JPH06301178A - Color developer for silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To provide a color developer having an improved preservation prop erty and allowing rapid processing without affecting the photographic characteris tic so much by containing specific two compounds and sulfurous acid ions. CONSTITUTION:A compound expressed by the formula I, a compound expressed by the formula II, and sulfurous acid ions of 1.5X10<-2>mol or below for a color developer of 1l. In the formula I, R1 indicates the alkyl group having the carbon number of 1-6, the hydroxyalkyl group having the carbon number of 2-6, the alkoxy group, or alkoxyalkyl group, R2, R3 indicate the hydrogen atom, the alkyl group having the carbon number of 1-6, the hydroxyalkyl group having the carbon number of 2-6, the alkoxyalkyl group, benzyl group, or aryl group respectively, and R2 and R3 or R1 and R3 may be bonded to form a ring. In the formula II, R4, R5 indicate the hydrogen atom or the alkyl group having the carbon number of 1-5 which may contain a substituent, respectively, and R4 and R5 do not concurrently indicate the hydrogen atom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials, and more particularly to a silver halide color using a preservative in place of hydroxylamine, which is harmful and harmful to humans. The present invention relates to a color developing solution for photographic light-sensitive materials.

[0002]

In color development, exposed silver halide is reduced to silver and at the same time oxidized primary aromatic amine developing agent reacts with a coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. Separately, components such as heavy metal ions contained in other processing solutions such as bleaching solutions and bleach-fixing solutions are also brought into and accumulated in the color developing solution by so-called back contamination.

To the color developing solution used for such color developing, a sulfite salt or a water-soluble salt of sulfite salt and hydroxylamine is usually added as a preservative (antioxidant) in order to increase its preservative property. ing. Of these, like the former,
Since fogging occurs remarkably with the use of sulfite alone over time, by using a sulfite and a water-soluble salt of hydroxylamine in combination with the latter, the preservative property of the developer is remarkably increased and It has been attempted to reduce fogging caused by the developing solution.

However, hydroxylamine has the following drawbacks and disadvantages.

That is, first of all, it has been reported that hydroxylamine is harmful to the human body [eg, PG Steche
r, `` The Merck Index An Encyclopedia of Chemical an
d Drugs "(The Merck Index Anne Encyclopedia of Chemical and Drugs)
8th.Ed. (1953)].

Secondly, even in the Poisonous and Deleterious Substances Control Law, in order to handle and sell hydroxylamine salt, it is necessary to register a general sales business of poisonous and deleterious substances and to set up a person in charge of handling, which is extremely difficult to handle. It is inconvenient.

Thirdly, hydroxylamine is a kind of black-and-white developer and has silver developability with respect to silver halide. Therefore, the utilization efficiency of silver halide in the silver halide color photographic light-sensitive material is poor, and it is necessary to use more silver halide or coupler in the light-sensitive material in order to obtain a desired dye concentration, which is economical. Is extremely detrimental to.

Fourthly, hydroxylamine is decomposed when heavy metal ions (for example, iron ions or copper ions) are mixed in the color developing solution to become ammonia, causing fogging on the color light-sensitive material, Further, it has a drawback that the photographic performance is adversely affected. From the viewpoint of economical efficiency and pollution, color developers tend to be low in replenishment in recent years, and the grade of raw materials such as potassium carbonate is being reduced for the purpose of cost reduction. The amount of the heavy metal ions accumulated in the developing solution is increasing more and more. Therefore, the occurrence of fogging, which is the fourth problem due to the decomposition of hydroxylamine, is becoming more severe.

Therefore, in the future, when performing in-store self-treatment or color copying equipped with a color developing system, it is strongly desired to develop a preservative which replaces hydroxylamine because of pollution problems.

As an alternative preservative to hydroxylamine, 2-anilinoethanol and dihydroxyalkene have been proposed in US Pat. Nos. 3,823,017 and 3,615,503, respectively. However, in all of these compounds, the compound itself is unstable, and the preservative effect in the color developing solution is extremely weak.

On the other hand, hydroquinone or N-alkyl
-In a developer containing p-aminophenol as a developing agent (for black and white photography), sucrose (sucrose) is known as a preservative, but sucrose is a color developing agent containing an aromatic primary amine as a developing agent. The liquid has little effect as a preservative.

Further, ascorbic acid and its derivatives are known as preservatives for black-and-white photographic developing solutions and color original image solutions, but they have the drawback of inhibiting color development and resulting in a marked decrease in color density. The developer is inferior to hydroxylamine.

Further, α-hydroxy aromatic alcohols described in JP-A No. 52-7779, hydroxamic acid compounds described in JP-A No. 52-27638, α-aminocarbonyl compounds described in JP-A No. 52-143020, and 52-143 Monosaccharides described in 102727, 52-140324
The amino acid derivatives described in No. 1 are disclosed.

However, when a large amount of a monosaccharide or amino acid derivative is used, it exhibits considerable homeostasis at room temperature, but it is easily decomposed by heat and has undesirable characteristics in terms of pollution.

D-glucosamine hydrochloride is known as a typical compound of the α-aminocarbonyl compound, but this compound is inferior in preservability to hydroxylamine.

Further, the hydroxamic acid compound has the same level of preservative property as hydroxylamine, but has the disadvantage of high cost.

Japanese Patent Publication No. 61-48698 discloses a technique in which hydroxylamine or its derivative and a bisulfite adduct of aldehyde are used together as a preservative for a color developing solution.
61-48699 discloses a technique in which diethanolamine is further used in combination with the above constitution. According to the study by the present inventors, the bisulfite addition compound of aldehyde shows a certain degree of stability even when used alone, but is insufficient in the stability.

Therefore, it is easily conceivable that a sulfite coexists in order to enhance the preservative ability, but it has been found that the following problems occur when the sulfite coexists. First, there is a problem that the density of the coloring pigment decreases. It is known that the concentration of the coloring dye decreases when the amount of sulfite added is increased. However, according to the study of the present inventors, a photosensitive material having a higher silver chloride content has a greater coloring dye concentration. It turned out to be easy to fall. Secondly, when used in a color developer for direct positive image formation, for example, a color developer represented by photo-fog development, increasing the amount of sulfite tends to cause yellow stains, resulting in a large loss of image quality. The problem also turned out.

Thirdly, in the case of rapid processing development, the concentration of sulfite ion and the presence of hydroxylamine greatly affect the rapidity, and it is necessary to reduce the sulfite ion concentration as much as possible and not use hydroxylamine. However, on the contrary, there is a problem that the homeostasis tends to deteriorate.

Therefore, it is considered that coexistence of the bisulfite addition compound of aldehyde with a certain amount of sulfite ion concentration is necessary from the viewpoint of preservability and developability. However, in the present time when rapid processing is required more and more, the above method alone is not sufficiently satisfactory, and for example, when processing is performed using a light-sensitive material having a high silver chloride content, aldehyde bisulfite addition is performed. It has been clarified by the study of the present inventors that the concentration is likely to be reduced even if the compound coexists.

[0021]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned drawbacks, to contain a preservative which is harmless to the human body and is easy to handle, and which is more effective than a conventional color developing solution using hydroxylamine. It is an object of the present invention to provide a color developing solution which has improved consistency and which does not significantly affect photographic characteristics and which can be rapidly processed.

[0022]

The above object of the present invention is to provide a compound represented by the following general formula [1], a compound represented by the following general formula [2] and 1.5 × 10 ^-2 per liter of color developer. It is achieved by a color developing solution for silver halide color photographic light-sensitive materials containing a molar amount of sulfite ion or less.

[0023]

[Chemical 4]

In the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms,
A hydroxyalkyl group having 2 to 6 carbon atoms, an alkoxy group or an alkoxyalkyl group, R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an alkoxyalkyl group, Benzyl group, aryl group or formula

[0025]

[Chemical 5]

In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
It represents a hydroxyalkyl group or an alkoxyalkyl group having 2 to 6 carbon atoms, and R ₂ and R ₃ and R ₁ and R ₃ may combine with each other to form a ring.

[0027]

[Chemical 6]

In the formula, R ₄ and R ₅ each represent a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms. However, R ₄ and R ₅ are not hydrogen atoms at the same time.

According to the study by the present inventors, a photosensitive material having a higher silver chloride content for rapid processing has a higher dependency on sulfite ion concentration, and a photosensitive material having a high silver bromide content can be used as a direct positive photosensitive material. It was found that there was a marked difference in the degree of yellow stain depending on the amount of sulfite. Further, from the viewpoint of homeostasis, it is presumed that the higher the sulfite ion concentration is, the higher the homeostasis ability is as described above. However, according to the study by the present inventors, it is certain that the sulfite concentration is increased to some extent. Although there is an advantage that the number of days of occurrence of tarling is shortened, the deterioration rate of sulfurous acid depends on the residual concentration of sulfurous acid, so that the deterioration rate becomes faster and, as a result, the remarkable homeostatic ability is increased. It turns out that I can't hope for a rise. However, when it is used in combination with the compound represented by the general formula [2], the homeostasis does not significantly deteriorate even if the sulfite ion concentration is lowered, and rather the presence of a certain amount of sulfite causes the homeostasis ability to coexist. Was found to be sufficient.

Therefore, for the above reasons, it has become possible to provide a color developing solution for a color light-sensitive material which is suitable for rapid processing without significantly impairing photographic characteristics. Moreover, as for the preservative property, the preservative ability can be increased more than that of the color developing solution using hydroxylamine.

In the present invention, among the compounds represented by the general formula [1], the compound represented by the following general formula [3] is particularly preferable.

[0032]

[Chemical 7]

In the formula, R ₆ is a hydrogen atom or has 1 to 6 carbon atoms.
(Preferably 1 to 3) alkyl group, R ₇ represents alkylene group having 1 to 6 carbon atoms, R ₈ represents hydrogen atom,
R ₉ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom
It represents an alkoxy group or a phenyl group of 6 and is preferably a hydrogen atom. R ₈ and R ₉ and R ₇ and R ₉ each represent a nitrogen-containing heterocycle which may be bonded to each other to form. n represents 0 or 1, and when R ₆ is a hydrogen atom, n is 1.

In the above general formula [3], examples of the alkyl group represented by R ₆ include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.

The alkylene group represented by R ₇ may be linear or branched and includes, for example, --CH _2- , --CH ₂ CH _2- , --CH ₂ CH ₂ CH _2- ,
-CH ₂ CHCH ₃ CH _2- , -CH ₂ CHC ₂ H ₅ CH _2- , -CHCH ₃ CH _2- ,
—CHCH ₃ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ — and the like.

The nitrogen-containing heterocycle formed by R ₈ and R ₉ is, for example,

[0037]

[Chemical 8]

It is a ring such as

Next, preferred specific examples of the compound represented by the above general formula [1] are shown.

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

The compound represented by the above general formula [1] may be added alone to the color developing solution, or may be added in combination of two or more kinds. Addition amount is 0.1 per liter of color developer.
˜50 g is preferred, more preferably 0.3 to 30 g.

In the above general formula [2], R ₄ and R ₅
Examples of the substituent of the alkyl group represented by include a sulfonic acid group, a hydroxyl group, an alkoxy group (a methoxy group, an ethoxy group, a propyloxy group, etc.), a carboxyl group, an amino group, and the like. , 28
Examples thereof include hydroxylamines described in 7,125, 3,293,034, 3,287,124 and the like.

Of the hydroxylamine derivatives represented by the general formula [2], compounds in which both R ₄ and R ₅ are not hydrogen atoms are preferably used for improving the preservability, and especially R
₄ , R ₅ is an ethyl group having a C number of 2 or more, a methoxyethyl group,
Most preferred are compounds such as ethoxyethyl groups.

Preferred specific exemplary compounds represented by the general formula [2] are shown below.

(1) CH ₃ --NH--OH (2) C ₂ H ₅ --NH--OH (3) (i) C ₃ H ₇ --NH--OH (4) C ₃ H ₇ --NH--OH (5) _{) HO-CH 2 -NH-OH} (6) CH 3 -O-C 2 H 4 -NH-OH (7) HO-C 2 H 4 -NH-OH (8) HOOC-C 2 H 4 -NH- OH (9) HO ₃ S-C ₂ H ₄ -NH-OH (10) N ₂ H-C ₃ H ₆ -NH-OH (11) C ₂ H ₅ -O-C ₂ H ₄ -NH-OH ( _{12) HO-C 2 H 4} -O-C 2 H 4 -NH-OH

[0050]

[Chemical 14]

[0051]

[Chemical 15]

These compounds are usually hydrochlorides, sulphates,
It is used in the form of salts such as p-toluenesulfonate, oxalate, phosphate and acetate.

The concentration of the compound represented by the above general formula [2] in the color developer is usually, for example, preferably 0.1 to 50 g / l, more preferably 0.3 to 30 g / l, particularly preferably 0.5 to 20 g. / L.

The above compounds may be used in combination of two or more kinds.

It is preferable to use an aldehyde bisulfite addition compound together with the color developing solution of the present invention from the viewpoint of improving the preservability of color development. The aldehyde bisulfite addition compound preferably used is a compound represented by the following general formula [4] or [5].

[0056]

[Chemical 16]

In the general formulas [4] and [5], A ₁ ,
A ₂ , A ₃ and A ₄ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group, M represents an alkali metal atom, and n represents an integer of 0 to 4. .

The alkyl group having 1 to 6 carbon atoms includes linear or branched ones, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, isopentyl group, hexyl group and isohexyl group. And the like, which may be substituted, and specifically include formyl group (for example, each group such as formylmethyl and 2-formylethyl), amino group (for example, each group such as aminomethyl and aminoethyl), hydroxyl. A group (eg hydroxymethyl,
Substituents such as 2-hydroxyethyl, 2-hydroxypropyl, etc.), alkoxy groups (eg, methoxy, ethoxy, etc.), halogen atoms (eg, chloromethyl, trichloromethyl, dibromomethyl, etc.) Can be mentioned. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and a valeryl group. The alkenyl group, a substituted, there is an unsubstituted group, the unsubstituted group is vinyl, each group such as 2-propenyl, as a substituted one, for example, 1,2-dichloro-2-carboxyvinyl, Examples include groups such as 2-phenylvinyl. The alkali metal atom represented by M is, for example, sodium or potassium.

Specific examples of the aldehyde which forms the addition compound represented by the general formula [4] or [5] will be described below, but the present invention is not limited thereto.

(A-1) Formaldehyde (A-2) Acetaldehyde (A-3) Propionaldehyde (A-4) Isobutyraldehyde (A-5) n-Butylaldehyde (A-6) n-Barrelaldehyde (A- 7) Isovaleraldehyde (A-8) Methylethylacetaldehyde (A-9) Trimethylacetaldehyde (A-10) n-hexaaldehyde (A-11) Methyl-n-propylacetaldehyde (A-12) Isohexaaldehyde (A -13) Glyoxal (A-14) Malonaldehyde (A-15) Succinaldehyde (A-16) Glutaraldehyde (A-17) Adipinaldehyde (A-18) Methylglyoxal (A-19) Acetoacetic aldehyde (A-19) -20) Glycolaldehyde (A-21) Ethoxyacetaldehyde (A-22) Aminoacetaldehyde (A-23) Betaine aldehyde (A-24) Chloral (A-25) Chloroacetaldehyde (A-26) Dichloroacetaldehyde (A-27) Bromal (A-28) Dibromoacetaldehyde (A-29) Iodoacetaldehyde (A-30) α-Chloropropionacetaldehyde (A-31) α-Bromopropionacetaldehyde (A-32) mucochloric acid Among these compounds, the bisulfite addition compound of formaldehyde and the bisulfite addition compound of acetaldehyde are preferable because of their large effects. The amount of the bisulfite addition compound of aldehyde added to the color developing solution is suitably 0.1 to 30 g / l, preferably 0.7 to 10 g / l.

In order to contain the sulfite ion in the color developer of the present invention at an ion concentration of 1.5 × 10 ^-2 mol or less per liter of the color developer, in addition to the addition of the bisulfite addition compound of the aldehyde, water-soluble sulfite is added. A salt such as sodium sulfite or potassium sulfite may be added.

The sulfite ion concentration is preferably 1.5 × 10 ^-2
Mol / l or less 1.0 × 10 ⁻⁴ mol / l or more. When the concentration of sulfite ion exceeds 1.5 × 10 ^-2 mol / l, the concentration decrease becomes large with respect to the high silver chloride light-sensitive material, and 1.0 × 10 ^-4 mol / l
When it is lower than 1, there is a problem that the homeostasis is deteriorated.

As the color developing agent used in the color developing solution of the present invention, a p-phenylenediamine compound having a water-soluble group is preferable from the viewpoint of obtaining the effect of the present invention.

The p-phenylenediamine-based compound having a water-soluble group is free from contamination of the light-sensitive material, as compared with the p-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Also, it has an advantage that the skin is not easily rashed.

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

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

[0067]

[Chemical 17]

[0068]

[Chemical 18]

[0069]

[Chemical 19]

[0070]

[Chemical 20]

[0071]

[Chemical 21]

[0072]

[Chemical formula 22]

The above-mentioned color developing agents are usually used in the form of salts such as hydrochlorides, sulfates and p-toluenesulfonates, and usually 1 × 10 ^-3 to 2 × 10 ^-1 mol / l of color developing solution are used. It is preferably used in the range, but from the viewpoint of rapid processing, the range of 1.5 × 10 ⁻³ to 2 × 10 ⁻¹ mol per liter of the color developing solution is more preferable.

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

As the alkaline agent, for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, boric acid, etc. may be used alone. Alternatively, they can be used in combination. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, 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 as required. Furthermore, if necessary, a development accelerator can be used. US Pat. No. 2,648,604 as a development accelerator
No. 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafuran, neutral salts such as thallium nitrate, U.S. Pat. No. 2,533,990, same
2,531,832, No. 2,950,970, No. 2,577,127, and polyethylene glycol and its derivatives described in JP-B-44-9504, and nonionic compounds such as polythioethers are included. Further, benzyl alcohol and phenethyl alcohol described in US Pat. No. 2,304,925 and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia and the like can be mentioned.

Further, 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. An organic solvent for increasing the solubility of the developing agent described in each publication can be used.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl. -p-Phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 to 10 g / l. In addition to these, competing couplers, fogging agents, colored couplers, development inhibitor releasing couplers (so-called DIR couplers), if necessary,
Further, a development inhibitor releasing compound or the like can be added.

Furthermore, various additives such as other anti-staining agents, anti-sludge agents, and multi-layer effect accelerators can be used.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to constant water. In general,
Concentrated aqueous solution containing multiple components, each of which can coexist stably
Alternatively, it can be obtained by adding a substance prepared in advance in a small container in a solid state into water and stirring the mixture.

The color developing solution of the present invention 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 12.0.

The processing temperature for color development using the color developing solution of the present invention is 30 ° C. or higher and 50 ° C. or lower. The higher the temperature, the faster the processing can be carried out in a short time. There is also a problem that it is easy to do, more preferably 30 ℃ or more
It should be below ℃.

After color development processing using the color developing solution of the present invention, processing is carried out with a processing solution having a fixing ability. When the processing solution having a fixing ability is a fixing solution, bleaching treatment is carried out before that. Done. As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the bleaching step, a metal complex salt of an organic acid is preferably used, and the metal complex salt oxidizes metal silver produced by development to convert it to silver halide. At the same time, it has the effect of coloring the uncolored part of the color former,
Its structure is such that an amino acid such as aminopolycarboxylic acid or oxalic acid or citric acid is coordinated with a metal ion such as iron, cobalt or copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt or a chelating agent. In addition, a pH buffer such as borate, oxalate, carbonate, and phosphate, and those known to be added to ordinary bleaching solutions such as alkylamines and polyethylene oxides can be appropriately added.

Further, the fixing solution and the bleach-fixing solution include ammonium sulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, and other sulfites, boric acid, borax, sodium hydroxide, The pH buffering agent comprising various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide can be used alone or in combination of two or more kinds.

When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate or sulfite. The bleach-fixing replenisher may contain these salts and be replenished to the processing bath.

In order to increase the activity of the bleaching solution and the bleach-fixing solution, air may be blown or oxygen may be blown in the bleach-fixing bath and the storage tank for the bleach-fixing replenisher, if desired, or appropriate oxidation is carried out. Agents such as hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

The pH of the bleach-fixing solution is preferably 3.0 to 9.0,
More preferably, it is in the range of 4.0 to 8.0.

After color development processing using the color developing solution of the present invention, after bleaching and fixing (or bleach-fixing) processing, it is possible to carry out stable processing without washing with water, or to carry out stable processing after washing with water. Good. In addition to the above steps, dura, neutralization,
Known auxiliary steps such as black-and-white development, reversal, and small amount water washing step may be added as necessary. Representative examples of preferred treatment methods include the following steps.

(1) Color development → bleach-fixing → washing (2) Color developing → bleaching fixing → washing with a small amount of water → washing (3) Color developing → bleaching fixing → washing → stable (4) Color developing → bleaching fixing → stable (5) ) Color development → bleach-fixing → 1st stability → 2nd stability (6) Color development → washing (or stable) → bleach-fixing → washing
(Or stable) (7) Color development → stop → bleach-fix → water wash (or stable) (8) color development → bleach → water → fix → water wash → stable (9) color development → bleach → fix → water wash → stable (10 ) Color development → bleaching → small amount water washing → fixing → 1st stability → 2nd stability (11) Color development → bleaching → small amount water washing → fixing → small amount water washing → water washing → stable (12) color development phenomenon → bleaching → fixing → stable (13 ) Color development → stop → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stability The color developing solution of the present invention is a color paper, color film, color positive film, color positive paper, color reversal film for slides, color reversal film for movies. ,
It can be applied to color photographic light-sensitive materials such as color reversal film for TV and color reversal paper.

There is no particular limitation on the light-sensitive material processed by the color developing solution of the present invention. For example, the silver halide composition may be any of those used in ordinary silver halide light-sensitive materials such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. . In the silver halide composition, the color developer of the present invention is particularly advantageous in preservability, developability and rapid processability for emulsion layers having a silver chloride content of 85 mol% or more, particularly 90 mol% or more. .

The crystal of the silver halide grain may be a normal crystal, a twin crystal or any other crystal, and an arbitrary ratio of {100} plane to {111} plane can be used. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, a layered structure with different inside and outside (core / shell type)
It may be the one. 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 (see JP-A-58-113934 and JP-A-59-170070) may be used. The silver halide grains are preferably substantially monodisperse grains, which may be obtained by any preparation method such as an acidic method, a neutral method or an ammonia method.

Since the particle size distribution of the monodisperse emulsion is almost normal distribution, the standard deviation can be easily obtained. From this, the relational expression (standard deviation / average particle size) x 100 = breadth of distribution (%)
When the definition of the breadth (%) of the distribution is defined by, the breadth of the distribution is preferably 20% or less, and more preferably 10% or less. In the case of spherical silver halide grains, the grain size is the diameter thereof, and in the case of other than spheres, the grain size is calculated as spheres having the same area.

The above-mentioned silver halide may be one in which seed grains 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 growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled so that the amount of silver ions corresponding to the growth rate of silver halide grains as described in, for example, JP-A-54-48521. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

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 dioxide. Thiourea, polyamine, etc .;
Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc. or water-soluble such as ruthenium, palladium, platinum, rhodium, iridium, etc. Salt sensitizers, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these act as sensitizers or antifoggants depending on the amount) Etc.) alone or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer are used together, a gold sensitizer and a selenium sensitizer are used together), and they may be chemically sensitized.

The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and the nitrogen-containing heterocyclic ring having at least one hydroxytetrazaindene and mercapto group is added before, during, or after the chemical ripening. You may include at least 1 sort (s) of a compound.

The silver halide is optically sensitized by adding 5 × 10 ^{−8 to} 3 × 10 ⁻³ mol of sensitizing dye to 1 mol of silver halide in order to impart photosensitivity to a desired photosensitive wavelength region. You may feel it. 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.

The light-sensitive material to which the present invention is applicable is a coupler, that is, a red-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer.
Those containing a compound capable of reacting with an oxidized product of a color developing agent to form a dye are preferable.

As the yellow coupler which can be used, a closed ketomethylene compound, an active point-o-aryl substituted coupler and an active point-o-so-called 2-equivalent type coupler.
Acyl-substituted couplers, active-point hydantoin compound-substituted couplers, active-point urazole compound-substituted couplers, active-point succinimide compound-substituted couplers, active-point fluorine-substituted couplers. Active point chlorine or bromine substituted coupler,
Active site-o-sulfonyl substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patent No. 2,875,057,
No. 3,265,506, No. 3,408,194, No. 3,551,155
No. 3, No. 3,582,322, No. 3,725,072, No. 3,891,44
5, West German Patent 1,547,868, West German Application Publication No. 2,219,91
No. 7, No. 2,261,361, No. 2,414,006, British Patent No.
1,425,020, JP-B-51-10783, JP-A-47-26133,
48-73147, 51-102636, 50-6341, 50-123
342, 50-130442, 51-21827, 50-87650,
Examples thereof include those described in Nos. 52-82424, 52-115219, and 58-95346.

Examples of magenta couplers that can be used include pyrazolone compounds, pyrazolotriazole compounds, pyrazolinobenzimidazole compounds, and indazolone compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers that can be used include U.S. Patent Nos. 2,600,788 and 2,983,608.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,506, No. 3,834,
908, 3,891,445, West German Patent 1,810,464, West German Patent Application (OLS) 2,408,665, 2,417,945,
No. 2,418,959, No. 2,424,467, Japanese Patent Publication No. 40-6031
No. 5, JP-A-51-20826, No. 52-58922, No. 49-129538
No. 49, No. 74027, No. 50-159336, No. 52-42121, No. 4
9-74028, 50-60233, 51-26541, 53-55122
And Japanese Patent Application No. 55-110943.

Examples of cyan couplers that can be used include phenol type and naphthol type couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers that can be used include U.S. Patent Nos. 2,369,929 and 2,434,272.
No. 2, No. 2,474,293, No. 2,521,908, No. 2,895,82
No. 6, No. 3,034,892, No. 3,311,476, No. 3,458,3
No. 15, No. 3,476,563, No. 3,583,971, No. 3,591,
No. 383, No. 3,767,411, No. 3,772,002, No. 3,93
No. 3,494, No. 4,004,929, West German patent application (OLS) No. 2,4
14,830, 2,454,329, JP-A-48-5983, 51-2
No. 6034, No. 48-5055, No. 51-146827, No. 52-69624,
Examples thereof include those described in No. 52-90932, No. 58-95346, and Japanese Patent Publication No. 49-11572.

In the silver halide emulsion layer and other photographic constituent layers, a colored magenta or colored cyan coupler,
You may use together couplers, such as a polymer coupler. For the colored magenta or colored cyan coupler, the description of Japanese Patent Application No. 193611/96 by the applicant can be referred to, and for the polymer coupler, the description of Japanese Patent Application No. 59-172151 by the present applicant can be referred to.

The addition amount of the above coupler is not limited, but
The amount is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ^{−2 to} 5 × 10 ⁻¹ mol per mol of silver.

The photographic material to which the present invention can be applied may contain various photographic additives in addition to the above. For example, Research Disclosure magazine 1
Antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents described in No. 7643. Agents and the like can be used.

In the light-sensitive material to which the present invention is applied, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

Examples of the support of the light-sensitive material to which the present invention is applied include a reflective support such as baryta paper and polyethylene-coated paper and a transparent support, and these supports are appropriately selected according to the purpose of use of the light-sensitive material. To be done.

In the light-sensitive material to which the present invention can be applied, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer. Can be appropriately combined and used as a constituent layer. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

The light-sensitive material may contain a DIR compound, and may further contain, in addition to the DIR compound, a compound which releases a development inhibitor upon development. For example, US Pat. No. 3,297,445, No. 3,379,529, West German patent application (OLS) No. 2,417,914, JP-A Nos. 52-15271, 53-9
No. 116, No. 59-123838, No. 59-127038, etc. are mentioned.

The above-mentioned DIR compound is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor or a development inhibitor precursor, and may be a non-diffusible DIR compound or a diffusible DIR compound. It may be.

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting action when released from the active site is introduced into the active site of the coupler. Patent No. 935,454, U.S. Patent No. 3,227,554, No. 4,095,954, No. 4,149,88
It is described in No. 6 etc.

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 mother nucleus of the coupler forms a dye, while releasing a development inhibitor. Further, in the present invention, U.S. Patent Nos. 3,652,345 and 3,928,041
No. 3, No. 3,958,993, No. 3,961,959, No. 4,052,21
3, JP-A-53-110529, JP-A-54-13333, JP-A-55-161237
A compound which releases a development inhibitor but does not form a dye when it undergoes a coupling reaction with an oxidant of a color developing agent, as described in JP-A No. 1994-242, etc., is also included.

Furthermore, JP-A-54-145135 and JP-A-56-11.
When reacted with an oxidant of a color developing agent as described in 4946 and 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Alternatively, it may be a so-called timing DIR compound, which is a compound that releases a development inhibitor by an elimination reaction.

Further, as described above in the coupler mother nucleus which forms a completely diffusible dye when reacted with an oxidant of a color developing agent described in JP-A-58-160954 and JP-A-58-162949. It may also be a Timing DIR compound having a timing group attached. Generally, these DIR compounds are preferably used in an amount of 2 × 10 ^{−5 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol per mol of silver in the emulsion layer.

[0113]

EXAMPLES The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited to these.

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

(Color Developer) Potassium Sulfite Amount that can obtain the sulfite ion concentration shown in Table 1 Sodium chloride 0.3 g Potassium carbonate 25.0 g Preservative (shown in Table 1) Chelating agent [Exemplified compound (43)] 0.6 g Color developing agent [Exemplified Compound 1) 5.0 g Fluorescent brightening agent below 2.0 g Development accelerator (described in Table 1) 3.0 g Potassium hydroxide and water were added to make 1 liter. The pH is 10.
It was 10.

[0116]

[Chemical formula 23]

Each color developer (No. 1 to No. 13) contained 4 ppm of ferric ion, 2 ppm of copper ion and 100 ppm of calcium ion.
(FeCl ₃ , CuSO ₄ · 6H ₂ O and CaCl ₂ are dissolved and added respectively), and the glass with an opening ratio of 30 cm ² / l (air contact area for 1 liter of developer is 30 cm ² ) at 50 ° C. Stored in a container. The appearance (coloring degree) of the color developing solution after 7 days 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 change, and the results are shown in Table 1.

Separately, the following layers were sequentially coated on a polyethylene-coated paper support from the side of the support to prepare a light-sensitive material. As the polyethylene coated paper, 6.8 wt% of anatase type titanium oxide was added to a mixture of 200 parts by weight of polyethylene having an average molecular weight of 100,000 and a density of 0.95 and 20 parts by weight of polyethylene having an average molecular weight of 2000 and a density of 0.80, and the extrusion coating method was used. A coating layer having a thickness of 0.035 mm was formed on the surface of a high-quality paper having a weight of 170 g / m ² , and a coating layer having a thickness of 0.040 mm was provided on the back surface with only polyethylene. After pretreatment by corona discharge on the polyethylene-coated surface of this support, the following layers were sequentially applied.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 4 mol% of silver bromide, said emulsion containing 350 g of gelatin per mol of silver halide and containing 1 mol of silver halide per mol of silver halide. 2,5-Sensitized dye (I) having the following structure was sensitized with 2.5 × 10 ⁻⁴ mol of sensitizing dye (using isopropyl alcohol as a solvent), and dissolved and dispersed in dibutyl phthalate.
Di-t-butylhydroquinone 200 mg / m ² and [Y-1] having the following structure as a yellow coupler were contained in an amount of 2.0 × 10 ^-1 mol per mol of silver halide, and the amount of silver was 300 mg / m ^2. There is.

Second layer: di-t-octylhydroquinone 300 mg / m ² dissolved and dispersed in cibutyl phthalate, 2- (2'-hydroxy-3 ', 5'-di-t- as an ultraviolet absorber Butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro
-Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
t- butylphenyl) -5-chloro - mixture of benzotriazole (1: 1: 1: 1) is applied so that the gelatin 1900 mg / m ² of gelatin layer containing 200 mg / m ^2.

Third layer: a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 2 mol% of silver bromide, said emulsion containing 450 g of gelatin per mol of silver halide and containing 1 mol of silver halide per mol of silver halide. 2,5-di-t-butylhydroquinone and magenta sensitized with 2.5 × 10 ⁻⁴ mol of a sensitizing dye (II) having the following structure and dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2: 1 As a coupler, [M-1] having the following structure was contained in an amount of 1.5 × 10 ⁻¹ mol per mol of silver halide, and the amount of silver was 230 mg / m ² and the AI dye was coated at 50 mg / m ² . In addition, 0.30 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was added as an antioxidant per mol of the coupler.

Fourth layer: 30 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) as an ultraviolet absorber. ) Benzotriazole, 2- (2'-hydroxy
-5'-t-butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di -t- butyl phenyl) -5-chloro - mixture of benzotriazole (2: 1.5: 1.5: 2) a gelatin layer containing 500 mg / m ^2, is coated so as to gelatin 1900 mg / m ² .

Fifth layer: a red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 3 mol% of silver bromide, said emulsion containing 500 g of gelatin per mol of silver halide and containing 1 mol of silver halide per mol of silver halide. Sensitizing dye (III) having the structure shown below, sensitized with 2.5 × 10 ⁻⁵ mol of 2,5-di-t-butylhydroquinone 150 mg / m ² dissolved and dispersed in dibutyl phthalate and the structure shown below as a cyan coupler [C-1] of silver halide 1
It contains 3.5 × 10 ^-1 mol per mol and is coated so that the amount of silver is 280 mg / m ² and the AI dye is 40 mg / m ² .

Sixth layer: a gelatin layer containing 90% gelatin.
It is applied so as to be 0 mg / m ² .

The silver halide emulsions used in the respective photosensitive emulsion layers (first, third and fifth layers) were prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was prepared. Chemically sensitized with 4-hydroxy-6 as a stabilizer
-Methyl-1,3,3a, 7-tetrazaindene (silver halide 1
2.5 g per mol), bis (vinylsulfonylmethyl) ether (10 mg per 1 g gelatin) as a hardener, and saponin as a coating aid.

[0128]

[Chemical formula 24]

[0129]

[Chemical 25]

After the color paper prepared by the above method was exposed, it was processed using the following processing steps and processing solutions.

Processing step (1) Color development 35 ° C 45 seconds (2) Bleach fixing 35 ° C 45 seconds (3) Washing alternative stabilization treatment 30 ° C 90 seconds (4) Dry 60 ° C-80 ° C 1 minute 30 seconds Treatment Liquid composition [Color developing tank liquid] The above color developing liquids (No. 1 to No. 13) [Bleaching fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) ) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Adjust the pH to 5.50 with aqueous ammonia or glacial acetic acid and add water to make a total volume of 1 liter.

[Stable tank solution as a substitute for washing with water] Orthophenylphenol 0.2 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% solution) 2.0 g Ammonia water 3.0 g Make up to 1 liter with water, and add pH 7.8 with ammonia water and sulfuric acid. And

An automatic processor was filled with the above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and the color paper sample was processed to measure the maximum density of yellow.
The results are shown in Table 1. However, the above maximum concentration is the developer No.
It was shown as a relative value with the concentration when 100 was used as 3.

[0134]

[Table 1]

From Table 1, the color developer contains the compound represented by the general formula [1] and the compound represented by the general formula [2] and the sulfite ion concentration is 1.5 × 10 ^-2 mol / l.
By setting the ^{ratio to} 1.0 × 10 ⁻⁴ or more and 1.0 × 10 ⁻² or less, the photographic characteristics due to the preservability while maintaining the good preservability of the color developing solution as compared with the conventional color developing solution. It can be seen that the decrease in density is reduced when a light-sensitive material having a high silver chloride content is rapidly processed, which is a bad side effect to

Example 2 Example 1 was repeated except that in the color developer, the preservative, the compound represented by the general formula [1], and the sulfite ion concentration were set as shown in Table 2 and the number of storage days was 10 days. The same experiment was performed. The results are shown in Table 2. The maximum density (yellow density) is shown as a relative value with developing solution No. 19 as 100.

[0137]

[Table 2]

From Table 2, within the range of the general formula [1],
It can be seen that the compound represented by the general formula [3] is particularly effective in increasing the color density without impairing the preservability.

Example 3 On a polyethylene-laminated paper support, the following layers were sequentially coated from the support side to prepare an internal latent image type photosensitive material.

First layer: cyan-forming red-sensitive silver halide emulsion layer 2,4-dichloro-3-methyl-6- [α-as a cyan coupler
(2,4-di-tert-amylphenoxy) butyramide] phenol 90 g, 2,5-di-tert-octylhydroquinone 2 g,
50 g of tricresyl phosphate, 200 g of paraffin and 50 g of ethyl acetate were mixed and dissolved, and a gelatin solution containing sodium dodecylbenzenesulfonate was added to the mixture to give an average particle size of 0.
Internal latent image type silver halide emulsion (prepared by the conversion method according to Example 1 described in US Pat. No. 2,592,250) dispersed to have a particle size of 6 μm (AgBr: AgCl = 70: 3).
0) was added and coating was carried out so that the silver amount was 400 mg / m ² , the AI dye was 20 mg / m ² , and the coupler amount was 360 mg / m ² .

Second Layer: Intermediate Layer 5 g of gray colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate 2.
100 ml of 5% gelatin solution was applied so that the amount of colloidal silver was 400 mg / m ² .

Third layer: magenta-forming green-sensitive silver halide emulsion layer 1- (2,4,6-trichlorophenyl) as a magenta coupler
-3- (2-chloro-5-octadecylsuccinimidoanilino)
-5-Pyrazolone 100g, 2,5-di-tert-octylhydroquinone 5g, Sumilizer MDP (Sumitomo Chemical Co., Ltd.) 50
g, paraffin 200 g, dibutyl phthalate 100 g and ethyl acetate 50 g were mixed and dissolved, and a gelatin solution containing sodium dodecylbenzenesulfonate was added to the mixture to give an average particle size of 0.6.
An internal latent image type silver halide emulsion (AgBr: AgCl = 60: 4) prepared in the same manner as the first layer, dispersed so as to have a thickness of μm.
0) was added and coated so that the amount of silver was 400 mg / m ² , the amount of AI dye was 20 mg / m ² , and the amount of coupler was 400 mg / m ² .

Fourth Layer: Yellow Filter Layer 2.5% gelatin solution containing 5 g of yellow colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate so that the colloidal silver becomes 200 mg / m ^2. Was applied to.

Fifth layer: yellow-forming blue-sensitive silver halide emulsion layer α- [4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α as a yellow coupler -Bivalyl-2-chloro-5- [γ- (2,4-di-tert-amylphenoxy) butyramide] acetanilide 120 g, 2,5-di-tert-
Octyl hydroquinone 3.5 g, paraffin 200 g, Tinuvin (Ciba Geigy) 100 g, dibutyl phthalate 1
An internal latent image type halogen prepared in the same manner as the first layer, in which 00 g and 70 ml of ethyl acetate were mixed and dissolved, and a gelatin solution containing sodium dodecylbenzenesulfonate was added and dispersed so that the average particle size was 0.9 μm. Silver halide emulsion (AgBr: AgCl =
80:20) was added, and the amount of silver was 400 mg / m ² , the amount of coupler was 400 mg /
It was applied so as to be m ² .

Sixth layer: protective layer Coating was carried out so that the amount of zetillane was 200 mg / m ² .

All of the above layers contained saponin as a coating aid. As a hardening agent, 2,4-dichloro-6-
Hydroxy-s-triazine sodium layers 2, 4 and 6
0.02 g per 1 g of gelatin was added thereto.

The internal latent image type photosensitive material sample was exposed through an optical wedge and then processed in the next step.

Treatment step (38 ° C.) Immersion (color developing solution) 8 seconds Color development 120 seconds (first 10 seconds, uniform exposure of the entire surface with 1 lux light) Bleach fixing 60 seconds Water washing 60 seconds Dry 60 to 80 ° C 120 seconds The composition of each processing solution is as follows.

(Color developer) Benzyl alcohol 15 ml Ethylene glycol 10 ml Potassium sulfite Amount to obtain sulfite ion concentration shown in Table 3 Potassium bromide 1.5 g Sodium chloride 0.3 g Potassium carbonate 25.0 g Preservative and development accelerator (see Table 3) ) The following chelating agent 0.6 g Color developing agent (Exemplified compound (1) / (3) = molar ratio 1/1) 7.5 g Optical brightener (same as in Example 1) 2.0 g Add potassium hydroxide and water It was 1 liter. The pH is 10.
It was 20.

[0150]

[Chemical formula 26]

(Bleach-fixing solution) Pure water 550 ml Ethylenediaminetetraacetic acid iron (III) ammonium salt 65 g Ammonium thiosulfate (70% aqueous solution) 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Pure water was added. 1 liter, p with ammonia water or dilute sulfuric acid
Adjust to H = 7.0.

The light-sensitive material was subjected to stepwise exposure by a conventional method and processed by the method described above, and the minimum reflection density (blue density) was measured. The colorability of the color developing solution was evaluated in the same manner as in Example 1. (The storage period is 10 days) The results are shown in Table 3.

[0153]

[Table 3]

From Table 3, for the internal latent image type light-sensitive material, the color developing solution according to the present invention has an increase in Dmin which is an undesired influence on the photographic characteristics to be equal to or less than that in the conventional color developing solution. It can be seen that the preservability of the color developing solution is improved. Furthermore, it is understood that the purpose of the present invention can be achieved to a higher degree because the color developer according to the present invention particularly preferably has a sulfite ion concentration of 1.0 × 10 ⁻⁴ or more and 1.5 × 10 ⁻² or less.

The same experiment was conducted by changing the compounds represented by the general formula [2] from (17) and (24) to (1), (13), (18) and (20). Almost similar results were obtained. Especially (18) and (20) were good.

Example 4 The compound represented by the general formula [4] or [5] was converted to (A-1)
To (A-2), (A-3), (A-4), (A-5), (A-1
4), (A-15) and (A-16) except that the same experiment as in Example 3 was carried out, and almost the same result as in Example 3 was obtained.

[0157]

According to the present invention, the following effects (a) to (c) can be obtained.

(A) A superior homeostasis is obtained when hydroxylamine is used without using hydroxylamine, which has the drawback of being a poisonous substance as a homeostasis.

(B) As described above, in the color developing solution, when it is desired to obtain practical preservability by using a preservative,
The unfavorable influence of the preservative on the photographic characteristics and the rapid processability and the means for preserving one of the preservatives are unavoidable that the other is deteriorated. And the above-mentioned relationship between rapid processability (especially for a light-sensitive material having an emulsion layer having a high silver chloride content) and preservability is improved. That is, for example, the preservability of the color developing solution can be improved while maintaining the conventional good level in color density and rapid processability.

(C) Since the present invention improves the preservability of the color developing solution as described above, when the silver halide color photographic light-sensitive material having an internal latent image type emulsion is fog-developed, color development is performed. The filter effect due to the coloring of the liquid is reduced, and stable photographic characteristics can be obtained.

Claims (1)

[Claims] 1. A compound represented by the following general formula [1], a compound represented by the following general formula [2] and not more than 1.5 × 10 ⁻² mol of sulfite ion per liter of a color developing solution. Color developer for silver halide color photographic light-sensitive materials. [Chemical 1] [In the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms.
6 hydroxyalkyl group, alkoxy group or alkoxyalkyl group, R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an alkoxyalkyl group, a benzyl group, aryl Group or formula In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms.
Of R ₂ and R ₃ , and R ₁ and R ₃ may combine with each other to form a ring. ] [Chemical 3] [In the formula, R ₄ and R ₅ each represent a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms. However,
R ₄ and R ₅ are not hydrogen atoms at the same time. ]