JPH07104576B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a color developing solution and a processing method for a silver halide color photographic light-sensitive material, and more specifically, a halogen having excellent photographic characteristics such as fog and maximum color density. The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials and a processing method.

BACKGROUND OF THE INVENTION Usually, in a method of processing a silver halide color photographic light-sensitive material to form a dye image, an oxidized p-phenylenediamine type color developing agent and a dye image-forming coupler are provided after imagewise exposure. And are reacted to form a dye image. In this method, a color reproduction method by a subtractive color method is usually applied, and cyan, magenta, and yellow dye images corresponding to red, green, and blue are formed on respective photosensitive layers. In recent years, in forming such a dye image, in order to shorten the development processing time, a high temperature development processing and a processing step are generally omitted. In particular, in order to shorten the development time, it is extremely important to increase the development speed in color development. The development speed in color development is affected by two directions. One is a silver halide color photographic light-sensitive material, and the other is a color developing solution. In the former case, above all, the composition of the grains of the silver halide emulsion used has a great influence on the development rate, and in the latter case, the conditions and composition of the color developing solution have a great influence on the development rate.

Conventionally, hydroxylamine and sulfite have been used as preservatives for color developing solutions. Hydroxylamine is particularly effective as a preservative for P-phenylenediamine color developing agents.

However, hydroxylamine has the drawback of being oxidized and decomposed to produce ammonia NH ₃ . This ammonia acts on the silver halide photographic light-sensitive material to cause ammonia fogging on the light-sensitive material. In particular,
Heavy metal ions present in color developers (Fe ³⁺ , Cu ^2+, etc.)
By this, hydroxylamine is more easily decomposed.

Various chelating agents have been conceived and used to chelate heavy metal ions and prevent their action. Specific examples of these chelating agents include aminopolycarboxylic acids, polyphosphoric acids, and organic phosphoric acids. However, although these chelating agents are effective for Fe ³⁺ , they are less effective for Cu ²⁺ .

In addition, due to the recent economic trend and the tendency to lower the replenishment of the color developing solution to reduce the amount of waste liquid, Cu ²⁺ and Fe in the color developing solution have been added.
^Since the concentration of ³⁺ tends to be high, it is more and more desired to eliminate the above-mentioned drawbacks.

On the other hand, a silver halide color photographic light-sensitive material (hereinafter, referred to as a light-sensitive silver halide emulsion substantially composed of silver chloride)
It is called a silver chloride color photographic light-sensitive material. ) Is developed more rapidly than conventional color photographic light-sensitive materials comprising silver bromide such as silver chlorobromide, silver chloroiodobromide and silver iodobromide emulsions and silver halide emulsions containing silver bromide, Moreover, since bromide ions and iodide ions that suppress the development reaction are not accumulated in the color developing solution, they are extremely useful as a light-sensitive material for rapid processing.
As a result of various studies using the silver chloride color photographic light-sensitive material suitable for this rapid processing, the present inventor has found that it has the following drawbacks.

That is, first, the hydroxylamine, which has been conventionally used as one of the preservatives, acts as a developer of silver chloride, silver development proceeds, and the color density of the dye image finally obtained. Has dropped.

Secondly, the sulfite salt used as another conventional preservative acts as a silver chloride dissolving agent, and the physical development by the color developing agent progresses rapidly, resulting in a silver developing reaction and a coupling reaction. Is out of balance. That is, the color development density was lowered because the silver development proceeded too far and the coupling reaction was delayed.

According to a study by the present inventors, it has been found that fogging is likely to occur particularly when metal ions are mixed. Although the fog is large as a whole, the fog of cyan color used for preventing the decrease of the dye image density is particularly large.

This heavy metal ion becomes a particular problem when a large amount of light-sensitive materials are continuously processed.

Further, in a development processing method in which a silver halide photographic light-sensitive material is continuously processed by an automatic developing machine or the like, in order to keep the components of the color developing solution within a certain concentration range in order to avoid a change in development finish characteristics due to a change in component concentration. Means are necessary. As such means, a method of replenishing a replenisher for compensating the deficient component and diluting the unnecessary increasing component is usually used. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method poses a serious economic and pollution problem. Therefore, in recent years, in order to reduce the overflow liquid, a so-called concentrated low replenishment system in which these replenisher liquids are concentrated and replenished in a small amount is widely used. The generation of fog due to ions becomes a problem, and its solution is strongly desired.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material that suppresses ammonia fogging, chelate heavy metal ions, and does not cause excessive development even when a silver chloride color photographic light-sensitive material is used. It is an object of the present invention to provide a color developing solution and a method for processing a silver halide color photographic light-sensitive material using the same.

[Structure of the Invention] The present invention comprises: after imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer,
In a method for processing a silver halide color photographic light-sensitive material, which is subjected to a treatment including at least a color developing step; the color developing solution used in the color developing step comprises a compound represented by the following general formula (I) and a general formula (II) below. ) And at least one compound selected from the compounds represented by (III); the silver halide emulsion layer contains silver halide grains composed of 80 mol% or more of silver chloride, and silver halide At least one cyan coupler selected from the cyan couplers represented by the following general formulas (CI) and (C-II) is contained in at least one of the emulsion layers; a silver halide color photographic light-sensitive material characterized by the following: Is the processing method of.

General formula (I) (In the formula, R ₁ and R ₂ each represent an alkyl group having 1 to 3 carbon atoms.) General formula (II) General formula (III) (In the above general formulas (II) and (III), R ₁ , R ₂ , R ₃ , R ₄ , R
₉ and R ₁₀ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₅ , or —COO.
R ₆ , Alternatively, it represents a phenyl group. Also, R ₅ , R ₆ , R ₇ and R ₈
Are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

General formula (C-I) General formula (C-II) (In the above general formulas (C-I) and (C-II), Y is -CO
R ₄ , -SO ₂ R ₄ , Represents -CONHCOR ₄ or -CONHSO ₂ R ₄ , (R ₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group , An aryl group or a heterocyclic group, or R ₁ and R ₅ may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded.), R ₃ is a ballast And Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine color developing agent. ) Further, at least one of the silver halide emulsion layers may contain a cyan coupler represented by the following general formula (C-III).

General formula (C-III) (In the general formula (C-III), one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group having 2 to 12 carbon atoms, and X is a hydrogen atom or the child. Is a straight-chain or branched-chain alkyl group having a number of 2 to 12, wherein X is a hydrogen atom or a group capable of splitting off by a coupling reaction with the oxidation product of the N-hydroxyalkyl-substituted p-phenylenediamine derivative color developing agent. R ₂ represents a ballast group.) [Specific Structure of the Invention] In the color developing solution used in the present invention, the following general formula (I) is used in place of hydroxylamine which has been used as a preservative. The compound shown (hereinafter referred to as the preservative of the present invention) is used.

General formula (I) (In the formula, R ¹ and R ² each represent an alkyl group having 1 to 3 carbon atoms.) In the general formula (I), R ¹ and R ² each have 1 to 1 carbon atoms.
The alkyl group having 1 to 3 carbon atoms represented by R ¹ and R ² may be the same or different, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and iso.
-Propyl group and the like.

R ¹ and R ² are preferably both ethyl groups.

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

These compounds of the present invention are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate and acetate.

The concentration of the compound (I) of the present invention in the color developing solution is preferably the same level as that of hydroxylamine usually used as a preservative, for example, 0.1 g / l to 50 g / l is used, and more preferably 0.5 g. It is / l to 30 g / l.

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

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 sulfite should be used as a preservative. However, it is known that the storage stability thereof is extremely poor when it is added to the color developing solution to cause a cross-oxidation reaction with the color developing agent. Hydroxylamine has little effect on the preservative of the black-and-white developing agent added to the color developer.

As a preservative of the main ingredient of black and white developer added to color developer
As an example of using N, N-diethylhydroxylamine, a color photographic light-sensitive material is developed by a reversal method using a color developing solution containing a coupler. It is known to be used with phenidone in the so-called external color 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 developer 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).

As a preservative for black and white developing agents added to color developers
Other examples of using compounds of the present invention, such as N, N-diethylhydroxylamine, in internal color developers are:
Technology for preserving the phenidone derivative added to the color developing solution (see JP-A-53-32035) and similarly technology for retaining the phenidone derivative 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.

As described above, some of the compounds of the present invention are already known as preservatives for black-and-white developing agents added to the color developing solution, but in the present invention, the compounds of the present invention are colored in the usual colors. It not only acts effectively as a preservative in the developer but also does not reduce the color density in combination with the specific couplers described in detail below, and further has the general formula (I
By using it in combination with at least one selected from the chelating agents represented by I) and (III), fogging due to the incorporation of heavy metal ions can be satisfactorily prevented, and there is no decrease in pH or tar, and a color developer. It was an unexpected and unexpected effect that the excellent stability was obtained.

In method for processing a silver halide color photographic material of the present invention, color development step sulfite concentration of the color developer used in the color developing solution per 2 × 10 ^-2 mol or less, particularly preferably 4 × 10 ^{- It is 3} mol or less.

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 image, 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.

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

The color developer used in the present invention contains at least one compound selected from the compound represented by the general formula (II) and the compound represented by the general formula (III) (hereinafter referred to as the chelating agent of the present invention). .

General formula (II) General formula (III) In the general formulas (II) and (III), R ₁ , R ₂ , R ₃ , R ₄ and R ₉
And R ₁₀ 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 , Alternatively, 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.

The alkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and R ₁₀ includes substituted and unsubstituted alkyl groups such as methyl group, ethyl group, iso-propyl group, n-propyl group, t- Examples thereof include a butyl group, an n-butyl group, a hydroxymethyl group, a hydroxyethyl group, a methylcarboxylic acid group and a benzyl group, and the alkyl group represented by R ₅ , R ₆ , R ₇ and R ₈ has the same meaning as described above. And further include an octyl group and the like.

Examples of the phenyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and R ₁₀ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Typical specific examples of the chelating agent of the present invention are shown below, but the chelating agent is not limited to these.

(II-1) 4-isopropyl-1,2-dihydroxybenzene (II-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (II-3) 1,2,3-trihydroxybenzene-5- Carboxylic acid (II-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (II-5) 1,2,3-trihydroxybenzene-5-carboxy-n-butyl ester (II-6) 5-t-butyl-1,2,3-trihydroxybenzene (II-7) 1,2-dihydroxybenzene-3,5,6-trisulfonic acid (II-8) 1,2-dihydroxybenzene-6- Chloro-
3,5-Disulfonic acid (II-9) 1,2-dihydroxybenzene-3,4,5,6-tetrasulfonic acid (III-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (III-2) 2,3,8-Trihydroxynaphthalene-6-sulfonic acid (III-3) 2,3-dihydroxynaphthalene-6-carboxylic acid (III-4) 2,3-dihydroxy-8-isopropyl-naphthalene (III-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-disulfonic acid can be mentioned, and sodium It can also be used as an alkali metal salt such as salt or potassium salt.

In the present invention, the compound (II) and / or (III) of the present invention can be used in the range of 5 mg to 20 g per developer, preferably 10 mg to 10 g, and more preferably 20 m.
Good results are obtained by adding g-3 g.

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

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 preferable.

The p-phenylenediamine compound having a water-soluble group is
Compared with para-phenylenediamine compounds that do not have a water-soluble group such as N, N-diethyl-p-phenylenediamine, not only does it have the advantage of not contaminating the light-sensitive material and being less prone to skin rash, In the invention, the object of the present invention can be efficiently achieved by combining with the compound represented by the general formula (I).

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as 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) nCmH2m + 1 (m and n are each It represents an integer of 0 or more), —COOH group, —SO ₃ group and the like.

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

Illustrative coloring phenomenon Among the color-developing agents exemplified above, the occurrence of fogging is small and preferred in the present invention is Exemplified No. (A-1),
(A-2), (A-3), (A-4), (A-6),
The compounds represented by (A-7) and (A-15) are preferred, and No. (A-1) is particularly preferred.

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, it is preferably used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developer, but from the viewpoint of rapid processing, it is 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per color developer. Is more preferable.

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.
US Pat. Nos. 2,648,604 and 3,67 as development accelerators.
1,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.No. 2,533,990, Second 2,531,832
No. 2,950,970, No. 2,577,127, and Shokoku Sho
Polyethylene glycol and its derivatives described in 44-9504, nonionic compounds such as polythioethers, organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine,
Triethanolamine and the like are included. Also US Patent No. 2,
Examples thereof include benzyl alcohol, phenethyl alcohol described in No. 304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

In the above, particularly for poorly soluble organic solvents typified by benzyl alcohol, by using the color developing solution for a long period of time, tar easily occurs particularly in running processing in a low replenishment system, and the generation of such tar is Adhesion to the processed paper sensitive material 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 to increase 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'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g / l. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound or the like can be added.

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

Each component of the above color developing solution can be prepared by sequentially adding and stirring to constant water. 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 color developer can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 13.0.

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the quicker the processing can be performed in a shorter time, which is preferable, but it is preferable that the temperature is not so high from the viewpoint of image storage stability, and the temperature is preferably 33 ° C. or higher and 45 ° C. or lower.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it can be set within 2 minutes.
It is also possible to perform in the range of 30 seconds to 1 minute 30 seconds.

In the present invention, a color developer containing at least one compound selected from the compound represented by the general formula (I), the compound represented by the general formula (II) and the compound represented by the general formula (III). Can be applied to any system as long as it is a system using, for example, various other methods including one-bath treatment, for example, a spray method of atomizing the treatment liquid, or a web by contact with a carrier impregnated with the treatment liquid. Although various processing methods such as a method or a developing method using a viscous processing solution can be used, the processing steps substantially include steps such as color development, bleach-fixing, washing with water or a stabilizing process in place thereof.

In the bleach-fixing step, the bleaching step and the fixing step may be separately provided, or a bleach-fixing bath in which bleaching and fixing are processed in one 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 acid of an organic acid. The complex acid is an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid in which a metal ion such as iron, cobalt or copper is coordinated. 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] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine Citric acid (or tartaric acid) [9] Ethyl Etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenediaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are preferably 5-450 g / l. 20-250g
Use with / l. 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. Also,
A bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and the above-mentioned silver halide fixing agent and a halide such as ammonium bromide are added, or conversely, a large amount of a halide such as ammonium bromide is added. It is also possible to use a bleach-fixing solution having a composition added to the above, and a special bleach-fixing solution having 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. . As the halide, other than ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonia iodide, etc. may be used. 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 the range of 5 g / l or more so that they can be dissolved, but generally 70 g to 250 g / l are used.

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 kinds. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents 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-B-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910.
No. 5, Japanese Patent Publication No. 45-8836, No. 53-9854, JP-A-54-7163
Various bleaching accelerators described in No. 4 and No. 49-42349 can be added.

The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally
Used at pH 5.0 to pH 9.5, preferably pH 6.0 to pH
Used below 8.5, further stated the most preferred pH is 6.5
Processed above 8.5. The processing temperature is 80 ° C. or lower and 3 ° C. or higher, preferably 5 ° C. higher than the processing solution temperature in the color developing tank
Although it is used at a lower temperature, it is preferably used at 55 ° C or lower while suppressing evaporation and the like.

In the present invention, following the color development and bleach-fixing steps, washing with water or treatment with an alternative washing solution,
So-called washing substitute stabilization treatment is performed.

The washing substitute solution and the treatment with the washing substitute solution of the present invention refer to a treatment and a treatment solution which are carried out in place of the washing treatment performed after the fixing step or the bleach-fixing step.

The conventional washing process is a processing solution of a pre-bath contained in a constituent film of a light-sensitive material, specifically, a large amount of thiosulfate or a chemical in a fixing or bleach-fixing solution, a silver complex salt or a developing solution. It is to remove the chemicals by washing with water, and the treatment method is to apply a large amount of running water to the photosensitive film surface and immerse it in a washing bath so that the washing water flows away as quickly as possible, or to remove the photosensitive material in a certain amount of water. There is a replacement water washing method in which immersion is repeated and replacement with fresh water after a certain period of time is repeated.Usually, only water is treated, but in order to increase the treatment speed, sodium sulfite or the like before the water washing treatment is added. A method of immersing in a bath containing salt for several minutes and then washing with water may be used. In any case, the washing process is performed with water. Therefore, in order not to cause troubles such as drying of the light-sensitive material due to residual chemicals such as thiosulfate in the light-sensitive material, image contamination during storage, discoloration or brown color, wash with a very large amount of washing water. It is necessary and equipment for discarding the water after the water washing treatment is also required, which is not preferable spatially and economically. The washing substitute solution and the washing substitute treatment of the present invention are improvements of these drawbacks, and the treatment liquid used is not just water but an antifungal, antiseptic and aqueous solution having a sterilizing means,
Further, if necessary, an aqueous solution containing a compound such as a chelating agent having a chelate stability number for ferric ions of 8 or more, an ammonia compound, an organic acid salt, a pH adjusting agent, a surfactant, a sulfite, an optical brightening agent, etc. Is.

In the conventional washing process, the unit area of the photosensitive material to be processed is 1
Compounds such as thiosulfate adhering to and penetrating the light-sensitive material were washed away by replenishing about 5 l to 150 l of water per m ² , but the unit of the light-sensitive material processed in the low replenishment washing process of the present invention. Compounds adhering to and permeating the light-sensitive material can be washed away with a replenishing amount of about 0.01 to 2.5 l per 1 m ^{2 of} area. Further, in the processing method of the present invention, as described above, the replenishment amount is very small compared to the conventional water washing processing, so that the water supply and discharge pipe facility for the automatic developing machine, which was indispensable in the conventional water washing processing step. Was not always necessary, and we were able to achieve downsizing of equipment.

Hereinafter, the treatment with the washing substitute solution applicable to the present invention will be described.

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

The treatment temperature of the washing substitute solution is 15 ° C to 60 ° C, preferably 20 ° C to 45 ° C. Also, the processing time is preferably as short as possible from the viewpoint of rapid processing, but usually 20 seconds to
The treatment time is 10 minutes, most preferably 1 to 3 minutes. In the case of the treatment with the washing substitute solution using a plurality of tanks, it is preferable that the treatment is performed in a shorter time in the former tank and longer in the latter tank. In particular, it is desirable to perform the treatment sequentially with a treatment time that is 20% to 50% longer than that of the previous tank. No washing treatment is required after the treatment with the washing substitute solution applicable to the present invention, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed.

In the case of a multi-tank countercurrent system, the method of supplying the washing substitute solution in the treatment step with the washing substitute solution applicable to the present invention is preferably to supply to the subsequent bath and overflow from the previous bath. Of course, it can also be processed in a single tank. As a method for adding the above compound, the above compound and other additives are added to the washing substitute tank (or stabilizing tank) as a concentrated liquid, or the above-mentioned compound and other additives are added to the washing substitute tank, and this is washed with water. There are various methods such as whether to use the supply solution for the alternative solution, but any addition method may be used.

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

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

According to a preferred embodiment of the present invention, the method of processing a silver halide color photographic light-sensitive material of the present invention comprises a compound of the present invention and a chelate of the present invention as a color developer, ie, a preservative, used in the present invention. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains composed of 80% by mol or more of silver chloride is processed using a color developer containing an agent.

The silver halide grains used in the silver halide color photographic light-sensitive material applied to the present invention are preferably silver halide grains containing at least 80 mol% of silver chloride, more preferably 90 mol% or more, Most preferably, it contains 95 mol% or more.

The silver halide emulsion containing silver halide grains consisting 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. The silver bromide content is 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and when silver iodide is present, 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 grain used in the present invention may be a normal crystal, a twin crystal, or another 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 have 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 (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-
No. 170070) can also be used.

The silver halide grains used in the present invention may be those obtained by any of the acid method, the neutral method and the 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 stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 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 (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the 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 kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and 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 ^{−8 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 kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes 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 allogenated emulsion, for example, West German Patent No. 929,080, U.S. Pat. No. 3,656,959, 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. 4414030, No. 52-
Those listed in No. 24844 and the like can be mentioned. Further, sensitizing dyes used in insulating silver halide emulsions are described, for example, in U.S. Pat.Nos. 1,939,210, 2,072,908, 2,739,149, 2,945,763, and British Patent 505,979. Representative examples thereof include cyanine dyes, merocyanine dyes, or complex cyanine dyes. 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, cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in U.S. Pat. It can be advantageously used in a sensitive silver allogenide emulsion.

These sensitizing dyes may be used alone or in combination.

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

A particularly preferable example of the spectral sensitization method is, for example, Japanese Patent Publication No. 43936/43936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43, No. 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 a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47
-25379, 48-38406, 48-38407, 54-345
No. 35, No. 55-1569, JP-A No. 50-33220, No. 50-38526
No. 51, No. 51-107127, No. 51-115820, No. 51-135528
No. 52-104916, No. 52-104917, etc.

Furthermore, examples of combinations of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines include, for example, JP-B-44-32753 and 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.

Further, examples of combinations of thiacarbocyanine with other carbocyanines include, for example, Japanese Patent Publication Nos. 43-4932 and 43
-4933, 45-26470, 46-18107, 47-8741
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.

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 described in JP-B-50-40659 can be used. It is used by dissolving it in the 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 be added with a water-soluble or decolorizable dye (AI dye), such as an oxonol dye or hemioxonol. 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. 1,277,429, JP-A-48-85130, No. 49-99620, No. 49-114420, No. 49-129537, No. 52-108115, No. 59-25845. No. 59-111640, No. 59-111641, U.S. Pat. , No. 3,260,601, No. 3,540,887, No. 3,575,704, No. 3,653,905, No. 3,718,472, No. 4,071,312, and No. 4,070,352.

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

According to another preferred embodiment of the present invention, the method for processing a silver halide color photographic light-sensitive material of the present invention comprises the compound of the present invention as a color developing solution used in the present invention, that is, a preservative, and the present invention. At least one of the silver halide emulsion layers using a color developer containing the chelating agent of formula (C-I), (C-II) and (C-III) It is intended to process a silver halide color photographic light-sensitive material containing a cyan coupler.

General formula (C-I) or (C-II) used in the present invention
The cyan coupler represented by will be described.

General formula (C-I) General formula (C-II) In the formula, Y is -COR ₄ , -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group,
It represents a cycloalkyl group, an aryl group or a heterocyclic group, and R ₄ and R ₅ may combine with the nitrogen atom to which they are bonded to form a 5- or 6-membered ring. ), And R ₃
Represents a ballast group, and Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine color developing agent.

In the general formulas (C-1) and (C-II), Y is -COR ₄ , It is a group represented by -CONHCOR ₄ or -CONHSO ₂ R ₄ . Here, R ₄ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (eg, an allyl group, Heptadecenyl group, etc.), cycloalkyl group, preferably a 5- to 7-membered ring (eg cyclohexyl etc.), aryl group (eg phenyl group, tolyl group, naphthyl group etc.), heterocyclic group, preferably nitrogen atom, oxygen atom Alternatively, a 5- to 6-membered heterocyclic group containing 1 to 4 sulfur atoms (for example, a furyl group, a thienyl group,
Benzothiazolyl group). R ₅ is a hydrogen atom or
It represents a group represented by R ₄ . R ₄ and R ₅ may combine with each other to form a 5-membered to 6-membered heterocycle containing a nitrogen atom. In addition, R ₄ and R ₅ can be introduced with any substituent, for example, an alkyl group having 1 to 10 carbon atoms (for example, ethyl,
i-propyl, i-butyl, t-butyl, t-octyl, etc.), aryl groups (eg, phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (eg, methanesulfone) Amide,
Butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl, carbamoyl group (eg, dimethyl). Sulfamoyl, phenylcarbamoyl etc.), oxycarbonyl group (eg ethoxycarbonyl, phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl etc.), heterocyclic group (eg pyridyl group, pyrarazolyl group etc.), alkoxy group, aryloxy Group, acyloxy group and the like.

In the general formulas (C-I) and (C-II), R ₃ is diffusion resistant to the cyan couplers represented by the general formulas (C-I) and (C-II) and the cyan dye formed from the cyan coupler. Represents a ballast group necessary for imparting
Preferred is an alkyl group having 4 to 30 carbon atoms, an aryl group or a heterocyclic group. For example, a linear or branched alkyl group (for example, t-butyl, n-octyl, t-octyl,
n-dodecyl etc.), alkenyl group, cycloalkyl group,
A 5-membered or 6-membered heterocyclic group can be mentioned.

In formulas (C-I) and (C-II), Z represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidation product of a color developing agent. For example, a halogen atom (eg (chlorine, bromine, fluorine etc.), a substituted or unsubstituted alkoxy group, an aryloxy group, a heterocyclic oxy group,
Examples thereof include an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, and a sulfonamide group. Further specific examples thereof are U.S. Pat. No. 3,741,563 and JP-A-57-37425.
Japanese Patent Publication No. 48-36894, Japanese Unexamined Patent Publication No. 50-10135, 50-11.
7422, 50-130441, 51-108841, 50-1203
No. 43, No. 52-18315, No. 53-105226, No. 54-14736
No. 54-48237, No. 55-32071, No. 55-65957,
56-1938, 56-12643, 56-27147, 59-
146050, 59-166956, 60-24547, 60-357
No. 31 and No. 60-37557.

In the present invention, as (C-I) and (C-II), the following general formula (C-IV), (C-V) or (C-VI) is used.
Cyan couplers represented by are more preferred.

General formula (C-IV) General formula (C-V) General formula (C-VI) In the general formula (C-IV), R ₃₄ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent is -SO.
₂ R ₃₇ , halogen atom (eg fluorine, bromine, chlorine etc.),
_{-CF 3, -NO 2, -CN,} -COR 37, -COOR 37, -SO 2 OR 37, At least one substituent selected from is included.

Here, R ₃₇ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group such as methyl, ethyl, tert-butyl, dodecyl, etc.), an alkenyl group, preferably 2 carbon atoms.
To 20 alkenyl groups (eg, allyl group, heptadecenyl group, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (eg, cyclohexyl group, etc.), aryl groups (eg, phenyl group, tolyl group, naphthyl group, etc.) , R ₃₈ is a hydrogen atom or a group represented by R ₃₇ .

A preferred compound of the phenolic cyan coupler represented by the general formula (C-IV) is a compound in which R ₃₇ is a substituted or unsubstituted phenyl group, and a substituent for the phenyl group is cyano, nitro, —SO ₂ R ₃₉ ( R ₃₉ is an alkyl group), a halogen atom,
A compound such as trifluoromethyl.

In the general formulas (CV) and (C-VI), R ₃₅ and R ₃₆
Is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg methyl, ethyl, tert-butyl, dodecyl etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (eg allyl, oleyl etc.), cyclo Alkyl group, preferably 5 to 7-membered ring group (eg cyclohexyl etc.), aryl group (eg phenyl group, tolyl group, naphthyl group etc.), heterocyclic group (nitrogen atom, oxygen atom or sulfur atom 1 to 4) Preferred are 5- to 6-membered heterocycles including, for example, a furyl group, a thienyl group, and a benzothiazolyl group.

The above R ₃₇ , R ₃₈ and the general formulas (CV) and (CVI)
Any substituent can be further introduced into R ₃₅ and R ₃₆ of, and specifically, general formulas (C-1) and (C-II)
Is a substituent that can be introduced into R ₄ or R ₅ . As the substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable.

Formula (C-IV), has the same meaning as (C-V) and (C-VI) Z and R ₃ in each formula (C-I) and (C-II). A preferred example of the ballast group represented by R ₃ is a group represented by the following general formula (C-VII).

General formula (C-VII) In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, l represents 0 or 1, and when K is 2 or more, two or more R _{41 s} are the same. R ₄₀ may be different, represents a linear or branched C 1-20 linear or branched, and substituted alkylene group such as an aryl group, R ₄₁ represents a monovalent group, preferably a hydrogen atom, a halogen atom ( For example, chromium, bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (eg, methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.). Group), aryl group (eg phenyl group), heterocyclic group (preferably nitrogen-containing heterocyclic group), alkoxy group, preferably linear or branched alkoxy group having 1 to 20 carbon atoms (eg methoxy, ethoxy). t-butyloxy, octyloxy, decyloxy, dodecyloxy and other groups), aryloxy group (eg phenoxy group), hydroxy, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (eg acetoxy group, benzoyloxy group) ), Carboxy, an alkyloxycarbonyl group, preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms, an aryloxycarbonyl group, preferably phenoxycarbonyl,
An alkylthio group, preferably an acyl group having 1 to 20 carbon atoms,
Preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably 1 to 20 carbon atoms
A linear or branched alkylcarboxamide, benzenecarboxamide or sulfonamide group, preferably having 1 to 1 carbon atoms.
20 linear or branched alkylsulfonamide group or benzenesulfonamide group, carbamoyl group, preferably C 1-20 linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group, sulfamoyl group, preferably carbon number It represents a linear or branched alkylaminosulfonyl group of 1 to 20 or a phenylaminosulfonyl group.

Next, specific compound examples of the cyan coupler represented by the general formula (C-I) or (C-II) are shown, but the cyan coupler is not limited thereto.

[Compound example]

The cyan coupler represented by the general formula (C-I) or (C-II) can be synthesized by various methods. For example, U.S. Pat. Nos. 2,772,162, 3,758,308, 3,880,661, and 4,124,396. No. 3,222,176, British Patent No. 975,773, No. 8,011,693, No. 8,011,694, JP-A-47-21139, No. 50-112038, No. 5-163537, No. 56-29235, and No. 56-29235. 55-99341, 56-116030, 52-69329, 56-55945, 56-80045, 50-134644, and British Patent 1,011,940, U.S. Patent 3,446,622.
No. 3,996,253, Japanese Unexamined Patent Publication Nos. 56-65134, 57-204543, 57-204544, 57-204545, Japanese Patent Application Nos. 56-131312, 56-131313, 56- 131314, 56-131309, 56-131311, 57-149791, 56-130459, JP-A-57-146050, 166956, 60-24547, 60-35731. No. 60-37557 and the like.

When the cyan coupler of the present invention represented by the general formula (C-I) or (C-II) is contained in the silver halide emulsion layer, it is usually about 0.005 to 2 per mol of silver halide.
It is used in a molar amount, preferably 0.01 to 1 mol.

Next, the cyan coupler represented by the following general formula (C-III) will be described in detail.

General formula (C-III) In the general formula ((C-III), one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group of at least 2 to 12, and X is a hydrogen atom or the N-hydroxyalkyl-substituted group. -P-phenylenediamine derivative represents a group capable of splitting off by a coupling reaction with an oxidized product of a color developing agent, and R ₂ represents ballast.

The cyan coupler which can be preferably used in the present invention can be represented by the above general formula (C-III).
-III) will be further described.

In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R ₁ and R in the general formula (C-III) is
For example, an ethyl group, a propyl group, and a butyl group.

In the general formula (C-III), a ballast group represented by R ₂ is used to give the coupler molecule sufficient bulkiness so that the coupler cannot be substantially diffused from the layer to which the coupler is applied to other layers. An organic group having a size and shape. A typical ballast group has a total carbon number of 8 to
There may be mentioned 32 alkyl groups or aryl groups, but the total number of carbon atoms is preferably 13 to 28. These alkyl group and aryl group may have a substituent, and examples of the substituent of the aryl group include an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a carboxyl group, an acyl group, an ester group and a hydroxy group. Group, cyano group, nitro group,
Carbamoyl group, carbonamido group, alkylthio group,
Examples thereof include an arylthio group, a sulfonyl group, a sulfonamide group, a sulfamoyl group and halogen. Further, examples of the substituent of the alkyl group include the substituents of the aryl group excluding the alkyl group.

The preferred ballast group is represented by the following general formula.

R ₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. As the substituent, an alkyl group,
Examples thereof include a hydroxy group, a halogen atom, and an alkylsulfonamide group, and the most preferable one is a branched alkyl group such as t-butyl group.

The group capable of leaving upon coupling, which is defined by X in the general formula (C-III), determines the number of equivalents of the coupler and influences the reactivity of the coupling, as is well known to those skilled in the art. . Typical examples are chlorine, halogen represented by fluorine, aryloxy group, substituted or unsubstituted alkoxy group, acyloxy group, sulfonamide group, arylthio group, heteroylthio group, heteroyloxy group, sulfonyloxy group, carbamoyloxy group. Groups and the like. As a more specific example, Japanese Patent Laid-Open No. 50-
10135, 50-120334, 50-130441, 54-48237, 51-146828, 54-14736, 47-37425, 50-123341, 58-95346. JP-B-48-36894, U.S. Pat.No. 3,476,
No. 563, No. 3,737,316, and No. 3,227,551.

Next, exemplary compounds of the cyan coupler represented by formula (C-III) will be described. Examples of the exemplified compound include, but are not limited to, those in which R ₁ , X, R ₂ and R are respectively specified in the general formula (C-III) as described below.

The method for synthesizing the exemplary compound of the cyan coupler of the general formula (C-III) according to the present invention is shown below, but other exemplary compounds can be synthesized by the same method.

Synthesis Example of Exemplified Compound C-101 [(1) -a] Synthesis of 2-nitro-4,6-dichloro-5-ethylphenol 2-nitro-5-ethylphenol 33 g, iodine 0.6 g and ferric chloride 1.5 g is dissolved in 150 ml glacial acetic acid. 40 ℃ to this
Then, 75 ml of sulfuryl chloride is added dropwise over 3 hours. The precipitate formed during the dropping is reacted and dissolved by heating under reflux after the completion of the addition of sulfuryl chloride. Heating under reflux takes about 2 hours. The reaction solution is poured into water and the produced crystals are purified by recrystallization with methanol. (1) -a was confirmed by nuclear magnetic resonance spectrum and elemental analysis.

[(1) -b] Synthesis of 2-amino-4,6-dichloro-5-ethylphenol 21.2 g of the compound of [(1) -a] was dissolved in 300 ml of alcohol, and a catalytic amount of Raney nickel was added thereto. Hydrogen was passed through at normal pressure until there was no hydrogen absorption. After the reaction, Raney nickel was removed and the alcohol was distilled off under reduced pressure. The residual [(1) -b] was subjected to the next acylation without purification.

Synthesis of [(1) -c] 2 [(2,4-di-tert-acylphenoxy) acetamido] -4,6-dichloro-5-ethylphenol Crude amino form obtained in [(1) -b] 18.5 g to 500 ml
Dissolved in a mixed solution of glacial acetic acid and 16.7 g of sodium acetate,
To this was added 2,4-di-tert-aminophenoxyacetic acid chloride 2
An acetic acid solution prepared by dissolving 8.0 g in 50 ml of acetic acid is added dropwise at room temperature. After dropping for 30 minutes and stirring for 30 minutes, the reaction solution is poured into ice water. The precipitate formed is taken, dried and recrystallized twice from acetonitrile to obtain the desired product. The target product was confirmed by elemental analysis and nuclear magnetic resonance spectrum.

The addition amount of the cyan coupler of the general formula (C-III) of the present invention is not limited, but silver 1 in the red-sensitive silver halide emulsion layer is
The amount is preferably 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ^{−2 to} 3 × 10 ⁻¹ mol per mol.

In the present invention, the cyan coupler of the present invention may be used in combination with other cyan couplers, examples of cyan couplers that can be used include phenol compounds, naphthol compounds, for example, U.S. Patents 2,369,929 and 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. 3,418,390, No. 3,458,315, No. 3,591,383, etc. The synthetic method is also described in the publication.

In the present invention, the general formula (C-I), (C-II) or (C
The cyan coupler represented by -III) can be used in combination with a conventionally known cyan coupler as long as the object of the present invention is not impaired. In addition, the general formula (C-
The cyan couplers I), (C-II) and (C-III) can also be used in combination.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. As a pyrazolone-based magenta coupler, US Patent 2,600,780
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,419,391, No. 3,519,429, No. 3,558,318, No. 3,684,514, No. 3,888,680, JP-A-49-29639, No. 49,111631, No. 49. -129538, 50-13041, JP-B-53-47167, 54-10491, 55-30615; pyrazolotriazole-based magenta couplers, U.S. Pat.No. 1,247,493, Belgium Examples of the couplers described in Patent 792,525, as the diffusion-resistant colored magenta couplers, generally used are compounds substituted with arylazo at the coupling position of a colorless magenta coupler, for example, U.S. Pat.Nos. 2,801,171 and 2,983,608. No. 3,005,712, No. 3,684,514, British Patent No. 937,621, JP-A Nos. 49-123625 and 49-31448.

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

As the photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used 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. Patents 2,875,057 and 3,265,506.
No. 3,664,841, No. 3,408,194, No. 3,277,155, No. 3,447,928, No. 3,415,652, Japanese Patent Publication No. 49-13576, No. 48-29432, No. 48-68834, No. 49-10736, No. 49-122335, 50-28834, 50-132926, etc. together with the synthetic 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 photosensitive silver halide emulsion layer.
2.0 mol.

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

Further, in addition to the DIR compound, a compound that releases a development inhibitor upon development is also included in the present invention.
297,445, 3,379,529, West German patent application (OLS) 2,417,914, JP-A-52-15271, 53-9116, 59-123838, 5
Examples thereof include those described in 9-127038.

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.

A typical example of such 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 active site of the coupler, for example, British Patent 935,454. , U.S. Pat. Nos. 3,227,554, 4,095,984, and 4,149,886.

The above-mentioned DIR coupler has a property that, when it undergoes a coupling reaction with an oxidized product of a color developing agent, the coupler nucleus forms a dye, while releasing a development inhibitor. Further, in the present invention, it is described in U.S. Pat.Nos. 3,652,345, 3,928,041, 3,958,993, 3,961,959, 4,052,213, JP53-110529, 54-13333, 55-161237, etc. Such compounds include compounds that release a development inhibitor but do not form a dye when they undergo a coupling reaction with an oxidized product of a color developing agent.

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

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

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 further contain various photographic additives. For example, antifoggant, stabilizer, ultraviolet absorber, described in Research Disclosure Magazine 17643,
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.

As the support of the silver halide color photographic light-sensitive material used in the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, provided with a reflective layer, or
A transparent support used in combination with a reflector, for example, a glass plate, 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 other ordinary transparent supports Good. 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. Also, US Patent 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 light-sensitive 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 light-sensitive silver halide emulsion layers may be composed 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 depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
In these constituent layers, a hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder, and the layer may be contained in the emulsion layer as described above. A variety of possible photographic additives can be included.

In the method of processing a silver halide color photographic light-sensitive material of the present invention, the above-mentioned substantially silver chloride is used as the silver halide color photographic light-sensitive material, and the coupler of the present invention is used to contain a coupler. If it is a light-sensitive material processed by the so-called internal development method, color paper, color negative film, color positive film, slide color reversal film, movie color reversal film, TV color reversal film, reversal color paper, etc. It can be applied to silver halide color photographic light-sensitive materials.

As described above, according to the present invention, for the silver halide color photographic light-sensitive material, which suppresses ammonia fogging, chelates heavy metal ions, and does not cause excessive development even when a silver chloride color photographic light-sensitive material is used. Color developer,
A method of processing a silver halide color photographic light-sensitive material using the same can be provided.

[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.

Example (1) A color developer having the following composition was prepared.

(Color developer) Potassium chloride 1.0 g Potassium sulfite 0.1 g Preservative (listed in Table 1) 10 g Chelating agent (listed in Table 1) 2.0 g Color developing agent [Exemplified compound (AI)] 5.5 g Potassium carbonate 30 g Add water to make 1 and add potassium hydroxide and sulfuric acid to pH 10.15
Adjust to.

Ferric ion 4ppm in the color developer, copper ions 2ppm and calcium ions 100 ppm (respectively _{FeCl 3, CuSO 4 · 6H 2} O
And CaCl ₂ are dissolved and added), and the opening ratio is 3 at 40 ° C.
0cm ² / l (air contact area is 30cm for 1 color developer)
^It was stored in the glass container of ² ) for 2 weeks.

The appearance (coloring degree) of the color developing solution after 2 weeks was observed. However, the appearance of the liquid was divided into the following four stages.

++ Generation of a large amount of tar ++ Blackening ＋ Browning (very discolored) − Almost no discoloration As is clear from the results shown in Table 1, when hydroxylamine sulfate is added as a preservative, the liquid appearance is slightly changed depending on the presence or absence of the chelating agent, but the liquid is discolored or blackened. This means that the color developing agent in the color developing solution has been oxidized and tar has started to occur. On the other hand, it is clear from Example (1) that the preservative of the present invention is remarkably improved by the combination with the chelating agent.

Example (2) A photosensitive material sample was prepared by sequentially coating the following layers from the support side on a polyethylene-supported paper support.

Layer 1 ... 1.0 g × 10 ⁻³ mol / mol dissolved in 1.0 g / m ² gelatin, 0.40 g / m ² (silver equivalent, the same applies hereinafter) blue-sensitive silver halide emulsion and 0.50 g / m ² dioctyl phthalate A layer containing m ² of the following yellow coupler (Y-1).

Layer 2 ... Intermediate layer consisting of 0.65 g / m ² of gelatin.

Layer 3 ... 1.20 g / m ² of gelatin, 0.24 g / m ² green-sensitive silver halide emulsion and 0.25 g / m ² of dioctyl phthalate 1.0 × dissolved in 10 ^-3 mol / m ² of the following magenta coupler (M -1)
Containing layers.

Layer 4--Intermediate layer consisting of 1.0 g / m ² of gelatin.

Layer 5 ... dissolved in 1.3 g / m ² gelatin, 0.27 g / m ² red-sensitive silver halide emulsion and 0.30 g / m ² dibutyl phthalate
A layer containing 1.75 × 10 ⁻³ mol / m ² of a cyan coupler (C-76).

Layer 6 A layer containing 0.30 g / m ² of Tinuvin 328 (UV absorber manufactured by Ciba Geigy) dissolved in 1.2 g / m ² of gelatin and 0.20 g / m ² of dioctyl phthalate.

Layer 7 ... Layer containing 0.45 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 step Processing temperature Processing time [1] Color development 35 ℃ As described in Table 2 [2] Bleach-fixing 35 ℃ 45 seconds [3] Washing with water 30 ℃ 90 seconds [4] Drying 60-80 ℃ 60 seconds Processing solution used The composition of is as follows.

[Color developer] Potassium chloride 1.0 g Potassium sulfite 0.25 g (2 × 10 ⁻³ mol) Preservative (Exemplified compound (I-1)) 2.0 g Chelating agent Exemplified compound (II-2) 1.0 g Color developing agent ( Exemplified compound A-1) 5.5g Potassium carbonate 30g Add water to make 1 and adjust pH to 10.15 with potassium hydroxide and sulfuric acid.
Adjusted to.

[Bleach-fixing solution] Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate 100ml (70% solution) Ammonium sulfite (40% solution) 27.5ml Add 1 to the total amount of potassium carbonate. Or adjust to pH 7.1 with glacial acetic acid.

Optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) to determine the maximum reflection density of the yellow dye when color developed for 10 minutes at 35 ° C
And the maximum reflection density of the yellow dye at this time.
The development time (development convergence time) required for the maximum reflection density of the yellow dye to be 80 is shown in Table (2). This result indicates the development completion time of the light-sensitive material used because it is the development convergence time of the blue sensitive emulsion layer having the slowest development speed.

As is clear from Table (2), in Sample Nos. 3 to 10 having a silver chloride content of 80% or more, the convergence time is short and rapid processing is possible. Especially 90% silver chloride content
The above sample Nos. 5 to 10 have a silver chloride content of 95%
It can be seen that the above sample Nos. 6 to 10 enable particularly rapid processing.

Example (3) The same color developing solution as in Example (1) was used except that the color developing solution of Example (1) was allowed to stand for 1 week at an opening ratio of 10 cm ² / l.
Using the light-sensitive material (Sample No. 8) used in Example (2),
Processing was carried out according to the processing step of Example (2) except that the color development processing time was 45 seconds.

After processing, the minimum densities of cyan, magenta and yellow dyes and the gamma value (gradient at density 0.3 to 0.8) were measured. As a result, the tendency of cyan, magenta, and yellow dyes in each treatment liquid was not changed. Table (3) describes the minimum density and gamma value of the yellow dye.

As is clear from Table (3), when the treatment liquid of the present invention was used, there was almost no change in the minimum concentration and gamma value even after storage (40 ° C. for 1 week), and it was compared to the conventionally used hydroxylamine salt. It is clear that the treatment liquid has a remarkable effect and is more suitable for rapid treatment than the gamma value.

Example (4) Using the color paper sample used in Example (2),
The same treatment was repeated using the treatment liquid used in Example (2) according to the treatment step of Example (2). However, the silver halide composition of the color paper sample was AgBr: AgCl 1:99 in the blue-sensitive emulsion layer, 5:95 in the green-sensitive emulsion layer, 5:95 in the red-sensitive emulsion layer, and the cyan coupler was set to the table ( The one described in 4) was used. In addition, the color development processing time was 45 seconds, and the concentration of potassium sulfite in the color developing solution was as shown in Table (4).
The chelating agent used was that described in Table (4) at 1.0 g / l. The color developer is ferric ion 4ppm, copper ion 2ppm and calcium ion 100ppm.
(FeCl ₃ , CuSO ₄ .6H ₂ O and CaCl ₂ were dissolved and added, respectively, and stored for 5 days under the same conditions as in Example (1). The maximum coloring density of the cyan dye after the treatment and The minimum color density was measured and is shown in Table (4).

As is clear from the results in Table (4), when the couplers other than the present invention are used, the maximum color density of cyan is greatly reduced and the minimum density is also high. On the other hand, the cyan coupler of the present invention shows almost no decrease in the maximum color density, but the minimum density is remarkably high when the chelating agent is not contained. However, the combination of the coupler of the present invention and the chelating agent resulted in satisfying both the maximum color density and the minimum density.

Further, the sample of the present invention was able to obtain a better maximum concentration by reducing the concentration of sulfite.

In Sample 38, C-10 was used as a cyan coupler.
Even with 2, C-1, C-3 and C-58, sample N
Compounds I-1 and II- as chelating agents in o.6
The same results as above were obtained using 4-II-7 and III-2 to III-4.

Comparison cyan coupler Example (5) Using the color light-sensitive material prepared in Example (2) (the silver halide composition is shown in Table (5)), as color developing solutions, Nos. 2, 4 and 6 (color developing agents) were used. None) was evaluated for silver developability after the following treatment.

Standard treatment process (treatment temperature and treatment time) [1] Current image 35 ℃ 45 seconds [2] Fixing 35 ℃ 45 seconds [3] Washing treatment 30 ℃ 90 seconds [4] Drying 60-80 ℃ 60 seconds (fixing Liquid) Ammonium thiosulfate (70% solution) 150 ml Ammonium sulfite (40% solution) 20 ml Water was added to adjust the total amount to 1, and the pH was adjusted to 7.00 with ammonium hydroxide or acetic acid.

Samples after development processing were PDA-65 (Konishi Roku Photo Industry Co.
The spectral reflection density of Dmax of the sample was measured by using orange light, and the difference between the spectral reflection density of Dmax and the spectral reflection density of Dmin was used as the representative characteristic of silver concentration.

The results are shown in Table (5).

As is clear from Table (5), in Samples Nos. 52 to 58 using hydroxyamine, the silver concentration is high and the silver development is advanced. Especially, samples with silver chloride content of 80% or more
It can be seen that silver development is progressing in Nos. 53-58.

However, in the color developing solution No. 6 using the exemplified compound I-1 of the present invention, silver development hardly occurs regardless of the content ratio of silver chloride.

Example (6) Samples 1, 3 and 6 used in Example (2) (however, the cyan couplers described in Table (6) were used) and Example (1) was used as a color developer. Developer N used in
Using o.6 (however, potassium sulfite is shown in Table (6)), the influence of the silver halide composition and the sulfite salt on the cyan density (maximum reflection density) was examined. Development processing and evaluation method were in accordance with Example (2).

As is clear from Table (6), when the silver halide composition of sample Nos. 66 to 69 is low, the cyan concentration is low due to the short development time, but the concentration of potassium sulfite and the type of cyan coupler are greatly affected. Do not receive On the other hand, sample No. 7
When the silver chloride content of 0 to 77 is 80 mol% or more, the developing speed is high, so the cyan concentration is high even if the developing time is short,
When a coupler other than the present invention is used, it largely depends on the amount of potassium sulfite, and particularly when potassium sulfite is 1.0 × 10 ⁻² mol or more, a remarkable concentration is exhibited, but when the coupler of the present invention is used, It can be seen that the cyan concentration does not decrease so much and that when the sulfite concentration is 4.0 × 10 ⁻³ or less, a very good maximum concentration can be obtained.

Example (7) A photosensitive material sample was prepared by sequentially coating the following layers from the support side on a polyethylene-supported paper support.

Layer 1 ... 1.0 × 10 ^-3 mol / m dissolved in 1.0 g / m ² of gelatin, 0.38 g / m ² (silver equivalent, the same applies hereinafter) of blue-sensitive silver halide emulsion and 0.50 g / m ² of dioctyl phthalate A layer containing ² of the yellow coupler (Y-1).

Layer 2 ... Intermediate layer consisting of 0.6 g / m ² of gelatin.

Layer 3 ... 1.0 × 1 dissolved in 1.15 g / m ² gelatin, 0.27 g / m ² green sensitive silver halide emulsion and 0.25 g / m ² dioctyl phthalate.
A layer containing 0 ^-3 mol / m ² of the magenta coupler (M-1).

Layer 4 ... Intermediate layer consisting of 1.1 g / m ² of gelatin.

Layer 5 ... 1.3g / m ² of gelatin was dissolved in dibutyl phthalate red-sensitive silver halide emulsion and 0.25 g / m ² of 0.28 g / m ²
A layer containing 1.7 × 10 ⁻³ mol / m ² of a cyan coupler (C-108).

Layer 6 ... A layer containing 1.01 g / m ² of gelatin and 0.31 g / m ² of Tinuvin 328 (UV absorber manufactured by Ciba Geigy) dissolved in 0.20 g / m ² of dioctyl phthalate.

Layer 7 ... A 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 (7).

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] Washing with water 30 ℃ 90 seconds [4] Drying 60-80 ℃ 60 seconds Composition of processing solution used Is as follows.

[Color developer] Potassium chloride 1.0 g Potassium sulfite 0.25 g (2 × 10 ⁻³ mol) Preservative (Exemplary compound (I-1)) 10.0 g Chelating agent (Exemplary compound (II-2)) 1.0 g Color developing Main drug 5.5g (Exemplified compound (A-1)) Potassium carbonate 30g Add water to make the total amount 1 and adjust to pH 10.15 with potassium hydroxide or sulfuric acid.

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

Optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) to determine the maximum reflection density of the yellow dye when color developed for 10 minutes at 35 ° C
And the maximum reflection density of the yellow dye at this time.
The development time (development convergence time) required for the maximum reflection density of the yellow dye to be 80 is shown in Table (7). This result indicates the development completion time of the light-sensitive material used because it is the development convergence time of the blue sensitive emulsion layer having the slowest development speed.

As is clear from Table (7), in Sample Nos. 80 to 87 having a silver chloride content of 80% or more, the convergence time is short and rapid processing is possible. Especially, the content rate of silver chloride is 90
% Of sample Nos. 82 to 87, especially with a silver chloride content of 9
It can be seen that particularly rapid processing is possible with 5% or more of sample Nos. 83 to 87.

Example 8 Using the color paper sample used in Example (7),
The same treatment was repeated using the treatment liquid used in Example (7) according to the treatment step of Example (7). However, the silver halide composition of the color paper sample was AgBr: AgCl 3:97 in the blue-sensitive emulsion layer, 3:97 in the green-sensitive emulsion layer, and 1:99 in the red-sensitive emulsion layer, and the cyan coupler was as shown in Table (8). ) Was used. Also, the color development processing time was 45 seconds, the concentration of potassium sulfite in the color developing solution was as shown in Table (8), and the chelating agent used was that shown in Table (8) at 1.0 g / l. did. The color developer is ferric ion 4ppm, copper ion 2ppm and calcium ion 100ppm.
FeCl ₃ , CuSO ₄・ 6H ₂ O and CaCl ₂ are added by dissolution,
The one used after being stored under the same conditions as in Example 1 for 5 days was used. The maximum and minimum color densities of the cyan dye after the treatment were measured and are shown in Table (8).

As is clear from the results in Table (8), when the coupler of the present invention is used, the maximum color density of cyan is greatly reduced and the minimum density is also high. On the other hand, the cyan coupler of the present invention shows almost no decrease in the maximum color density, but the minimum density is remarkably high when the chelating agent is not contained. However, the combination of the coupler of the present invention and the chelating agent resulted in satisfying both the maximum color density and the minimum density.

Further, in the sample of the present invention, it was possible to obtain a better maximum color density by reducing the concentration of sulfite.

Even if the exemplary compounds C-109 and C-128 were used as the cyan coupler in the sample No. 75, the sample No. 73
As the chelating agent, exemplified compounds II-1, II-4 to
Even if II-6 and III-2 to III-4 were used, the same effect as above could be obtained.

Example (9) Using the color light-sensitive material prepared in Example (7) (silver halide composition is shown in Table (9)), N was used as a color developing solution.
The silver developability of o.2, 4 and 6 (no color developing agent) was evaluated by the following processing.

Standard treatment process (treatment temperature and treatment time) [1] Current image 35 ℃ 45 seconds [2] Fixing 35 ℃ 45 seconds [3] Washing treatment 30 ℃ 90 seconds [4] Drying 60-80 ℃ 60 seconds (fixing Liquid) Ammonium thiosulfate (70% solution) 150 ml Ammonium sulfite (40% solution) 20 ml Water was added to adjust the total amount to 1, and the pH was adjusted to 7.00 with ammonium hydroxide or acetic acid.

Samples after development processing were PDA-65 (Konishi Roku Photo Industry Co.
The spectral reflection density of Dmax of the sample was measured with orange light using a product manufactured by K.K.), and the difference from the spectral reflection density of Dmax was used as a representative characteristic of silver concentration.

The results are shown in Table (9).

As is clear from Table (9), in Samples Nos. 109 to 115 using hydroxylamine, the silver concentration is high and the silver development is progressing. Samples with a silver chloride content of 80% or more
It can be seen that silver development is progressing in Nos. 110 to 115. However, color developer No. 6 using the exemplified compound I-1 of the present invention
In that case, silver development hardly occurs regardless of the content ratio of silver chloride.

Example (10) Samples 78, 80 and 83 used in Example (7) (however, cyan couplers described in Table (10) were used) and used as a color developer in Example 1. Developer No.6
(However, potassium sulfite is shown in Table (10)) was used to examine the effect of silver halide composition and sulfite on cyan concentration (maximum reflection density).

Development processing and evaluation method were in accordance with Example (7).

As is clear from Table (10), when the silver halide composition is sample No. 123 to 126, the cyan concentration is low due to the short development time, but the concentration of potassium sulfite and the type of cyan coupler are greatly affected. Do not receive On the other hand, sample No. 1
In the case of 27 to 134, when the silver chloride content is 80 mol% or more, the developing speed is high, so the cyan density is high even if the developing time is short,
When a coupler other than the present invention is used, it is present in a large amount in the amount of potassium sulfite, and when the potassium sulfite is 1.0 × 10 ⁻² mol or more, a particularly remarkable decrease in concentration is exhibited, but when the coupler of the present invention is used, It can be seen that there is little decrease in the cyan concentration, and when the sulfite concentration is 4.0 × 10 ⁻³ or less, a very good maximum concentration can be obtained.

Continuation of the front page (56) References JP-A-59-228251 (JP, A) JP-A-63-502222 (JP, A) US Patent 3746544 (US, A)

Claims (2)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material, which comprises subjecting a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer to imagewise exposure, and then performing at least a color development step. The color developer used in the color developing step contains a compound represented by the following general formula (I) and at least one compound selected from compounds represented by the following general formulas (II) and (III); The silver halide emulsion layer contains silver halide grains consisting of 80 mol% or more of silver chloride; and at least one of the silver halide emulsion layers has the following general formulas (C-I) and (C-II). A method for processing a silver halide color photographic light-sensitive material, comprising at least one cyan coupler selected from the cyan couplers represented by: General formula (I) (In the general formula (I), R ₁ and R ₂ each represent an alkyl group having 1 to 3 carbon atoms.) General formula (II) General formula (III) (In the above general formulas (II) and (III), R ₁ , R ₂ , R ₃ ,
R ₄ , R ₉ and R ₁₀ are each a hydrogen atom, a halogen atom,
Sulfonic acid group, C1-C7 alkyl group, -O
R ₅ , -COOR ₆ , Or represents a phenyl group. R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ) General formula (CI) General formula (C-II) (In the above general formulas (C-I) and (C-II), Y is -CO
R ₄ , -SO ₂ R ₄ , Represents -CONHCOR ₄ or -CONHSO ₂ R ₄ , (R ₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group , An aryl group or a heterocyclic group, or R ₄ and R ₅ may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded.), R ₃ is a ballast And Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine color developing agent. ) 2. The processing method according to claim 1, wherein at least one of the silver halide emulsion layers contains a cyan coupler represented by the following general formula (C-III). General formula (C-III) (In the general formula (C-III), one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group having 2 to 12 carbon atoms, and X is a hydrogen atom or the aforementioned N. -Hydroxyalkyl-substituted-p-phenylenediamine derivative represents a group capable of splitting off by a coupling reaction with an oxidized product of a color developing agent, and R ₂ represents a ballast group.)