed to the cyan couplers C-20, C-35, and C-46 (equimolar amounts) of the present invention as shown in Table 4 in the same manner. The experiment was performed.

These samples were cut into pieces, subjected to wedge-shaped exposure according to a conventional method, and processed (hereinafter referred to as manual processing) using a piece processing apparatus according to the following process.

Processing Step Processing Temperature (° C) Bath Processing Time 1. Color development 37.8 1 3 minutes 15 seconds 2. Bleaching 38 1 3 minutes 15 seconds 3. Fixed 35-38 13 minutes 15 seconds 4. Rinse bath 30-34 2 2 minutes 5. Stability 30-34 1 1 minute 5 seconds 6. Drying 1 2 minutes 10 seconds The following color developing solution, bleaching solution, fixing solution, bath solution and stabilizing solution were used.

Using the optical densitometer PDA-65 (manufactured by Konishi Roku Kogyo Co., Ltd.), measure the transmission density of cyan dye on the processed sample, create a sensitometric curve, and measure the minimum transmission density of cyan dye. did. Next, the slope (gamma value) from the density point of the transmission density (fog + 0.3) of the cyan dye to the density point of the transmission density (fog + 1.8) was calculated.

The same metal ions as in Example 1 were added to the color developing solution after the processing, and stored at 38 ° C. for one week. After storage, the same processing was repeated, the lowest density of the cyan dye was measured, and the cyan gamma value was calculated.

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

As is evident from Table 4, when a preservative or a cyan coupler other than the present invention was used, the fog concentration and gamma of cyan were significantly increased, whereas the hydroxylamine derivative of the present invention was significantly increased. (I-1, I-18, I-21)
It is clear that the combination of the coupler of the present invention (C-20, C-35, C-46) suppresses both fog and gamma increase, and gives good results.

Example 3 A sample similar to that of Example 2 was prepared and processed except that the magenta coupler (M-1) used in Example 2 was changed as shown in Table 5 and the cyan coupler was changed to C-20. Was. However, magenta as well as cyan fog density fluctuation and cyan gamma value fluctuation were measured in the same manner. The results are shown in Table 5.

As is clear from Table 5, the stability of the magenta dye image was improved by using the exemplified compounds (1), (3), (7) and (14) as the magenta coupler in the preservative of the present invention. In addition, a surprising improvement effect of reducing the gamma variation of cyan by 0.04-0.05 was also obtained.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-3532 (JP, A) JP-A-62-92952 (JP, A) JP-A-63-4234 (JP, A) JP-A-58-58 17439 (JP, A) JP-A-59-184341 (JP, A) JP-A-61-179438 (JP, A) US Patent 3,746,544 (US, A) US Patent 4,267,716 (US, A)

Claims (2)

(57) [Claims] An imagewise exposed light having at least one silver halide emulsion layer containing a compound represented by the following general formula [C] on a support, provided that the chlorine content in the total halogen is as follows: Except for a silver halide color photographic light-sensitive material having an emulsion layer containing 50 mol% or more of silver halide, a silver halide color photographic light-sensitive material was prepared by coloring a compound containing a compound represented by the following general formula [I]. A method for processing a silver halide color photographic material, wherein the processing is performed in a processing step including at least a step using a developer. General formula [C] (Wherein R ₁ is -CONR ₄ R ₅ , -NHCOR ₄ , -NHCOOR ₆ , -NHSO
₂ R ₆ , —NHCONR ₄ R ₅ or —NHSO ₂ NR ₄ R ₅ , R ₂ is a monovalent group, R ₃ is a substituent, X is a hydrogen atom or an oxidized aromatic primary amine developer a group that splits off by reaction with, 1 0 or 1, m is an integer of 0 to 3, R ₄ and R ₅ are each a hydrogen atom, an aromatic group, an aliphatic group or Hetoro ring group, R ₆ represents an aromatic group, aliphatic group or heterocyclic group, and when m is 2 or 3, those R ₃ are each identical, including those different and bonded to each other to form a ring, and, R ₄ And R ₅ , R ₂ and R ₃ , R ₂
And X are combined to form a ring. However, 1 is 0
In the formula, m is 0, R ₁ is —CONHR ₇ , and R ₇ represents an aromatic group. ) General formula [I] (Wherein, R ₁₁ and R ₁₂ each represent an alkyl group or a hydrogen atom, provided that R ₁₁ and R ₁₂ are not both hydrogen atoms at the same time, and that R ₁₁ and R ₁₂ form a ring including.) 2. The color developing solution according to claim 1, wherein said color developing solution contains at least one compound selected from compounds represented by the following general formulas [II] and [III]. A method for processing a silver halide color photographic light-sensitive material as described above. General formula [II] General formula [III] (General formula [II] and [III] in, L is an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -O-L ₈ -O-
L ₈ - or -L ₉ -Z-L ₉ - represents a. Where Z is N-
L ₁₀ −R ₂₈ , NR ₃₀ or Represents L _{1 to} L ₁₃ each represent an alkylene group. R _{21 to} R ₃₁ each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt). Provided that at least two of R _{21 to} R ₂₄ are carboxylic acid groups (including their salts) or phosphonic acid groups (including their salts)
And at least two of R _{25 to} R ₂₇ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof). )