JPS62255944A - Liquid color-developer and method for processing silver halide color photographic sensitive material using the same - Google Patents

Abstract

PURPOSE:To obtain the titled developer having a good storage stability and less tendency for generating a color stain by incorporating diethyl hydroxyamine, etc., and poly(alkyleneimine) to a processing solution for the color processing of the photosensitive material. CONSTITUTION:The liquid color-developer contains at least one of the compd. selected from the group comprising diethyl hydroxyamine, dimethyl hydroxyamine and poly(alkyleneimine) shown by the formula where R1 is 1-6C alkylene group, R2 is alkyl group, (n) is an integer of 500-20,000. The poly(alkyleneimine) is exemplified by poly(ethyleneimine), poly(propyleneimine) and poly(N-methylethyleneimine), etc. Thus, by incorporating poly(alkyleneimine) together with diethylhydroxyamine or dimethylhydroxyamine to the liquid color- developer, the developer having the good storage stability and less tendency for generating the color stain is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials and a method for processing silver halide color photographic light-sensitive materials using the developer, and in particular, to a method for processing silver halide color photographic light-sensitive materials. The present invention relates to a color developer with improved properties and color staining, and a method for processing silver halide color photographic materials using the color developer.

[Background of the Invention] Processing of silver halide color photographic materials basically consists of two steps: color development and desilvering, and desilvering consists of a bleaching and fixing step or a bleach-fixing step.

In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

In color development, exposed silver halide is reduced to silver, and at the same time, an oxidized aromatic primary amine color developing agent, typically a p-phenylenediamine type developing agent, reacts with a coupler to form a dye. do. In this process,
Halogen ions generated by reduction of silver halide are eluted and accumulated in the developer. In addition, components such as inhibitors contained in silver halide photographic light-sensitive materials are also eluted into the color developing solution and are multiplied by N. In the 1A silver process, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble tl salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously.

In color developing solutions, development inhibiting substances accumulate when silver halide color photographic light-sensitive materials are developed as described above, but -5 color developing agents, benzyl alcohol, etc. are consumed or accumulated in photographic light-sensitive materials. brought out,
The 1 degree of those components is decreasing. Therefore, in the development processing method in which silver halide color photographic light-sensitive materials are continuously processed using an automatic processor, the components of the color developer are kept within a certain concentration range in order to avoid changes in the development finish characteristics due to changes in the concentration of the components. A means is needed to maintain it. As such a method, a method of replenishing a replenisher is usually used to supplement the missing components and dilute the unnecessary increased components.

The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow liquid, developer regeneration methods using ion exchange resin method or electrodialysis method, concentrated low replenishment method,
Another proposed method is to add a regenerant to the overflow liquid and use it again as a replenisher. Among these, the concentrated low replenishment method does not particularly require new equipment and is easy to manage, so it can be said to be an extremely suitable method for small-scale laboratories such as minilabs.

On the other hand, in ordinary color developing solutions, sulfite or sulfite and hydroxylamine are used as preservatives to prevent oxidation of aromatic primary amine color developing agents, such as p-phenylenediamine-based developing agents. A water-soluble salt is added.

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, the coexisting small m
It decomposes under the catalytic action of metal ions, especially iron ions, which not only reduces the preservation effect, but also generates ammonia when decomposed, which can cause fog and stains on color photographic materials, and It is known that abnormalities in characteristics, especially hard contrast in the shoulder area, occur and reduce processing stability.

These metal ions, especially iron ions, are introduced into the color developer by splashing, conveyance leaders, belts, hangers for hanging the film, etc., and ferric salts of organic acids are usually introduced into the color developer as a bleaching agent. This is caused by so-called back contamination, where the bleach and bleach-fix solutions used are brought in.

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 hydroxyalkylidene-diphosphonic acid sequestering agent and a lithium salt in combination, as described in U.S. Pat. No. 3,839,045a,
Patent No. 3.746.544? technology using a polyhydroxy compound and an aminopolycarboxylic acid sequestering agent in combination, as described in U.S. Patent No. 4,264,7
Examples include the technique of using a polyhydroxy compound and an aminopolyphosphonic acid gold ion sequestering agent in combination, as described in Specification No. 16, but even these techniques have not been able to solve the above problems. is the current situation.

This reduction in process stability due to hydroxylamine salts is further amplified in low replenishment processes.

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 due to decomposition of the hydroxylamine salt and 141 formation of the shoulders become even more noticeable.

Furthermore, under these circumstances, there was almost no engraving in the conventional multi-replenishment process. For example, the surrounding metals contained in the reagent,
In particular, it has become clear that copper ions accelerate the decomposition of hydroxylamine salts. For this copper ion,
It has been found that it is difficult to render the substance harmless by using conventional chelating agents.

Therefore, the present inventors investigated various preservatives that do not have the drawback of hydroxylamine salts, such as reduced processing stability, and have high preservative ability, and found that diethylhydroxylamine is a particularly excellent preservative. and dimethylhydroxylamine. However, as a result of further studies, the present inventors found that when diethylhydroxylamine and/or dimethylhydroxylamine is added to a color developer, there is a problem in that the color developer is colored yellow. It has been found that this coloring stains containers for storing color developing solutions, processing tanks of automatic processors, replenisher tanks, vibrators, and even photosensitive materials.

[Object of the Invention] Therefore, the first object of the present invention is to provide a color developing solution which has excellent storage stability and has little brown staining.

A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which is excellent in fogging and high contrast in shoulder areas and causes less color staining of the light-sensitive material, by using the above-mentioned color developing solution. It is in.

[Structure of the Invention] The first object of the present invention is achieved by a color developing solution containing poly(alkyleneimine) and at least one selected from diethylhydroxylamine and dimethylhydroxylamine, and the second object is , in a method for processing a silver halide color photographic material, which performs a treatment including at least a color development step after imagewise exposure of the silver halide color photographic material, wherein the color developer used in the color development step is diethyl hydroxyl. This was achieved by a method for processing a silver halide color photographic material containing at least one selected from amine and dimethylhydroxylamine and poly(alkyleneimine).

[Specific Structure of the Invention] The color developing solution of the present invention uses at least one selected from diethylhydroxylamine and dimethylhydroxylamine (hereinafter referred to as the present invention) in place of droxylamine, which has been conventionally used as a preservative. (referred to as a compound). These compounds of the present invention are usually free amines, hydrochlorides, sulfates, D-toluenesulfonates, oxalates,
It is used in the form of phosphate, vinegar salt, etc. The amount of addition may be as long as it can effectively achieve the object of the present invention, but it is preferably 0.001 mol to 60 mol, more preferably o, oos mol to 40 mol per 11 of the color developer.
Used in the molar range. Note that when diethylhydroxylamine and dimethylhydroxylamine are used together, the amounts added indicate the total amount of both.

Among the compounds of the present invention, N,N-diethyl and droxylamine, for example, are known to be used as preservatives for black and white developing agents in color developing solutions to which black and white developing agents are added.

Hydroquinone, hydroquinone monosulfonic acid, phenidone, para-aminophenol, etc., which are usually main agents for black and white phenomena, are relatively stable when used as black and white developing agents in a black and white developer, and sulfite M salt is used as a preservative. Although it is sufficiently preserved through use, it is known that when added to a color developing solution, a cross-oxidation reaction occurs with the color developing agent, resulting in poor storage stability. To preserve the black and white developing agent added to these color developing solutions,
Hydroxylamine has little effect.

An example of using N,N-diethylhydroxylamine as a preservative for a black and white developing agent added to a color developer is when a color photographic material is developed by a reversal method using a color developer containing a coupler. It is known to be used together with phenidone in the so-called external color development method. The role of phenidone in this case is to increase the development speed of external photosensitive materials with poor developability and to increase the density of dye images.

In a magenta color developing solution that does not contain phenidone, N,N-diethylhydroxylamine is
It is known that it actually has an adverse effect on the storage stability of external color developing solutions by destroying couplers (see Japanese Patent Publication No. 45-22198).

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

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

The color developer of the present invention contains poly(alkyleneimine). Poly(alkylene imines) consist of repeating substituted or unsubstituted alkylene chain positions connected to each other via nitrogen atoms. These are well-known commercially available substances. Representative poly(alkyleneimine)s include compounds represented by the following general formula [I].

General formula [I] +R+ N→possible (in the formula, R1 represents an alkylene group having 1 to 6 carbon atoms, R2 represents an alkyl group, and n is 500 to 20,0
Represents an integer of 00. ) The alkylene group having 1 to 6 carbon atoms represented by R1 above may be linear or branched, and is preferably an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, a butene group, an isobutyne group, and a dimethyl ethylene group. group, ethylethylene group, etc. R2
The alkyl group represented by preferably has 1 to 4 carbon atoms.
It is an alkyl group 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 R1 is an ethylene group is most preferred for the purposes of the present invention. Specific examples of poly(alkyleneimine) used in the color developer of the present invention 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) FAI-4 Poly(isobutyneimine) PAI-5 Poly(N-methylethyleneimine) P,l-
6 poly(N-β-hydroxyethylethyleneimine) PAI-7 poly(2,2-dimethylethyleneimine) PA>8 poly(2-ethylethyleneimine) PAI
-9 poly(2-methylethyleneimine) poly(alkyleneimine) can be used in the color developer at any rate that can achieve the objectives of the invention, but generally 0.1/12 of the color developer. ~soog is preferred, and more preferably used in the range of 0.59 to 300g.

It has been shown in JP-A No. 56-117 that when the poly(alkylene imine) of the present invention is used together with hydroxylamine in a color developing solution, the storage stability of the color developing solution can be improved and the concentration of Ml subsalt can be reduced. It is described in Publication No. 94349. However, in this method, especially when heavy metals are mixed in, hydroxylamine decomposes and storage stability decreases, so it is not only insufficient as a storage stability improvement technique, but also has an excellent effect as a preservative and prevents heavy metals from mixing. The coloration of the liquid that occurs when diethylhydroxylamine and dimethylhydroxylamine, which the present inventors have discovered as a strong preservative for coloring, is used in the coloring liquid.
The above-mentioned patent publication does not mention at all that polyalkyleneimine effectively solves the problem of contamination of photosensitive materials, containers, etc. caused by such contamination. In other words, the problem of coloring of the liquid and contamination of photosensitive materials and containers due to it does not occur with hydroxylamine, but is a problem that specifically occurs when diethylhydroxylamine or dimethylhydroxylamine is used. The existence of polyalkylene imines has not been previously known, and the fact that polyalkyleneimines can effectively solve this problem is a completely unexpected and surprising effect.

The color developing solution used in the present invention preferably further contains at least one compound selected from the following general formulas [I11] to [■].

General formula [■ General formula [IV] (In the general formulas ['l [I] and [IV], L is an alkylene group, a cycloalkylene group, a phenylene group, -La -
0-La represents -0-La- or -19-Z-L. Here, Z is L12 R9L12-RRHR++ and 1 to +3 each represent an alkylene group.

R1 to R++ each represent a hydrogen atom, water MM, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts). However, at least two of R1-R4 are carboxylic acid groups (including salts thereof) or phosphonic M groups (
At least two of R5 to R7 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof). ) In the general formulas [11[] and [rV], the alkylene group, cycloalkylene group, and phenylene group represented by , and the alkylene groups represented by L1 to L13 include those having a substituent.

Next, preferred specific examples of the compounds represented by the general formulas [1 [[] and (■1) are listed below.

[Exemplary compounds] [1[[-1]ethylenediaminetetraacetic acid [1[[-
2] Diethylenetriaminepentaacetic acid [DI-3] Ethylenediamine-N-(β-hydroxyethyl)-N,N
' , N'-triacetic acid [1 [[-41 propylene diamine tetraacetic acid [111
-51 triethylenetetraminehexaacetic acid II [[-6
]Cyclohexanediaminetetraacetic acid CI[[-7]
1.2-diaminobrobandetraacetic acid [I[1-8]
1.3-Diaminopropan-2-ol-tetraacetic acid [1[[-9]ethyl ether diamine tetraacetic acid [1]
-10] Glycol ether diamine tetraacetic acid [1111] Ethylene diamine tetrapropionic acid [[
1-12] phenylenediaminetetraacetic acid [I[[-1
3] Ethylenediaminetetraacetic acid disodium salt [II-14] Ethylenediaminetetraacetic acid tetra(
trimethylammonium) salt [III-15] ethylenediaminetetraacetic acid tetrasodium salt [III-16] diethylenetriaminepentaacetic acid pentasodium salt [1 [[-17] ethylenediamine-N-(β-hydroxyethyl)-N, N', N '-Triacetic acid sodium salt [1-18] Propylene diamine tetraacetic acid sodium salt [I [1-19] Ethylenediamine tetramethylene phosphonic acid [1[[-201 Cyclohexanediamine tetraacetic acid sodium salt [I[[-211 diethylenetriamine pentamethylene Phosphonic acid [111-22] Cyclohexanediamine tetramethylene phosphonic acid [rV-1] Nitrilotriacetic acid [IV-2] Iminodiacetic acid [IV-311 Nitrilotripropionic acid [■-4] Nitrilotrimethylene phosphonic acid [IV-5] Iminodiacetic acid Methylenephosphonic acid [IV-6] nitrilotriacetic acid trisodium salt Among these chelating agents represented by the general formula [1 [1] or [IV], which compound is particularly preferably used from the viewpoint of the desired effect of the present invention? is [ll-1], [I
I[-2], [[[[-51, [[I-8], [l-1
91, [IV-11 and NV-/I].

The addition port of the chelating agent represented by the general formula [111] or [IV] is 0.1 to 20 per 11 color developing solutions.
It is preferably used in a range of 9 g, and particularly preferably in a range of 0.3 to 10 g from the viewpoint of the purpose of the present invention.

General formula [Vl K+ General formula [Vl, ] (In the above general formula [Vl and U [VI], R+, R
2.

R3 and R4 each represent a hydrogen atom, a halogen atom, a sulfone mW, or an alkylphenyl group having 1 to 7 carbon atoms. Further, Rs, R6, R7 and R8 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R2 represents -OH or a hydrogen atom, R1 is a halogen atom, a sulfone M group, or has 1 carbon atom.
-7 represents a or a phenyl group. ) In the general formula [Vl and [■], R+.

Examples of the alkyl group represented by R2, Ra and R4 include methyl group, ethyl group, 1so-propyl group, n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group. group, benzyl group, etc., and the alkyl group represented by Rs, Rs, R7 and R8 is as defined above,
Further examples include octyl group.

In addition, the engineering group (represented by R+, R2, R3 and R4) is a phenyl group, a 2-hydroxyphenyl group, a 4-
7minophenyl group and the like.

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

(V-1) 4-isopropyl-1,2-dihydroxybenzene (V-2) 1.2-dihydroxybenzene-3゜5-disulfonic acid (V-3) 1.2.3-trihydroxybenzene-5-
Carboxylic acid (V-4) 1.2.3-trihydroxybenzene-5-
Carboxymethyl ester (V-5) 1.2.3-trihydroxybenzene-5-
Carboxy-〇-butyl ester (V-6) 5-t-butyl-1.2.3-trihydroxybenzene (Vl-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (Vl-2) 2.3.8 -Tri and Droxynaphthalene-
6-sulfonic acid (Vl-3>2.3-dihydroni-1-sinaphthalene-6
-Carboxylic acid (Vl-4) 2. 3-dihydroxy-8-isopropyl-naphthalene (Vl-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 general formula [Vl or [Vl]
The compound represented by 5111Q to 20 (
It can be used in the range of 1, preferably 10 mq to
Good results are obtained by adding 10 g, more preferably 1 to 3 g of 20II.

General Formula [V Summer] (In the above general formula [■], R+, R2 and R3 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts) or a phosphoric acid group (including its salts). However, R+
, at least one of R2 and R3 is a hydroxyl group,
and at least one of R+, R2 and R3 is a carboxylic acid group (including its salt) or a phosphoric acid group (including its salt).

n+, n2J5 and n3 each represent an integer from 1 to 3. ) In the general formula [■], R+, R2 and R3 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts) or a phosphorus Fi group (including its salts),
Carvone Ml and phosphorus! Examples of the salts include salts of alkali metal atoms, salts of alkaline earth atoms, and salts of alkali metal atoms such as sodium and potassium are preferable. Further, at least one of R+, R2 and R3 is a hydroxyl group, and at least one of R+, R2 and R3 is a carboxylic acid! ! (including its salts) or a phosphate group (including its salts).

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

R+, R2 and R3 are each preferably selected from a hydroxyl group, a carboxylic acid group (including its salts), and a phosphoric acid group (including its salts).

nl, n2 and n3 each represent an integer of 1 to 3.

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

1+1, -= : = = E =
Eo o oo, oo
.

+ 1 1 1
1 (J CJ (J
(J.

Q C,l O-〇-General formula ■] General formula [In ■1, R1 is a didroxyalkyl group having 2 to 6 carbon atoms, R2 and R3 are a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, respectively. , carbon number is an integer of ~6, X and Z each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms.

Among the compounds represented by the general formula [■], the compounds represented by the following general formula [■a] are particularly preferably used.

R1 is preferably a hydroxyalkyl group having 2 to 4 carbon atoms, and R26 and R3 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 [■] are as follows.

Ethanolamine, jetanolamine, triethanolamine, di-isopropanolamine, 2-methylamineethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1-propatur, 3-dimethylamino-
1-propertool, isopropylamine 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 [■] and [■1] are suitable for color developing solution 1j! from the viewpoint of the desired effects of the present invention. It is preferably used in a range of 3 g to 100 g, more preferably in a range of 6 g to 50 (+).

The above-mentioned diethylhydroxylamine and dimethylhydroxylamine of the present invention may be used in combination with other preservatives. Examples of preservatives that can be used in combination include sulfite sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, and potassium bisulfite. Examples include salts, and bisulfite adducts of aldehydes or ketones, such as formaldehyde bisulfite adducts 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 in order to reduce coloration and color staining.

A p-phenylenediamine compound having a water-soluble group is
Compared to paraphenylenediamine compounds that do not have water-soluble groups such as N,N-diethyl-〇-phenylenediamine,
Not only does it have the advantage of not causing contamination of photosensitive materials and does not cause irritation to the skin, but in particular, in the present invention, the object of the present invention can be efficiently achieved by combining it with a compound represented by the general formula [II]. can be achieved.

The water-soluble group is 7 of the p-phenylenediamine compound.
Examples include those having at least one amino group or benzene nucleus, and specific water-soluble groups include -(CH2)n -CH20H1 -(CH2)m -NH8O2-(CH2)n-CH3
, -(GHz >II 0-(CH2)n-CH3, -(
CH2CH20)n Cm +2 m+1 (m and hn each represent an integer of 0 or more), -COOH
Preferred examples include -8O3H group and -8O3H group.

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

Mysterious lower 1. Kasahirakama, J Exemplary color development agent (A-1) H, C2C, H, NH302CH3 (A-2) H, C, C, H, OH (A-3) Hs Ct Ct H40H N+2 (A-4) HsCz C*H40CH2 (A-5) HsC2C5H-SO3M (A-6) H,CC,H,OH (A-7) HOH,C2C2H4OH (A-8) H=C4C4H*SO3H (A-9) HsC4C3HiSO3H (A -10) HCH2C0OH \N/ HsC< , GCH2CH2O"17 CHsHsC
< )CH2CH2OsudingCHkoNH.

(A-13) Hs C< )CHt CHxO廿C2Hs(A-14
) H6ノCH2CHz O廿Ct Hs (A-15) HsC2C2H4NH30*CHs 鴇/ (A-16) Hs C2C2H40H Among the above-mentioned color developing agents, those that cause less coloring and color staining are preferred for use in the present invention. Example No. <A-
1>, (A-2>, (A-3), (A-4>, (A-6
>, <A-7) and (A-15), with (A-1) being particularly preferred.

The above color developing agents are usually hydrochloride, sulfur M salt, 1)-1-
It is used in the form of salts such as luenesulfonate.

The color developing agent having a water-soluble group used in the present invention is
1X per 1ffi of normal color developer 10-2~2X
It is preferable to use the amount in the range of 10'' mol, but from the viewpoint of rapid processing, it is preferable to use 1.5 x 10' per color developer.
A range of ˜2×10” moles is more preferred.

The color-forming visual imaging 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 and No. 58-24137 are used, and specifically, for example, 2',4'-stansulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4 '-(2
,4,6-doliisobrobyl)benzenesulfonamide-2-methyl-4-N-(2-methanesulfonamidoethyl)ethylaminodiphenylamine, 2'-methanesulfonamide-4'-(2,4,6- doliisobrovir)benzenesulfonamido-4-(hydroxytrisethoxy)diphenylamine, 4-N-(2-methanesulfonamidoethyl)ethylamino-2-methyl-2'
, 4'-bis(2,4゜6-dolyisobrobyl)pensenesulfonamide diphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'-(2,4,6-doliisobrobyl)benzenesulfonamide diphenylamine,
4-methoxy-2'-methanesulfonamide-4' -
(2,4,6-)-lyisobrobyl)benzenesulfonamide diphenylamine, 4-dihexylamino-4'
-(2,4,6-dolyisobrobylbenzenesulfonamido)diphenylamine, 4-n-hexyloxy-
3'-Methyl-4'-(2,4,6-doliisobuO
bilbenzenesulfonamide) diphenylamine, 4-
N.

N-diethylamino-4'-(2,4,6-dolyisobrobylbenzenesulfonamide)diphenylamine,
Examples include 4-N,N-dimethylamino-2-phenylsulfonyl-4'-(2,4,6-doliisobrobylbenzenesulfonamide)diphenylamine.

The amount of the dye precursor added to the photosensitive material is preferably 0.5 to 22+eg, more preferably 4 to 12 mg per 100 C, J of the photosensitive material.

In the present invention, it is preferable to use a triazyldilbene fluorescent whitening agent represented by the following general formula [IX] in the color developing solution according to the present invention, since color staining can be further reduced.

General formula [IX] In the formula, X+, X2, Y+ and Y2 are each a hydroxyl group, a halogen atom such as chlorine or bromine, or a molbolim L alkoxy! (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy, 0-sulfonoxy, etc.), alkyl groups (e.g., methyl, ethyl, etc.), aryl groups (e.g., phenyl, methoxyphenyl, etc.), amino groups, Alkylamino groups (e.g. methylamino, ethylamino, propylamine, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di(β- and droxyethyl)amino, β-sulfoethylamino, N-(β-sulfoethyl)-N '-methylamine, N-(β-hydroxyethyl-N'-methylamine, etc.), arylamino group (e.g. anilino, o-1m
-1p-sulfoanilino, 0-1m-1p-chloroanilino, 0-1de-1p-toluidino, 0-1m-1p-
carboxyanilino, o+, l-1p-hydroxyanilino, sulfonaphthylamino, 0-1m-1p-aminoanilino, 0-1m-1p-anilino, etc.). M
represents a hydrogen atom, sodium, potassium, ammonium or lithium.

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

to
Rokurn
The triazylstilbene whitening agent represented by the Z-1 formula [IX] is, for example,
It can be synthesized by the usual method described in "Fluorescent Brightener" (published in August 1976), page 8.

These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per 12 of the color developing solution used in the present invention.

The color developer of the present invention may contain the following developer components in addition to the above components.

Examples of alkaline agents include sodium hydroxide, potassium hydroxide, silicates, sodium carbonate, potassium carbonate,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Sodium, tripotassium phosphate, borax, etc. can be used alone or in combination. Furthermore, due to the necessity of preparation or for the purpose of increasing the sulfur strength, disodium hydrogen phosphate, dipotassium hydrogen phosphate, etc.
Various salts can be used, such as sodium bicarbonate, potassium bicarbonate, and borates.

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

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

Examples of the phenomenon accelerator include various pyridinium compounds as typified by U.S. Patent No. 2.6481604, U.S. Pat. cationic dyes, neutral salts such as thallium nitrate, U.S. Pat.
No. 533,990, No. 2,531,832, No. 2
, 950,970@, 2.577, 127, and nonionic compounds such as polyethylene glycol, derivatives thereof, and polythioethers described in Japanese Patent Publication No. 44-9504. Also, U.S. Patent No. 2,304,9
In addition to benzyl alcohol and phenethyl alcohol described in No. 25, acetylene glycol, methyl edyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines can be mentioned.

In the above, organic solvents that are poorly soluble in water, such as benzyl alcohol, tend to generate tar due to long-term use of color developing solutions, especially during running processing in low replenishment systems. If they adhere to the vapor-sensitive material to be processed, they may even cause serious malfunctions that significantly impair the commercial value of the material.

In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome to prepare the color developing solution itself, such as requiring a stirring device, but even the use of such a stirring device can reduce its dissolution rate. Due to its poor performance, there is a limit to its development accelerating effect.

Furthermore, poorly soluble organic solvents reduce the biochemical oxygen demand ff
The pollution load value such as 1 (BOD) is large, and it is impossible to dispose of it in sewers or rivers, etc., and the Fjl! Since liquid treatment has problems such as requiring a great deal of labor and expense, it is preferable to reduce or eliminate its usage as much as possible.

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. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol).
, phenidone, N,N'-diethyl-〇-aminephenol hydrochloride, N,N.

N',N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the amount added is usually 0.01 (preferably 1 to 1.0 g#!). Competitive couplers, fogging agents, colored couplers, inhibitor-releasing couplers (so-called DIR
Coupler) or a development inhibitor-releasing compound can also be added.

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

Each component of the above-mentioned color developing solution can be prepared by sequentially adding and stirring a certain amount of water. In this case, components with low solubility in water can be mixed with the above-mentioned solvent such as triethanolamine and added. More generally, a concentrated aqueous solution or solid state of a plurality of components that can coexist stably in a small container is added to water and stirred to prepare XGL, and the color developer of the present invention is prepared. can be obtained as

In the present invention, the above color developing solution can be used at any pH, but from the viewpoint of rapid processing, IIH95 to 13.
0, more preferably pi-19,
8 to 13.0.

In the present invention, the processing temperature for color development is 30
C. or more and 50.degree. C. or less, the higher the temperature, the faster the treatment is possible, which is preferable, but from the viewpoint of storage stability, it is better not to be too high, and it is preferable to process at 33.degree. C. or more and 45.degree. C. or less.

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 it is preferably carried out in the range of 30 seconds to 1 minute and 30 seconds. .

The present invention can be applied to any system that uses a color developing solution containing at least one selected from diethylhydroxylamine and dimethylhydroxylamine and also containing polyalkyleneimine. First, various other processing methods may be used, such as a spray set in which the processing liquid is atomized, a web method using contact with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid. However, the processing steps essentially consist of steps such as color development, bleach-fixing, washing with water, or alternative stabilization processing.

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

Bleaching agents that can be used in the bleach-fix solution used in the present invention are metal complex salts of organic acids. The Iff 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. The most preferred organic acid used to form such a metal complex salt of an organic acid is a polycarboxylic acid. 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] Dihydroxyethylglycine citric acid (or Tartar M) [9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylenediamine tetrapropionic 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' - Sodium triacetate [18] Sodium propylene diamine tetraacetate [1] Sodium nitriloacetate [20] Sodium hexanediamine tetraacetate l, more preferably 2
Use at 0 to 250g/2. 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 ethylenediaminetetraacetate iron (I[I) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, Bleach-fix solutions with a composition containing a large amount of a halide such as halides, and special bleach-fix compositions containing a combination of iron ethylenediaminetetraacetate (I [[) complex salt bleaching agent and a large amount of a halide such as ammonium bromide] A liquid etc. can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The silver halide fixing agents contained in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples include thioVA salts such as ammonium Ta acid, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, and thioethers. These fixing agents are used in an amount of 5a/i or more, within the range that can be dissolved, but generally 70 (] to 25
Use at 0 g/l.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, specific chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent or the like can be contained as appropriate.

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

f) The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 or higher and 1)H of 9.5 or lower, preferably p) -16.0 or higher and a pH of 8.5 or lower,
More specifically, 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.

The water washing substitute stabilizer that can be applied to the present invention will be described below.

The DH of the water washing alternative stabilizing liquid applicable to the present invention is preferably in the range of 5.5 to 10.0, more preferably p
H6.3 to 9.5, particularly preferably pH7
,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 stabilization treatment temperature ranges from 15°C to 60°C, preferably from 20°C to 45°C. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 20 seconds to 10 minutes, most preferably 1 minute to 3 minutes, and in the case of multiple tank stabilization treatment, the first stage tank should be used in a shorter time. It is preferable that the treatment time in the subsequent tank is long. Especially 20% of the anterior tank
It is desirable to process sequentially with ~50% more processing time)
.

After the stabilization treatment that can be applied to the present invention, no water washing treatment is required at all, but rinsing with a small amount of water in a very short 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 for adding it, such as whether it is used as a supply liquid, it may be added by any method.

In this way, in the present invention, treatment with a stabilizing solution refers to a treatment for stabilization treatment that is performed immediately after treatment with a bleach-fixing solution and does not substantially involve washing with water.
The processing liquid used for this stabilization treatment is called a water washing alternative stabilizing liquid,
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 crystals of the silver halide grains used in the present invention may be normal crystals, twin crystals, or other crystals, and have (100) planes and (111) planes.
) Any surface ratio can be used.

Further, the crystal structure of these silver halide grains may be uniform and weak from the inside to the outside, or may have a layered structure (core-shell type) with different inside and outside. 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. Furthermore, tabular silver halide grains (JP-A-58
-113934, patent application No. 59-170070)
You can also use

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

Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, control I) H1+1Ag, etc. in the reaction vessel, and adjust the amount of silver ion to match the growth rate of silver halide grains, for example, as described in JP-A No. 54-48521. It is preferable to implant and mix the and halide ions sequentially and simultaneously.

Preparation of silver halide grains according to the present invention is preferably carried out as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions are prepared using activated gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers:)! Original sensitizers, such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothia Zolium chloride etc. or such as ruthenium, palladium, platinum, rhodium,
Sensitizers of water-soluble salts such as iridium, specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chloroparadate (these types can be used as sensitizers or fog suppressants depending on the size of the layer) Even if chemically sensitized by using a combination of gold sensitizer and sulfur sensitizer (for example, combination of gold sensitizer and sulfur sensitizer, combination of gold sensitizer and selenium sensitizer, etc.), 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.

In the silver halide used in the present invention, an appropriate sensitizing dye is added in an amount of 5 x 10-3 to 3
-3 mol may be added for optical sensitization. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929.080, U.S. Pat.
, 231,658, 2.493.748, 2.
No. 503゜776, No. 2,519,001, No. 2.9
No. 12.329, No. 3.656.959, No. 3,6
No. 72,897, No. 3,694,217, No. 4.0
No. 25,349, No. 4,046,572, British Patent 1
, No. 242.588, Equity [[(No. 44-14030,
Examples include those described in No. 52-24844. Further, as a sensitizing dye used in a green-sensitive silver halide emulsion, for example, U.S. Patent No. 1,939,201
No. 2,072,908, No. 2.739.149, No. 2.945.763@, British Patent No. 505.979, etc. This can be cited as a representative example. In general, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 9,234, No. 2.270,378, No. 2,442
．． No. 710, No. 2,454,629, No. 2,776.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 280 and the like.

Furthermore, U.S. Patent Nos. 2,213,995 and 2,493
．． No. 748, No. 2,519,001, West German Patent No. 929
．． Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may contain cyanine or
Optical sensitization may be performed in a desired wavelength range by a spectral sensitization method using merocyanine dyes alone or in combination.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
4, No. 59-116647, and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-
No. 11114, No. 47-25379, No. 48-384
No. 06, No. 48-38407, No. 54-34535, No. 55-1569, JP-A No. 5o-33220, No. 50-38526, No. 51-107127, No. 51
-115820, 51-135528, 52-
No. 104916, No. 52-104917, and the like.

Regarding combinations of benzoxazolocarbocyanine (oxacarbocyanine) and other carbocyanines, for example, Japanese Patent Publication No. 32753/1986 and Japanese Patent Publication No. 44-32753;
No. 6-11627, JP-A-57-1483, and regarding merocyanine, for example, JP-B No. 48-384.
No. 08, No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753,
No. 58-91445, No. 59-116645, No. 5
No. 0-33828 and the like.

Regarding combinations of thiacarbocyanine and other carbocyanins, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 46-18107, No. 47-8741, JP-A-59
Furthermore, the method described in Japanese Patent Publication No. 49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol as described in Japanese Patent Publication No. 40659/1984 is prepared in advance. It is used by dissolving it in a hydrophilic solvent.

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

Photographic configuration β of the silver halide color photographic light-sensitive material of the present invention
A dye (AI dye) that is water-soluble or decolorable with a color developing solution can be added to the dye, and the AI dye includes oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 58
No. 4.609, No. 1,277.429, Japanese Unexamined Patent Publication No. 1977
-85130, 49-99620, 49-1
No. 14420, No. 49-129537, No. 52-
No. 108115, No. 59-25845, No. 59-1
No. 11640, No. 59-111641, U.S. Patent No. 2,
No. 274,782, No. 2,533.472, No. 2,
No. 956,079, No. 3.125.448, No. 3,
No. 148.187, No. 3,177.078, No. 3
, 247.127, 3,260,601, 3.
No. 540.887, No. 3.575.704, No. 3.6
No. 53.905, No. 3.718.472, No. 4,07
Examples include those described in No. 1°312 and No. 4.070.352N.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use from X10-3 to 5X10" mol, more preferably from IX10' to 1x10" mol.

. - As the couplers that can be used in the present invention, various yellow couplers, magenta couplers, and cyan couplers can be used without any particular restrictions. These couplers may be so-called 2-power type or 4-power n-type couplers, and in combination with these couplers, it is also possible to use a diffusible dye-releasing coupler or the like.

The photographic coupler used in the present invention is preferably a phenolic compound or a naphthol compound as a cyan coupler, for example, U.S. Pat. No. 2,369.929,
No. 2,434,272, No. 2,474.293, No. 2,895,826, No. 3.253.924,
3.034.892, 3.311.476, 3,386,301, 3,419°390, 3
, 458,315, 3,476.563, 3,
531, 383, etc., and methods for synthesizing these compounds are also described in the same publication.

Examples of photographic magenta couplers include compounds such as pyrazolone, pyrazolotriazole, virazolizbenzimidazole, and indasilone. As a pyrazolone magenta coupler, U.S. Patent No. 2,600,
No. 788, No. 3,062,653, No. 3,127,2
No. 69, No. 3,311,476, No. 3.419.39
No. 1, No. 3,519,429, No. 3.558.318
No. 3,684゜514, No. 3.888.680, JP-A No. 49-29639, No. 49-111631, No. 49-129538, No. 50-130414,
Compounds described in Japanese Patent Publication Nos. 53-47167, 54-10491, and 55-30615: As birazolotriazole magenta couplers, U.S. Pat.
, No. 247,493 and Belgian Patent No. 792.525. As a diffusion-resistant colored magenta coupler, a compound having an arylazo substitution at the coupling position of a colorless magenta coupler is generally used. For example, U.S. Patent No. 2,801,171;
．． No. 983,608, No. 3.005.712, No. 983,608, No. 3.005.712, No.
3,684,514, British Patent No. 937.621, JP-A-49-123625, and JP-A-49-31448.
Colored magenta couplers of the type described in No. 19,391, in which the dye flows out into the processing solution by reaction with an oxidized form of a developing agent, can also be used.

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

Examples of these are U.S. Pat.
No. 65,506, No. 3.664.841, No. 3.40
8. No. 194, No. 3,277, No. 155, No. 3,44
No. 7,928, No. 3.415.652, Special Publication No. 1973
-13576, JP-A-48-29432, JP-A-48-
No. 68834, No. 49-10736, No. 49-122
No. 335, No. 50-28834, No. 50i32926
The method of synthesis is described in the issue.

The use of the above-mentioned diffusion-resistant couplers in the present invention is generally limited to 0.0% per mole in the light-sensitive silver halide emulsion layer.
It is 5 to 2.0 moles.

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

Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development are also included in the present invention, such as those disclosed in U.S. Pat. No. 3.297.445, U.S. Pat. , 417,914, JP-A No. 52-15271, JP-A No. 53-9116, JP-A No. 53-9116,
Examples include those described in No. 59-123838 and No. 59-127038.

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

A typical example of such an IR compound is a DIR coupler, in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the active site of the coupler. , No. 454, US Pat. No. 3,227,554, US Pat. No. 4,095.984, US Pat. No. 4,149,886, and the like.

When the above DIR coupler undergoes a coupling reaction with an oxidized color developing agent, the coupler core forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Moreover, in the present invention, U.S. Pat.
No. 41, No. 3,958,993, No. 3,961,95
No. 9, No. 4,052,213, JP-A-53-1105
2'J@, No. 54-13333, No. 55-16123
It also includes compounds that release a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 7, but do not form a dye.

Furthermore, JP-A-54-145135 and JP-A-56-1
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. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
IR compounds are also included in the invention.

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

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1.times.10@-1 mole to 10.times.10@-1 mole 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, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color inhibitors, color fixing agents, hardeners, etc. described in Research Disclosure Magazine No. 17643, Surfactants, plasticizers, wetting agents, etc. can be used.

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

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

For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2,761
, No. 791 and No. 2,941,898 can also be used to simultaneously coat two or more layers.

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

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

Hydrophilic colloids that can be used in the emulsion layers as described above can be similarly used as binders in these constituent layers, and can also be contained in the emulsion layers as described above. Various photographic additives can be included.

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

[Specific Effects of the Invention 1] As explained above, according to the present invention, a color developing solution which is excellent in storage stability and color staining is proposed, and furthermore, by using this color developing solution, fogging and It has been possible to provide a method for processing a silver halide color photographic light-sensitive material, which has excellent processing stability for high-contrast shoulder areas and causes less color staining of the light-sensitive material.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereto.

[Example 1] Color developer N 0.1 to 10 having the following composition was prepared.

(Color developer) Potassium bromide 1.0g Sub5A
Potassium acid 2.5g preservative
(Listed in Table 1) Chelating agent (Exemplary compound 1 [[-1) 2.0(] (Exemplary compound V-2)
0.61J color developing agent (exemplary compound A-1)
4.38 (+potassium carbonate
3G 1J alkanolamine (listed in Table 1) Add water to bring the pH to 12, and adjust the pH to 1 with potassium hydroxide and sulfuric acid.
Adjust to 0, Is.

The molecular weights of the polyalkyleneimines used here were all about 50,000.

First, the appearance (yellow coloring degree) of the color developer was observed, and the results are listed in Table 1. However, the appearance of the liquid was evaluated on the following four levels.

++ 10 Significant yellow coloring + 10 Yellow coloring + Slight yellow coloring - No yellow coloring Next, add ferric ion 4DOm and copper ion 21) I) In (respectively) to the above color developer !3, CLI
304.6H20 (dissolved and added) was added, and the opening ratio was 150 cf// at 35°C! The concentration of the color developing agent in the color developing solution was analyzed using the cerium sulfate method while being stored in a glass container (air contact area is 150 Cf for 1 fl of the color developing solution) until the concentration of the color developing agent reached O. The number of days was determined as the lifespan of the color developer.

These results are also shown in Table 1.

Below is the remaining number one? si Table 1 Hydroxylamine sulfate does not cause yellow coloration of the color developer, but the life of the color developer is short when metal ions are mixed. On the other hand, when dimethylhydroxylamine or diethylhydroxylamine is used, the life of the color developing solution is long when metal ions are mixed in, but when poly(alkylene imine) is not added, there is a noticeable color in the liquid tube. However, it can be seen that the color of the liquid tube disappears by adding poly(alkyleneimine).

[Example 21] 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...1.200/i' gelatin, 0.4
Blue-sensitive silver halide emulsion (AgBr:AG Cf=4:96) and U
O, dissolved in 55 g/f dioctyl phthalate 1
．． The following yellow coupler (Y
-R).

Layer 2: Intermediate layer consisting of 0.70 g/t'' gelatin.

Layer 3...1.20(]/f gelatin, 0.2
2+1/11' green-sensitive silver halide emulsion (AgBr
:AgCf1=3:97) and a layer containing magenta coupler (M-R) of 10-3 mol (1/f) of 1,OX dissolved in 0.30 (+/f) dioctyl phthalate.

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

Layer 5...1.20 (1/f gelatin, 0.2
8 (1/l” red-sensitive silver halide emulsion (A(l Br
1,75
A layer containing molar v/V of the following cyan coupler (C-R).

Layer 6...1.0! II/f gelatin and 0
．． 0 dissolved in 251 J/f of dioctyl phthalate,
320/f layer containing Tinuvin 328 (ultraviolet absorber manufactured by Ciba Geigy).

Layer 7: A layer containing gelatin of 0.480/f.

In addition, 2,4-dichloro-6-hydroxy-5-t-lyazine sodium was used as a hardening agent in layers 2, 4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

These samples were subjected to wedge-shaped exposure in a conventional manner and then processed according to the following processing steps.

Treatment process Treatment temperature Treatment time (1) For color development @ 35℃ 45 seconds (2)'f
A White fixing 35℃ 45 seconds (3) Washing with water
30℃ 90 seconds (4) Drying 60~8
The color developing solution used at 0°C for 60 seconds was the following No. 1.
It is 1-20.

(Color developer) Potassium chloride 1.0g Potassium sulfite 0.3g Preservative
(Listed in Table 2) Chelating agent (Exemplary compound V-2> 0.5° (Exemplary compound lll-8)
2.0 (] Color developing agent (Exemplary compound A-1>
5.31J potassium carbonate 30
9 Alkanolamine (listed in Table 2) Add water and 1! and p)-110,1 with potassium hydroxide and sulfuric acid.
Adjust to 5.

The molecular types of the polyalkyleneimines used here were approximately so and ooo.

The bleach-fix solution used had the following composition.

[Bleach-fix solution 1 Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60. Og ethylenediaminetetraacetic acid F11 3.0 (1 Ammonium thiosulfate (70% solution) 100.0112 Ammonium sulfite (40% solution) 27.5wN Add water to bring the total volume to 111, adjust to pH 7.1 with potassium carbonate or glacial acetic acid do.

The processed sample was measured using an optical densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.) to measure the inverse IJi of the cyan dye at 11 degrees, and create a sensitometric curve, as well as the minimum reflection density of the magenta dye and the yellow color. The lowest concentration of dye was measured. Next, the slope (gamma value) of the cyan dye from the density point of 0.8 degrees opposite 011 degrees to the density point 1.8 degrees opposite 01 Wi degrees 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.

After storage, repeat the same process to remove the minimum amount of magenta dye (
g) The concentration was determined and the cyan gamma value was calculated.

The difference in the minimum reflection density of the yellow dye before storage, the minimum anti-0A81 degree of the magenta dye before and after storage, and the difference in cyan gamma value are determined and listed in Table 2. Table 2 also shows the difference in 11H before and after storage.As is clear from Table 2, hydroxylamine sulfate has less yellow stain, but the magenta fog density and cyan gamma after storage are lower. The increase is remarkable. On the other hand, with dimethylhydroxylamine and diethylhydroxylamine, increases in magenta fog density and cyan gamma after storage are small, but yellow stain is high when poly(alkyleneimine) is not added. However, it can be seen that when the preservative of the present invention and poly(alkylene imine) are used together, the magenta fog density is low, the cyan gamma does not increase, and the yellow stain is significantly reduced.

[Example 3] The same experiment as in Example 2 was repeated using the same color developer No. 16 as in Example 2 except that chelating agents V-2 and Ill-8 were not added. However, the magenta fog increased by an additional 0.02, and the cyan gamma increased by an additional +0.2.

In addition, color developer Nos. 21 to 26 were prepared by changing the chelating agent of color developer No. 0.16 in Example 2 as shown in Table 3, and the same experiment as in Example 2 was repeated, but the The same results as in Example 2 were obtained.

Below - Margins Ji, ji [Example 4] Color developer No. 16 of Example 2, J3, exemplified compounds (A'-2>, (A'-4) and (A'-9) (all triadylstilbene optical brightener)
(When 1/l was added and an experiment similar to Example 2 was conducted, the yellow stain was further improved by 0.01.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment written statement July 23, 1985

Claims (8)

[Claims] (1) A color developing solution containing at least one selected from diethylhydroxylamine and dimethylhydroxylamine and poly(alkyleneimine). (2) The poly(alkyleneimine) has the following general formula [
The color developing solution according to claim (1), which is a compound represented by [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkylene group having 1 to 6 carbon atoms, R_2 represents an alkyl group, and n is 500 to 20
,000 integer. ) (3) The color developing solution according to claim (2), wherein in the general formula [I], R_1 is an ethylene group. (4) In the general formula [I], n is 500 to 2,
The color developing solution according to claim 2 or 3, wherein the color developing solution is an integer of 000. (5) A method for processing a silver halide color photographic material, in which a process including at least a color development step is performed after the silver halide color photographic material is imagewise exposed, wherein the color developer used in the color development step is 1. A method for processing a silver halide color photographic material, comprising at least one selected from diethylhydroxylamine and dimethylhydroxylamine and poly(alkyleneimine). (6) The poly(alkyleneimine) has the following general formula [
A method for processing a silver halide color photographic light-sensitive material according to claim (5), characterized in that the compound is a compound represented by the formula I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkylene group having 1 to 6 carbon atoms, R_2 represents an alkyl group, and n is 500 to 20
,000 integer. ) (7) The method for processing a silver halide color photographic material according to claim (6), wherein in the general formula [I], R_1 is an ethylene group. (8) In the general formula [I], n is 500 to 2,
A method for processing a silver halide color photographic material according to claim 6 or 7, wherein the silver halide color is an integer of 000.