JP2552449B2 - Color developing solution and method for processing silver halide color photographic light-sensitive material using the color developing solution - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color developing solution and a processing method for a silver halide color photographic light-sensitive material, and particularly to a color developing solution having improved storage stability and the color developing solution. The present invention relates to a method for processing a silver halide color photographic light-sensitive material using a developer.

Background of the Invention Generally, a silver halide color photographic light-sensitive material is exposed and then processed with a color developing solution containing a color developing agent. Aromatic primary amines are usually used as color developing agents, but aromatic primary amine color developing agents are generally very easily oxidized, and oxygen in the air is high in a highly alkaline solution such as a color developing solution. Easily oxidized by.

Therefore, sulfite is generally used for the purpose of preserving the aromatic primary amine color developing agent. Sulfite is generally in the form of a sulfite or bisulfite of an alkali metal such as sodium or potassium, which is a compound widely used as a preservative of a developing agent in a black and white developer, The amount used in the color developer is extremely limited. That is, sulfite sulfonates the oxide of the color developing agent generated in the color developing reaction process, and thus inhibits the coupling reaction between the oxide of the color developing agent and the coupler, and particularly uses a coupler having a slow coupling reaction. To reduce the color density of the silver halide emulsion layer. Therefore,
The sulfite concentration in the color developer is usually kept low.
The low concentration of sulfite causes the color developing agent to be gradually oxidized in the presence of sulfite, but these problems are addressed by the use of hydroxylamine as described in U.S. Pat.No. 3,746,544. Be improved.

On the other hand, in color photographic processing, continuous processing is usually performed by an automatic developing machine while replenishing the replenisher according to the processing of the light-sensitive material, but replenishment of the replenisher inevitably causes a large amount of overflow. Being discarded, this method has become a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow, a so-called concentrated low replenishment process in which the amount of the replenisher is reduced and a small amount of the concentrated replenisher is replenished is becoming popular. With such a processing method, since the residence time of the color developing solution in the processing tank of the automatic developing machine becomes long, the oxidation of the color developing agent progresses further. This tendency can be improved by increasing the sulfite concentration in the color developing solution, but such a method results in a significant decrease in dye concentration as described above. Further, as described above, hydroxylamine effectively suppresses the progress of the oxidation of the color developing agent that occurs when the sulfite concentration is low, or is rapidly oxidized when the sulfite is exhausted, so increasing the amount of hydroxylamine has almost no effect. Absent.

[Object of the Invention] Therefore, a first object of the present invention is to provide a color developing solution having excellent storage stability.

A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which causes less decrease in dye concentration by using the developer.

[Structure of the Invention] A first object of the present invention is to provide an aromatic primary amine type color developing agent having a water-soluble group and at least one selected from diethylhydroxylamine and dimethylhydroxylamine in an amount of 1 mol of the color developing agent. In contrast, a color developing solution containing 8.1 mol or more of a compound represented by the following general formula [I] and a triazylstilbene-based optical brightening agent is achieved.

General formula [I] (In the formula, R ₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₂
And R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. ) A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which comprises subjecting a silver halide color photographic light-sensitive material to image-wise exposure and then performing at least a color development step. It is achieved by using the color developing of the present invention as the color developing solution used.

[Specific Structure of the Invention] In the color developing solution of the present invention, at least one selected from diethylhydroxylamine and dimethylhydroxylamine is added to 1 mol of the color developing agent in place of hydroxylamine which is conventionally used as a preservative. In contrast, it contains 8.1 mol or more. These compounds of the present invention are usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.
The amount of addition may be any amount as long as it is 8.1 mol or more per 1 mol of the color developing agent, but in order to suppress stains and the like, it is in the range of 8.1 mol to 60 mol, more preferably 8.1 mol to 40 mol, relative to 1 mol of the main agent. Used in. In addition, about the addition amount of these, when diethylhydroxylamine and dimethylhydroxylamine are used together, the total amount of both is shown.

Among the compounds of the present invention, for example, N, N-diethylhydroxylamine is known to be used as a preservative of a black and white developing agent in a color developing solution obtained by converting the black and white developing agent into a compound.

Usually, black and white developing agents such as hydroquinone, hydroquinone monosulfonic acid, phenidone and para-aminophenol are relatively stable when used as a black and white developing agent in a black and white developing solution, and by using sulfurous acid as a preservative. It is well maintained, but it is known that when it is added to a color developing solution, it causes a cross oxidation reaction with a color developing agent, and its storage stability is extremely poor. To maintain the black and white developing agent added to the color developer,
Hydroxylamine has little effect.

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

Further, in a magenta color developing solution containing no such phenidone, N, N-diethylhydroxylamine is
It is known that destruction of the coupler rather adversely affects the storage stability of the external color developing solution (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 of a black and white developing agent added to a color developing solution is, in an internal color developing solution, in a color developing solution. A technique for preserving the added phenidone derivative (see JP-A-53-32035) and a technique for retaining the phenidone derivative together with hydroquinones (see JP-A-52-153437) can be mentioned. .

As described above, the compound of the present invention is conventionally known to be used as a preservative for a black and white developing agent added to a color developing solution, but a preservative for a color developing agent in a normal color developing solution is used. Is not known as.

The color developer of the present invention contains the compound represented by the general formula [I].

In the general formula [I], R ₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, and benzyl. Group or formula In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.

Of the compounds represented by the above general formula [I], the compound represented by the following general formula [Ia] is preferably used.

General formula [I a] (In the formula, R ₄ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₅ and R ₆ each represent 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 above general formula [I] 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.

The use of the compound represented by the general formula [I] of the present invention as an antioxidant in a color developer is described in, for example, US Pat. No. 3,823,017. Further, JP-A-54-3532 describes that the concentration of sulfite can be lowered by using it in combination with hydroxylamine. However, as a result of various studies on the latter technique, the present inventors cannot fully prevent the so-called tarring, in which the preservative effect is insufficient by such a method, and the liquid coloring and the color developing agent are oxidatively polymerized and tarted. However, it has been found that the storage stability is remarkably reduced due to the decomposition of hydroxylamine particularly when a heavy metal is mixed. This heavy metal is brought into a bleaching solution or a bleach-fixing solution in which a ferric salt of an organic acid is usually used as a bleaching agent in a color developing solution by, for example, a splash, a transport leader, a belt or a hanger for hanging a film. It is mixed in the color developing solution as an impurity in a so-called back contamination or a reagent forming the color developing solution, but it is easily accumulated particularly in the concentrated and low replenishment process described above.

The present inventors have found an alkyl-substituted hydroxylamine as a preservative that replaces hydroxylamine, which is difficult to decompose even when a heavy metal is mixed, but such a hydroxylamine derivative does not necessarily have a preservative ability comparable to that of hydroxylamine. It has been found that it does not have the ability to do so and has resistance to heavy metals, but lacks the preservative ability as an absolute ability when heavy metals are not mixed.

Therefore, as a result of further studies by the present inventors, among the alkyl-substituted hydroxylamine derivatives, particularly diethylhydroxylamine and / or dimethylhydroxylamine was used in an amount of 8.1 mol or more per mol of the color developing agent and the above general formula was used. It was found that the combined use of the compound represented by [I] markedly increased the preservative ability and suppressed the sulfite concentration to a low level, or it was possible to eliminate it altogether.

These facts indicate that diethylhydroxylamine and / or
Alternatively, even when dimethylhydroxylamine and the compound represented by the general formula [I] of the present invention are used in combination, when the amount of diethylhydroxylamine and / or dimethylhydroxylamine added is less than 8.1 mol per mol of the color developing agent,
The preservative ability is inferior to the case where the hydroxylamine and the compound of the general formula [I] are used in combination, and when the hydroxylamine and the compound of the general formula [I] are used in combination, even if the addition amount of the hydroxylamine is increased, The preservative ability does not increase, and in addition to diethylhydroxylamine and dimethylhydroxylamine, other alkyl-substituted hydroxylamine derivatives should be used in combination with the compound of general formula [I] and the amount of hydroxylamine derivative should be increased. However, since it has a low preservative ability, it is a very specific phenomenon, which cannot be expected from the conventionally known methods.

From the viewpoint of the effect of the present invention, these compounds represented by the general formula [I] are preferably 4 to 30 mols, more preferably 5 to 20 mols, per mol of the aromatic primary amine color developing agent. Used in the molar range.

The color developer used in the present invention preferably further contains at least one compound selected from the following general formulas [II [to [VI]].

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 -Z-L ₉ - represent. Where Z is
N-L ₁₀ -R _10, N-R ₁₂ or Represents

L _{1 to} L ₁₃ each represent an alkylene group.

R _{3 to} R ₁₃ are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a sulfonic acid group (including its salt)
Represents However, at least two of R _{3 to} R ₁₃ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least two of R _{7 to} R ₉ are carboxylic acids. An acid group (including its salt) or a phosphonic acid group (including its salt). ) In the general formulas [II] and [III], the alkylene group represented by L, the cycloalkylene group and the phenylene group, and the alkylene group 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.

[Exemplified 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-Diaminepropanetetraacetic acid [II-8] 1,3-Diaminepropane-2- All-tetraacetic acid [II-9] Ethyletherdiaminetetraacetic acid [II-10] Glycoletherdiaminetetraacetic acid [II-11] Ethylenediaminetetrapropionic acid [II-12] Phenylenediaminetetraacetic acid [II-13] Ethylenediaminetetraacetic acid Disodium salt [II-14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt II-15] Ethylenediaminetetraacetic acid tetrasodium salt [II-16] Diethylenetriaminepentaacetic acid pentasodium salt [II-17] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid sodium salt [II-17] II-18] Propylenediaminetetraacetic acid sodium salt [II-19] Ethylenediaminetetramethylenephosphonic acid [II-20] Cyclohexanediaminetetraacetic acid sodium salt [II-21] Diethylenetriaminepentamethylenephosphonic acid [II-22] Cyclohexanediaminetetramethylene Phosphonic acid [III-1] Nitrilotriacetic acid [III-2] Iminodiacetic acid [III-3] Nitrilotripropionic acid [III-4] Nitrilotrimethylenephosphonic acid [III-5] Iminodimethylenephosphonic acid [III-6] Nitrilotriacetic acid Sodium salt These general Among the chelating agents represented by the formula [II] or [III], as the compounds particularly preferably used from the viewpoint of the effect of the present invention, [II-1], [II-2],
Examples include [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 up to 5 g is particularly preferably used.

General formula [IV] General formula [V] (In the above general formulas [IV] and [V], R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₅ , -COOR ₆ , Or, it represents a phenyl group. Also, R ₅ , R ₆ , R ₇ and R ₈
Each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₂ represents -OH or a hydrogen atom, R ₁ represents a halogen atom, a sulfonic acid group, or a carbon number of 1 to 1.
An alkyl group of 7, -OR ₅ , -COOR ₆ , Or, it represents a phenyl group. In the above general formulas [IV] and [V], examples of the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a methyl group,
Examples thereof include ethyl group, iso-propyl group, n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group and benzyl group, and R ₅ , R ₆ and The alkyl group represented by R ₇ and R ₈ has the same meaning as described above, and further includes an octyl group and the like.

Examples of the phenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Typical specific examples of the compound represented by the above general formula [IV] or [V] are shown below, but the invention is not limited thereto.

(IV-1) 4-isopropyl-1,2-dihydroxybenzene (IV-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (IV-3) 1,2,3-trihydroxybenzene-5- Carboxylic acid (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 (V-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (V-2) 2,3,8-trihydroxynaphthalene-6-
Sulfonic acid (V-3) 2,3-dihydroxynaphthalene-6-carboxylic acid (V-4) 2,3-dihydroxy-8-isopropyl-
Naphthalene (V-5) 2,3-dihydroxy-8-chloro-naphthalene-6-sulfonic acid Among the above compounds, as a compound particularly preferably used in the present invention, 1,2-dihydroxybenzene-3,5-
Examples thereof include disulfonic acid, which can also be used as an alkali metal salt such as sodium salt and potassium salt.

In the present invention, the compound is 5 mg to 2 per developer.
It can be used in the range of 0 g, preferably 10 mg ~ 10
Good results are obtained by adding g, more preferably 20 mg to 3 g.

The compounds of the present invention may be used alone or in combination. Furthermore, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2,
Other chelating agents such as phosphonocarboxylic acid such as 4-tricarboxylic acid and polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

General formula [VI] (Represented in the general formula [VI], R _1, R ₂ and R ₃ 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 _1, R ₂ and R
_{3 At} least one is a hydroxyl group, and at least one of R ₁ , R ₂ and R ₃ is a carboxylic acid group (including its salt) or a phosphoric acid group (including its salt). n ₁ , n ₂ and n ₃ each represent an integer of 1 to 3. ) In the general formula [VI], R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof). Examples of the salts of phosphoric acid groups include salts of alkali metal atoms and salts of alkaline earth metal atoms, and preferred salts of alkali metal atoms such as sodium and potassium. Further, at least one of R ₁ , R ₂ and R ₃ is a hydroxyl group, and at least one of R ₁ , R ₂ and R ₃ is
A carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof). R ₁ , R ₂ and R ₃ are preferably selected from a hydroxyl group, a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof).

n ₁ , n ₂ and n 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.

The addition of the compounds represented by the above [IV], [V] and [VI] can be used in the range of 0.1 to 100 g, preferably 1 to 50 g, per 1 color developing solution.

In the present invention, the concentration of sulfite in the color developing solution can be reduced, but it is preferably 0.6 × 10 ^-3 mol or less per color developing solution.

In the present invention, by setting the concentration of the sulfite to a certain value or less, it is possible to more favorably prevent a decrease in the coloring density of the dye pixel, and it is preferable to achieve the effect of the present invention more efficiently. It is a condition.

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

As the color developing agent used in the color developing solution used in the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because it causes less fogging.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the light-sensitive material and is less likely to cause skin contamination than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-henylenediamine. Not only has the advantage that the skin is less likely to become rashed, but the object of the present invention can be efficiently achieved especially by combining with the compound represented by the general formula [I] in the present invention.

The water-soluble group are those having at least one is listed p- phenylenediamine compounds of amine or on the benzene nucleus, a specific water-soluble group _{- (CH 2) n-CH} 2 OH, - ( _{CH 2) m-NHSO 2 -} (CH 2) n-CH 3, - (CH 2) mO- (CH 2) n-CH 3, - (CH 2 CH 2 O) nCmH 2m-1 (m and n are Each represents an integer of 0 or more), —COOH group, —SO ₃ H group and the like.

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

Illustrative coloring phenomenon Among the above-illustrated color developing agents, the occurrence of fogging is small, and therefore, the color developing agent preferably used in the present invention is No. (A-).
1) (A-2), (A-3), (A-4), (A-
6), (A-7) and (A-15), and particularly preferably No. (A-1).

The color developing agent is usually used in the form of salt such as hydrochloride, sulfate, p-toluenesulfonate.

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.

In the present invention, it is preferable to use a triazyl stilbene-based fluorescent whitening agent represented by the following general formula [VII] in the color developing solution according to the present invention because fogging is further reduced.

General formula [VII] 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 (for example, methoxy, ethoxy, methoxyethoxy, etc.),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
An aryl group (eg, phenyl, methoxyphenyl, etc.),
Amino group, alkylamino group (for example, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β
-Hydroxyethyl) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N′-methylamino,
N- (β-hydroxyethyl-N′-methylamino and the like), arylamino groups (for example, anilino, o-, m
-, P-sulfoanilino, o-, m-, p-chloroanilino, o-, m-, p-toluidino, o-, m-, p-
Carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M
Represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds can be mentioned, but not limited to these.

The triazyl stilbene whitening agent represented by the general formula [VII] is, for example, “Fluorescent Whitening Agent” edited by Chemical Industry Association (Showa
It can be synthesized by the usual method described on page 8).

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

As the alkaline agent other than the carbonate, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination, The effect of the present invention, that is, the precipitation is not generated, and it can be used in combination within a range of maintaining the pH stabilizing effect. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

Inorganic and organic antifoggants can be added if necessary.

Further, a development accelerator can be used if necessary. U.S. Pat.Nos. 2,648,604 and
3,671,247, various pyridinium compounds represented by JP-B-44-9503, and other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.Nos. 2,533,990, 2,531,8
No. 32, No. 2,950,970, No. 2,577,127, and polyethylene glycol and its derivatives described in JP-B-44-9504, and nonionic compounds such as polythioethers. Further, benzyl alcohol, phenethyl alcohol described in U.S. Pat. No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like can be mentioned.

In the above, particularly for poorly soluble organic solvents typified by benzyl alcohol, tar is liable to be generated particularly during running processing in a low replenishment system by using the color developing solution for a long time, and the generation of such tar is Depending on the proximity of the processed paper to the photosensitive material, it may even cause a serious failure that significantly impairs its commercial value.

In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome to use a stirring device to adjust the color developing solution itself, but also the use of such a stirring device results in poor solubility. Therefore, there is a limit to the effect of promoting development.

Furthermore, poorly soluble organic solvents have a large pollution load value such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since there are problems such as requiring labor and cost, it is preferable to reduce or eliminate the use amount as much as possible.

Furthermore, in the color developer of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509 are described. The compound can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl. -P-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g /. Besides this,
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, other various additives such as stain inhibitors, anti-sludge agents, baking soda effect accelerators, etc. can be used.

Each component of the color developer is added to a certain amount of water in order,
It can be prepared by stirring. In this case, a component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Also, more generally, a plurality of components each of which can coexist stably in a concentrated aqueous solution, or in a solid state prepared in advance in a small container is added to water and prepared by stirring to prepare a color developing solution of the present invention. Obtainable.

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

In the present invention, the processing temperature for color development is 30
The higher the temperature is from 50 ° C. to 50 ° C., the faster the rapid processing is possible, which is preferable. However, the image storage stability is preferably not so high, and the temperature is preferably from 33 ° C. to 45 ° C.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention 2, it is preferably within 2 minutes.
Further, it is preferable to carry out in the range of 30 seconds to 1 minute 30 seconds.

In the present invention, an aromatic primary amine color developing agent and at least one selected from diethylhydroxylamine and dimethylhydroxylamine are contained in an amount of 8.1 mol or more per 1 mol of the color developing agent, and the general formula [ I] can be applied to any system as long as it uses a color developer containing the compound represented by the formula [I]. For example, various treatment methods including one-bath treatment, for example, a spray method of atomizing the treatment liquid, or Various processing methods such as a wetting method by contact with a carrier impregnated with a processing solution or a developing method with a viscous processing solution can be used, but the processing step is substantially color development, bleach-fixing, washing with water or a stable alternative thereto. It consists of processes such as chemical treatment.

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 prepared by coordinating a gold ion such as iron, cobalt or copper with an organic acid such as aminopolyalboric acid or oxalic acid or citric acid. The most preferred organic acid used to form such a metal acid salt of an organic acid includes 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] Propylenediaminetetradifacid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyletherdiaminetetraacetic acid [10] Glycoletherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic 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'-triacetate sodium salt [18] Propylenediaminetetraacetate sodium salt [19] Nitriloacetate sodium salt [20] Cyclohexanediaminetetraacetate sodium salt 20-2
Use at 50g /. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. A bleach-fixing solution having 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 a bleaching agent of ethylenediaminetetraacetate iron (III) complex salt;
On the contrary, a bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added, and further, a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. A special bleach-fix solution can also be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in which they can be dissolved in an amount of 5 g / or more, but generally 70 g to 250 g /.

The bleach-fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffering agents such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds.
Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. Preservatives such as hydroxyamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organics such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate.

The bleach-fixing solution used in the present invention includes JP-A-46-280,
Japanese Patent Publication Nos. 45-8506 and 46-556, Belgian Patent No. 770,9
No. 10, JP-B-45-8836, JP-B-53-9854, JP-A-54-71
Various bleaching accelerators described in JP-A Nos. 634 and 49-42349 can be added.

The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally p
Used at H5.0 or higher and pH9.5 or lower, preferably pH6.0 or higher
Used below 8.5, and further stated the most preferred pH is 6.5
Processed above 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 alternative stabilized ground solution for water washing applicable to the present invention will be described.

The pH of the washing substitute alternative solution applicable to the present invention is 5.5 to 10.
The range is 0. As the pH adjusting agent which can be contained in the stabilizing solution for washing with water applicable to the present invention, any of generally known alkali agents or acid agents can be used.

The treatment temperature of the stabilizing treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ℃ ~ 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 that the treatment be performed sequentially with a treatment time that is 20% to 50% longer than that of the preceding tank. After the stabilization treatment applicable to the present invention, no water washing treatment is required,
Rinsing with a small amount of water and surface cleaning within an extremely short period of time can be optionally performed as needed.

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

As described above, in the present invention, the treatment with the washing substitute stabilizing solution refers to a treatment for stabilizing treatment in which the stabilizing treatment is performed immediately after the treatment with the treating solution having a bleach-fixing ability and the washing treatment is not substantially performed. The treatment liquid used for the stabilization treatment is called a water washing substitute stabilizer, and the treatment layer is called a stabilizing bath or a stabilizing tank.

The stabilization tank in the stabilization treatment applicable to the present invention is 1 to
It is preferably 5 tanks, particularly preferably 1 to 3 tanks, and at most 9 tanks or less.

The silver halide grains used in the silver halide color photographic light-sensitive material applicable to the present invention are silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, chloroiodo odor. Any of silver halide and a mixture thereof can be used,
Particularly, it is a silver halide grain containing at least 80 mol% of silver chloride, preferably 90 mol% or more, more preferably 95 mol% or more.

In a silver halide color photographic light-sensitive material consisting of a silver halide emulsion containing such silver halide grains, the color developing solution of the present invention is particularly advantageous because the dye concentration is remarkably lowered due to hydroxyamine or sulfite. Applied.

The silver halide emulsion containing silver halide grains composed of 80 mol% or more of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride.
In this case, silver bromide is not more than 20 mol%, preferably 10 mol%.
Or less, more preferably 5 mol% or less, and when silver iodide is present, it is 1 mol% or less, preferably 0.5 mol% or less. Such a silver halide grain substantially consisting of silver chloride according to the present invention contains 80% by weight or more of all the silver halide grains in the silver halide emulsion layer in which the silver halide grain is contained. It is preferable that it is made to exist, and it is more preferable that it is 100%.

The crystal of the silver halide grains used in the present invention may be a normal crystal, a twin crystal or any other crystal, and any ratio of [100] plane to [111] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (JP-A-58-113934, Japanese Patent Application No. 59-113934)
No. 170070) can also be used.

The silver halide grains used in the present invention may be obtained by any of the preparation methods such as an acid method, a neutral method, and an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When the silver halide grains are grown, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521 is used. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as primary sensitizers.
Tin salts, thiourea dioxide, polyamines, etc .; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3
-Methylbenzothiazolium chloride or the like or a sensitizer of a water-soluble group such as ruthenium, palladium, platinum, rhodium or iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (of these Some of them act as a sensitizer or an antifoggant depending on the amount thereof, etc.) alone or in combination (eg, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium). It may be chemically sensitized by combined use with a sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one hydroxytetradesignden and a nitrogen-containing heteromer having a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−3 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide, in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various sensitizing dyes can be used, and one or two sensitizing dyes can be used.
A combination of two or more species can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent No. 929.080, U.S. Pat.
31,658, 2,493,748, 2,503,766, 2,
519,001, 2,912,329, 3,656,959, and
No. 3,672,897, No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No.44-14
Examples thereof include those described in No. 030 and No. 52-24844. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.Nos. 1,939,201, 2,072,908, 2,739,149, and 2,945,763.
Typical examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes as described in British Patent No. 505,979. Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, U.S. Pat.Nos. 2,269,234, 2,270,378, and 2,
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in Nos. 442,710, 2,454,629, and 2,776,280. Furthermore, U.S. Patents 2,213,995 and 2,4
Cyanine dyes, merocyanine dyes or complex cyanine dyes as described in No. 93,748, No. 2,519,001, West German Patent No. 929,080, etc. can be advantageously used for a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion. .

These sensitizing dyes may be used alone or in combination.

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

As a particularly preferable spectral sensitizing method, a typical one is, for example, Japanese Patent Publication No. 43-4936 relating to a combination of benzimidazole carbocyanine and benzoxazolocarbocyanine.
No. 43-22884, No. 45-18433, No. 47-37443,
48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
53926, 59-116646, 59-116647 and the like.

Further, as a combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831, 47-11114, and
47-25379, 48-38406, 48-38407, 54-3
4535, 55-1569, JP-A-50-33220, 50-385.
No. 26, No. 51-107127, No. 51-115820, No. 51-135528
No. 52-104916 and No. 52-104917.

Further, as regards the combination of benzoxazolocarbocyanine (oxa carbocyanine) with other carbocyanines, see, for example, JP-B-44-32753 and JP-B-46-11627.
JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408, 48-41204, and 50-
40662, JP-A-56-25728, 58-10753, 58-9
1445, 59-116645, 50-33828 and the like.

As regards the combination of thiacarbocyanine with another carbocyanine, for example, JP-B-43-4932,
43-4933, 45-26470, 46-18107, 47-87
41, JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dyes can be advantageously used.

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 described in JP-B-50-40659 is used in advance. Is used by dissolving in a hydrophilic organic solvent.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Oxonol dye,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 584,60.
No. 9, No. 1,227,429, JP-A No. 48-85130, No. 49-9.
9620, 49-114420, 49-129537, 52
-108115, 59-25845, 59-111640, 59-111641, U.S. Pat.Nos. 2,274,782, 2,533,4
No. 72, No. 2,956,079, No. 3,125,448, No. 3,148,
No. 187, No. 3,177,078, No. 3,247,127, No. 3,26
0,601, 3,540,887, 3,575,704, 3,6
No. 53,905, No. 3,718,472, No. 4,071,312, No. 4,
The thing described in 070,352 can be mentioned.

These AI dyes are generally used in an amount of 2 per mol of silver in the emulsion layer.
It is preferable to use x10 ^{-3 to} 5 x 10 ^-1 mol, and more preferably 1 x 10 ^-2 to 1 x 10 ^-1 mol.

The photographic coupler used in the present invention is preferably a phenol compound or a naphthol compound as a cyan coupler, for example, U.S. Pat.
No. 2,434,272, No. 2,474,293, No. 2,895,826, No. 3,253,924, No. 3,034,892, No. 3,311,476,
No. 3,386,301, No. 3,419,390, No. 6,458,315
No. 3,476,563, No. 3,531,383, etc., and methods for synthesizing these compounds are also described in the publication.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolino-benzimidazole-based and indazolone-based compounds. As a pyrazolone-based magenta coupler, U.S. Pat.
No. 8, No. 3,062,653, No. 3,127,269, No. 3,311,4
No. 76, No. 3,419,391, No. 3,519,429, No. 3,558,
No. 318, No. 3,684,514, No. 3,888,680, JP-A-49-2
9639, 49-111631, 49-129538, 50-1304
No. 1, Japanese Patent Publication No. 53-47167, No. 54-10491, No. 55-30615
Examples of the pyrazolotriazole-based magenta couplers include the couplers described in U.S. Pat. No. 1,247,493 and Belgian Patent 792,525.
As the diffusion-resistant colored magenta coupler, a compound obtained by arylazo-substituting the coupling position of a colorless magenta coupler is generally used.
2,801,171, 2,983,608, 3,005,712, and
3,684,514, British Patent No. 937,621, JP-A-49-123625
No. 49-31448.

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 a reaction of an oxidized product of a developing agent, can be used.

As a photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylaceteanilide type yellow coupler which is generally widely used,
Hivaloyl acetanilide type yellow couplers can be used. Further, a 2-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction is also advantageously used. Examples of these are U.S. Pat.Nos. 2,875,057 and 3,265,5.
No. 06, No. 3,664,841, No. 3,408,194, No. 3,277,155
No. 3,447,928, 3,415,652, Japanese Patent Publication No.49-13
576, JP-A-48-29432, 48-68834, 49-107.
No. 36, No. 49-122335, No. 50-28834, No. 50-132926
, Etc. together with the synthesis method.

The amount of the above diffusion-resistant coupler used in the present invention is generally from 0.05 to 1 mol per mol of silver in the light-sensitive 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 which releases a development inhibitor upon development is also included in the present invention. For example, U.S. Patent Nos. 3,297,455 and 3,379,529, West German patent application (OL
S) 2,417,914, JP-A Nos. 52-15271, 53-9116,
Examples thereof include those described in Nos. 59-123838 and 59-127038.

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

Thus, a typical example of a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitory action when released from the active site is introduced into the coupler active site, for example, British Patent No. 935,454. , U.S. Pat. No. 3,2
27,554, 4,095,984, 4,149,886, etc.

The above-mentioned DIR coupler forms a dye when the mother nucleus of the coupler reacts with the oxidation product of the color developing agent,
On the other hand, it has the property of releasing a development inhibitor. In the present invention, U.S. Pat.Nos. 3,652,345, 3,928,041, and 3,
958,993, 3,961,959, 4,052,213, JP-A-53-110529, 54-13333, 55-161237, etc. and the oxidation reaction of the color developing agent and the coupling reaction. Also included are compounds which, when released, release a development inhibitor but do not deform the dye.

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.

Further, the timing group as described above is present in the coupler mother nucleus which forms a completely diffusible dye when it reacts with the oxidized product of the color developing agent described in JP-A-58-160954 and JP-A-58-162949. It also includes a bound timing DIR compound.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure 17643. Agent,
A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardening agent, a surfactant, 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, the hydrophilic colloid used for preparing the emulsion includes gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, a protein such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support of the silver halide color photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support having a reflective layer, or a reflective plate, such as a glass plate, Examples include a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and may be other ordinary transparent supports. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Pat.No. 2,761,
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 791 and No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic paper light-sensitive material, an arrangement of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order from the support side is preferred. . Each of these light sensitive silver halide emulsion layers may consist of two or more layers.

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, and various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are appropriately used as constituent layers. It can be used in combination. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

In the method of processing a silver halide color photographic light-sensitive material of the present invention, as a silver halide color light-sensitive material, a color paper, as long as it is a light-sensitive material processed by a so-called internal development method containing a coupler in the light-sensitive material, It can be applied to any silver halide color photographic light-sensitive material such as color negative film, color positive film, slide color reversal film, movie color reversal film, TV color reversal film and reversal color paper.

[Specific Effect of the Invention] As described above, according to the present invention, a silver halide color photographic light-sensitive material having excellent storage stability of a color developer and excellent photographic characteristics of the maximum color density of a dye image obtained can be obtained. A treatment method could be provided.

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

[Reference Example 1] Color developer Nos. 1 to 30 having the following compositions were prepared.

(Color developer) Potassium chloride 1.0 g Potassium sulfite 0.2 g (0.0013 mol /) Preservative (shown in Table 1) Chelating agent (Exemplified compound II-) 5.0 g Color developing agent (Exemplified compound A-1) 4.38 g ( 0.01 mol /) Potassium carbonate 30 g Triethanolamine (TEA) 11 g (0.074 mol /) Add water to make 1 and adjust pH to 10.1 with potassium hydroxide and sulfuric acid.
Adjust to 5.

Half of the above color developing solutions Nos. 1 to 30 remain unadded, and the other half contain 4 ppm of ferric ion, 2 ppm of copper ion and 100 ppm of calcium ion (FeCl ₃ , CuSO ₄ .6H ₂ O and CaCl _{2 respectively).}
(Dissolved and added), and the opening ratio was 150 cm ² /
It was stored for 10 days in a glass container having an air contact area of 150 cm ² for the color developer of 1. The appearance (coloring degree) of the color developing solution after 1 week was observed.

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

++ Generation of a large amount of tar ++ Blackening + Coloring (quite discoloration) -Almost no discoloration. Also, the concentration of the color developing agent in the color developing solution is analyzed by the cerium sulfate method, and the concentration of the color developing agent becomes 0. Was determined as the life of the color developer.

 These results are also shown in Table 1.

As is clear from Table 1, when hydroxylamine sulfate (HAS) is used as a preservative, No.1A to No.10A, which does not contain metal, has relatively good storage stability, but the liquid appearance is considerably blackened. There is. In addition, N mixed with metal ions
From o.1B to No.10B, the preservability is remarkably lowered, and it is understood that tar is generated.

On the other hand, in the preservatives of the present invention, such as diethylhydroxylamine (DEHA) and dimethylhydroxylamine (DMHA), when the amount is less than 8.1 mol per mol of the color developing agent, No. 11A to No. 14A which does not mix metal ion and No.21A ~ N
With o.24A, although storage stability is equivalent to or less than No.1A to No.10A, tar is also generated, but even if metal ions are mixed (No.11B to No.14B and No.21B to No. .24B) has almost no change in storage stability.

However, DEHA or DMHA was added to 8.1 mol per 1 mol of color developing agent.
No. 1 that does not mix metal ions when added in excess of mol
5A ~ No. 20A and No. 25A ~ No. 30A and No. 15B ~ No. 20B mixed with metal ions and No. 25B ~ No. 30B any color developing solution liquid appearance, both storage stability, It turns out that it is extremely good.

[Reference Example 2] Using the color developer used in Reference Example 1, the same experiment as in Reference Example 1 was repeated. However, here, the types of preservatives and the addition amounts thereof were as described in Table 2, and the amounts of triethanolamine and the addition amount of potassium sulfite were also as described in Table 2.

The residual amount of the color developing agent was analyzed by the cerium sulfate method to determine the life of the color developing solution as in Reference Example 1, and the results are shown in Table 2.

As is clear from Table 2, when only sulfite is contained as a preservative (No.31 to 34), the storage stability can be improved to some extent by increasing the amount of sulfite, but hydroxylamine sulfate is used as a preservative. (HAS), Diethylhydroxylamine (DEHA), Dimethylhydroxylamine (DM
When only HA is included (No.35 to No.40), the storage stability is extremely poor. On the other hand, when HAS and triethanolamine are used in combination (No.41, 42, 47, 50, 53), some storage stability is obtained when metal ions are not mixed,
Although the storage stability is further improved by increasing the amount of sulfite, the storage stability is remarkably reduced due to the incorporation of metal ions. On the other hand, when DEHA or DMHA is used in combination with triethanolamine, when the amount of DEHA or DMHA added is small (N
o.43,45) Although the storage stability is poor, increasing the addition amount (No.44,46) improves the storage stability and increasing the amount of sulfite (No.48,49,51, 52,54,55) The storage stability is further improved. Further, it can be seen that in Nos. 44, 46, 48, 49, 51, 52, 54 and 55, good storage stability is maintained even if metal ions are mixed.

[Reference Example 3] The same experiment as in Reference Example 1 was repeated using the color developing solution used in Reference Example 1. However, here, the kind and the addition amount of the preservative are as described in Table 3, and instead of 11 g of triethanolamine, the alkanolamine represented by the general formula [I] shown in Table 3 is used. The amount indicated in the table was added, and the life of the color developing solution was determined in the same manner as in Reference Example 1, and the results are shown in Table 3.

As is clear from Table 3, no matter which compound represented by the general formula [I] is used, good storage stability can be obtained.

[Reference Example 4] On a polyethylene-laminated paper support, the following layers were sequentially coated from the support side to prepare a silver halide photosensitive material.

Layer 1 ... gelatin ^{1.20g / m 2, 0.40g / m} 2 ( in terms of silver, hereinafter the same) blue-sensitive silver halide emulsion (AgBr: AgCl = 4: 96 ) and dissolved in dioctyl phthalate 0.55 g / m ² 1.0 × 10
^-3 mol g / m ² of yellow coupler (Y-1) layer layer ² ... 0.70g / m 2 containing the intermediate layer layer 3 ... 1.20g / m ² made of gelatin gelatin of 0.22 g / m ² Amount containing the green-sensitive silver halide emulsion (AgBr: AgCl = 3: 97) and 1.0 × 10 ⁻³ mol g / m ² of the following magenta coupler (M-1) dissolved in 0.30 g / m ² of dioctyl phthalate. .

Layer 4 ... Intermediate layer consisting of 0.70 g / m ² of gelatin.

Layer 5 ... gelatin 1.20 g / m ^2, of 0.28 g / m ² red-sensitive silver chlorobromide emulsion (AgBr: AgCl = 4: 96 ) and 0.25 g / m ² of 1.75 × dissolved in dibutyl phthalate ^10-3 A layer containing the following cyan coupler (C-1) in mol g / m ² .

Layer 6 A layer containing 1.02 g / m ² of gelatin and 0.32 g / m ² of Tinuvin 328 (UV absorber manufactured by Tiga Geigy) dissolved in 0.25 g / m ² of dioctyl phthalate.

Layer 7: Layer containing 0.48 g / m ² of gelatin. As a hardening agent, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to layers 2, 4 and 7 so that the amount was 0.017 g per 1 g of gelatin.

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

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

Processing process Processing temperature Processing time [1] Color development 35 ℃ 45 seconds [2] Bleach fixing 35 ℃ 45 seconds [3] Water washing 30 ℃ 90 seconds [4] Dry 60-80 ℃ 60 seconds Color developing solution is a reference example. The preservative used in Example 1 was used, but 0.10 mol of the preservative described in Table 4 was added, and triethanolamine and potassium sulfite were added in the amounts described in Table 4. Further, the chelating agent shown in Table 4 was added in an amount as shown in Table 4. The bleach-fix solution used had the following composition.

[Bleach fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Add water to make the total amount 1 Adjust to pH 7.1 with potassium or glacial acetic acid.

The same amount of the same metal ions as in Example 1 was added to the color developing solution, and the color developing solution was stored under the same conditions as in Example 1 and developed three times immediately after storage (immediate day), after 3 days and after 7 days. The minimum concentration of magenta dye and the maximum concentration of yellow dye in the liquid were measured using an optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo KK), and the results are shown in Table 4.

As is clear from Table 4, when HAS is used as a preservative and TEA is not used (Sample Nos. 1 to 3), the storage stability is increased by the addition of sulfite, but the maximum reflection density of the yellow dye is Low, the minimum reflection density of the magenta dye is high when the capacity of the color developer remains. In contrast, HAS and T
When EA was also used (Sample Nos. 4 to 6), the sulfite was 0.
However, the minimum reflection density of the magenta dye is high even though it has some storage stability. The storage stability is further improved by adding sulfite, but the maximum reflection density of the yellow dye is low and the minimum reflection density of the magenta dye is high. On the other hand, a system in which DEHA or DMHA and TEA are used together (Sample No. 7-1
In 4), even when the amount of sulfurous acid is 0, the storage stability is good, so that it is not necessary to add a sulfite, and therefore a high maximum reflection density of the yellow dye is obtained. Further, it is understood that although the minimum reflection density of the magenta dye is low, it can be further improved by using the chelating agent together.

[Example 1] The exemplary compound (A'-) was added to the color developing solution used in Reference Example 4.
2), (A'-4) and (A'-9) (all of which are triazyl styrene benzene optical brighteners) were added in an amount of 2 g / each. The lowest concentration was improved by 0.01 to 0.02.

[Reference Example 5] Color developing agent (A- in the color developing solution used in Reference Example 4).
When 1) was changed to (B-1) or (B-2) below and the same experiment was conducted, the minimum magenta density of the unexposed area deteriorated by 0.02. Similarly, the color developing agent (A-1) of Reference Example 4 was replaced with the exemplified compound (A-2),
When (A-4) and (A-15) were changed to perform the same experiment as in Reference Example 4, almost the same results were obtained.

Reference Example 6 The sample used in Reference Example 4 (however, the silver halide composition was
(Shown in the table) and used as a color developer in Reference Example 1 (however, the preservative and potassium sulfite are the fifth
(Shown in the table), the same metal ion as in Reference Example 1 was added in the same amount, and stored under the same conditions as in Reference Example 1. Immediately after storage (immediately) and after 7 days, the product was treated twice and halogenated. We examined the effect of silver composition, preservative and sulfite concentration on the maximum reflection density of yellow dye. The results are shown in Table 5.

As is clear from the table, when HAS is used and the sulfite is 0 (Sample Nos. 15 to 21), the dye concentration on the same day decreases when the silver chloride content is 80 mol% or more, and the storage stability of the liquid is stable. Although the property is poor, by adding sulfite (Sample No.22 to 2
8), the storage stability of the liquid is improved, but the silver chloride content is 80
The decrease of the dye concentration becomes more remarkable when the amount is more than mol%. On the other hand, when DEHA or DMHA is used (Sample No. 29 to 4
2) There is little decrease in dye concentration, and even if the amount of sulfite is 0, the storage stability of the liquid is good, so it is not necessary to add further sulfite, and therefore, even if the content of silver chloride is 80% or more, good dye concentration is achieved. Can be obtained.

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Claims (2)

(57) [Claims] 1. An aromatic primary amine color developing agent having a water-soluble group and at least one selected from diethylhydroxylamine and dimethylhydroxylamine in an amount of 8.1 mol or more per 1 mol of the color developing agent.
A color developer containing a compound represented by the following general formula [I] and a triazylstilbene-based optical brightening agent. General formula [I] (In the formula, R ₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₂
And R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. ) 2. A method of processing a silver halide color photographic light-sensitive material, which comprises subjecting a silver halide color photographic light-sensitive material to imagewise exposure and then performing a processing including at least a color development step. Contains an aromatic primary amine color developing agent having a water-soluble group and at least one selected from diethylhydroxyamine and dimethylhydroxylamine in an amount of 8.1 mol or more per 1 mol of the color developing agent, and has the following general formula: A method of processing a silver halide color photographic light-sensitive material, which comprises a compound represented by [I] and a triazylstilbene-based optical brightening agent. General formula [I] (In the formula, R ₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₂
And R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. )