JP2544610B2 - Color developing solution for silver halide color photographic light-sensitive materials with improved stability and safety - Google Patents

Description

The present invention relates to a color developer for a silver halide color photographic light-sensitive material, and more specifically, it is a preservative that replaces hydroxylamine, which is harmful to humans and is a poisonous substance. And a color developing solution for a silver halide color photographic light-sensitive material.

[Background of the Invention]

In color development exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the 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.

The color developer used for such color development is usually
In order to increase its preservative property, a sulfite or a water-soluble salt of sulfite and hydroxylamine is added as a preservative (antioxidant). Among them, like the former, when the sulfite is used alone, fogging occurs remarkably over time.Therefore, by using the sulfite and the water-soluble salt of hydroxylamine together, the stability of the developer is maintained. Is significantly increased, and the generation of fogging due to aged developer is reduced.

However, hydroxylamine has the following drawbacks and disadvantages.

That is, firstly, it has been reported that hydroxylamine is harmful to the human body [eg, PGStecher, “The Merc.
k Index An Encyclopedia of Chemical and 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 agent for poisonous and deleterious substances and to set up a person in charge of handling, which is extremely inconvenient to handle. Is.

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.

Fourth, hydroxylamine decomposes when heavy metal ions (for example, iron ions or copper ions) are mixed in the color developing solution to produce ammonia, which causes fogging on the color light-sensitive material and also improves photographic performance. It has a drawback that it has a bad effect on 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-house self-treatment or color copying equipped with a color developing system, it is strongly desired to develop a preservative that replaces hydroxylamine because of pollution problems.

As preservatives replacing 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, in a developer (for black and white photography) containing hydroquinone or N-alkyl-p-aminophenol as a developing agent, sucrose (sucrose) is known as a preservative, but sucrose is an aromatic primary amine. A color developing solution containing as a developing agent has little effect as a preservative.

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

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

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

And 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 a derivative thereof and a bisulfite adduct of aldehyde are used in combination as a preservative for a color developing solution. The technique of using is disclosed. 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 was revealed 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.

Third, in the case of rapid processing development, the presence of sulfite ion concentration and hydroxylamine greatly affects the rapidity, and it is necessary to reduce sulfite ion concentration as much as possible and to use no hydroxylamine. 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, with the need for rapid processing in the future,
The above method alone is not sufficiently satisfactory, and for example, in the case of processing using a light-sensitive material having a high silver chloride content, even if the bisulfite addition compound of aldehyde coexists, the concentration tends to decrease. It became clear by the study of the present inventors.

[Object of the Invention]

Therefore, the object of the present invention is to solve the above-mentioned drawbacks, and it is not necessary to contain hydroxylamine, which is harmful to the human body as a preservative, and the preservability is improved as compared with conventional color developing solutions using hydroxylamine. Moreover, it is to provide a color developing solution which can be rapidly processed without significantly affecting photographic characteristics.

[Structure of Invention]

The above-mentioned object of the present invention comprises a bisulfite addition compound of an aldehyde, a compound represented by the following general formula [1] and at least one hydroxylamine derivative selected from the following (1) to (4), and sulfite: It is achieved by a color developing solution for silver halide color photographic light-sensitive materials, which contains ions at a concentration of 1.5 × 10 ^-2 mol or less and contains substantially no hydroxylamine.

General formula [1] In the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms.
Is a hydroxyalkyl group, an alkoxy group or an alkoxyalkyl group, R ₂ and R ₃ are each a hydrogen atom or a carbon
~ 6 alkyl group, C2-6 hydroxyalkyl group, alkoxyalkyl group, benzyl group, aryl group or formula In the 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.

The combined use of bisulfite addition compounds of aldehydes with sulfites is described in JP-B-61-48698 and JP-B-61-48699, and from the viewpoint of homeostasis, it is sufficient to use a large amount of the compound. It can be easily estimated that it has a homeostatic property, but there is also a problem in that, for example, in the photographic performance, the density of the coloring dye decreases, and the addition amount dependency is large, so that the optimum addition amount is limited. ing.

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 the sulfite ion concentration, and even a high silver bromide-containing photosensitive material can be directly positive photosensitive material depending on the amount of sulfite. It was found that there was a marked difference in the degree of yellow stain. 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 used in combination with an aldehyde bisulfite addition compound, the homeostasis does not significantly deteriorate even if the sulfite ion concentration is lowered,
Rather, it was found that coexistence of a certain amount of sulfite was sufficient as the preservation ability.

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.

However, as described above, even if the sulfurous acid concentration is lowered from the viewpoint of rapid processing and homeostasis, rapidity is required, for example, when processing a high silver chloride-containing light-sensitive material, or a color negative film using a silver iodobromide emulsion. The inventors of the present invention have found that the problem that the color density is not sufficiently obtained when the above process is carried out in a short time is examined.

Among the compounds represented by the general formula [1], the compound represented by the following general formula [2] is particularly preferable.

General formula [2] In the formula, R ₄ is a hydrogen atom or has 1 to 6 carbon atoms (preferably 1
~ 3) alkyl group, R ₅ represents an alkylene group having 1 to 6 carbon atoms, R ₆ represents a hydrogen atom, R ₇ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms. 6 represents an alkoxy group or a phenyl group, and is preferably a hydrogen atom.
Further, R ₆ and R ₇ , and R ₅ and R ₇ each represent a nitrogen-containing heterocycle which may be bonded to each other to form. n represents 0 or 1, and when R ₄ is a hydrogen atom, n is 1.

In the above general formula [2], examples of the alkyl group represented by R ₄ include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.

The alkylene group represented by R ₅ may be linear or branched, and 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 ₆ and R ₇ is, for example, And a nitrogen-containing heterocycle formed by R ₅ and R ₇ is, for example, It is a ring such as.

Next, preferable specific examples of the compound represented by the general formula [1] will be shown.

(DA-1) N ₂ N-CH ₂ CH ₂ OH (DA-13) H ₂ N-CH ₂ CH ₂ CH ₂ OH (DA-19) H ₂ NCH _{2 3} OC ₃ H ₇ (i) (DA-20) H ₂ NCH _{2 3} OC ₃ H ₇ (DA-21) H ₂ NCH _{2 3} O-CH ₃ (DA-22) H ₂ NCH _{2 3} OC ₂ H ₅ (DA-23) H ₂ NCH _{2 4} OH (DA-24) H ₂ NO-CH ₃ (DA-28) H ₂ NCH _{2 2} OC ₂ H ₅ (DA-29) H ₂ NCH _{2 2} O-CH ₃ (DA-30) H ₂ NCH _{2 2} OC ₃ H ₇ (i) (DA-31) H ₂ N-CH ₂ -OC ₂ H ₅ (DA-32) H ₂ N-CH ₂ -OC ₃ H ₇ (DA-34) H ₂ NOC ₂ H ₅ (DA-36) H ₂ NCH _{2 4} OC ₃ H ₇ (DA-37) H ₂ NCH _{2 4} OC ₂ H ₅ The above compounds may be added alone to the color developing solution,
It is also possible to add two or more kinds in combination.

The addition amount is preferably 0.1 to 50 g, and more preferably 0.3 to 30 g, per 1 color developer.

The aldehyde bisulfite addition compound preferably used in the present invention is a compound represented by the following general formula [3] or [4].

General formula [3] General formula [4] In the formula, 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 0. Represents an integer of 4;

The alkyl group having 1 to 6 carbon atoms includes linear or branched ones, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, an isopentyl group, a hexyl group and an isohexyl group. Or may be substituted, and specifically, formyl group (for example, each group such as formylmethyl and 2-formylethyl), amino group (for example, each group such as aminomethyl and aminoethyl),
Hydroxyl group (for example, groups such as hydroxymethyl, 2-hydroxyethyl, -hydroxypropyl, etc.), alkoxy group (for example, groups such as methoxy, ethoxy, etc.), halogen atom (for example, groups such as chloromethyl, trichloromethyl, dibromomethyl, etc.) ) And the like.

Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and a valeryl group.

The alkenyl group includes substituted and unsubstituted groups, the unsubstituted group includes groups such as vinyl and 2-propenyl, and the substituted group includes, for example, 1,2-dichloro-2
Groups such as carboxyvinyl and 2-phenylvinyl. The alkali metal atom represented by M is, for example, sodium or potassium.

Hereinafter, specific examples of the aldehyde that forms the addition compound represented by the general formula [3] or [4] will be described, 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) Iso Valeraldehyde (A-8) Methylethylacetaldehyde (A-9) Trimethylacetaldehyde (A-10) n-Hexaldehyde (A-11) Methyl-n-propylacetaldehyde (A-12) Isohexaldehyde (A-13) Glyoxal (A-14) Malonaldehyde (A-15) Succinic aldehyde (A-16) Glutaraldehyde (A-17) Adipine aldehyde (A-18) Methylglyoxal (A-19) Asatoacetic acid aldehyde (A-20) Glycolaldehyde (A-21) Ethoxyacetaldehyde (A-2 2) Aminoacetaldehyde (A-23) Betaine aldehyde (A-24) Chloral (A-25) Chloroacetaldehyde (A-26) Dichloroacetaldehyde (A-27) Bromar (A-28) Dibromoacetaldehyde (A-29) Iodo Acetaldehyde (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 Great effect and preferable.

The amount of the bisulfite addition compound of aldehyde added to the color developer is suitably 0.1 to 30 g / l, preferably 0.7 to 1
It is 0 g / l.

In order to make the color developer of the present invention contain sulfite ion at an ion concentration of 1.5 × 10 ^-2 mol or less per color developer, in addition to the addition of the bisulfite addition compound of the aldehyde, a water-soluble sulfite, for example, Sodium sulfite,
It suffices to add potassium sulfite or the like.

Sulfite ion concentration is preferably 1.5 × 10 ^-2 mol / l or less
It is 1.0 × 10 ⁻⁴ mol / l or more. Sulfite ion concentration is 1.5 ×
^10-2 density reduction increases mol / exceeds l and for the high chloride silver photosensitive material, reduction in preservability is problematic and less than 1.0 × 10 ^-4 mol / l.

In the present invention, the hydroxylamine derivative (1) to (4) (hereinafter referred to as “hydroxylamine derivative of the present invention”) is usually a hydrochloride, a sulfate, a p-toluenesulfonate, an oxalate or a phosphate. , Used in the form of salts such as acetate.

The concentration of the hydroxylamine derivative of the present invention is usually
For example, 0.1 to 50 g / l is preferable, more preferably 0.3 to 30 g
/ l, particularly preferably 0.5 to 20 g / l.

Two or more kinds of the hydroxylamine derivatives of the present invention may be used in combination.

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 has less contamination of the light-sensitive material and has less skin contamination than the p-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Also has the advantage that the skin is less likely to get rash.

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) 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.

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

The above color developing agents are usually used in the form of salts such as hydrochlorides, sulfates and p-toluenesulfonates, and are usually used in the range of 1 × 10 ⁻³ to 2 × 10 ⁻¹ mol per 1 color developing solution. However, from the viewpoint of rapid processing, color developer 1
The range of 1.5 × 10 ^{-3 to} 2 × 10 ^-1 mol 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 and the like can be used alone or 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. As the development accelerator, U.S. Pat.Nos. 2,648,604 and 3,671,247, JP-B-44-9503
Various pyridinium compounds represented by the publication of No. 6, other cationic compounds, cationic dyes such as phenosafuran, neutral salts such as thallium nitrate, US Pat.
No. 533,990, No. 2,531,832, No. 2,950,970, No.
2,577,127 and Japanese Patent Publication No. 44-9504, and nonionic compounds such as polyethylene glycol and its derivatives and polythioethers are included. U.S. Pat.No. 2,304,92
Benzyl alcohol, phenethyl alcohol and others described in No. 5, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers,
Examples include pyridine and ammonia.

Further, the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, 44-9509 described each publication An organic solvent for increasing the solubility of the developing agent 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 (meth), 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), development inhibitor releasing compounds and the like can be added.

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

Each component of the color developing solution can be prepared by sequentially adding to a certain amount of water and stirring. In general, a plurality of components, each of which can coexist in a stable manner, can be obtained as a concentrated aqueous solution or by adding in water a mixture prepared in advance in a small container in a solid state and stirred.

The color developer 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, it is used at pH 9.8 to 12.0.

The processing temperature for color development using the color developing solution of the present invention is
The temperature is 30 ° C or higher and 50 ° C or lower, and the higher the temperature, the quicker the treatment can be performed, which is preferable. However, conversely, there is a problem that the preservability is easily deteriorated. More preferably, the temperature is 30 ° C or higher and 45 ° C or lower.

After color development processing using the color developing solution of the present invention,
The treatment liquid having a fixing ability is used. When the treatment liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. 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 a function of coloring the uncolored portion of the color-developing agent, and its structure is such that an organic 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 desirable to include a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt, or a chelating agent. In addition, pH of borate, oxalate, carbonate, phosphate, etc.
A buffering agent, alkylamines, polyethylene oxides and the like which are known to be added to a normal bleaching solution can be appropriately added.

Further, fixing solutions and bleach-fixing solutions include sulfites such as ammonium sulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite and sodium metabisulfite, boric acid, borax, sodium hydroxide and potassium hydroxide. , Sodium carbonate, potassium carbonate,
A single pH buffer or two or more pH buffers composed of various salts such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained.

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

In order to increase the activity of the bleaching solution and the bleach-fixing solution, air may be blown thereinto or oxygen may be blown in the bleaching-fixing bath and the storage tank of the bleach-fixing replenisher, or a suitable oxidizing agent such as, for example, Hydrogen peroxide, bromate, persulfate and the like may be added appropriately.

The pH of the bleach-fixing solution is preferably 3.0 to 9.0, more preferably 4.0 to 8.0.

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

(1) Color development → bleach-fixing → washing with water (2) Color developing → bleach-fixing → washing with a small amount of water → water washing (3) Color developing → bleach-fixing → washing → stable (4) Color developing → bleach-fixing → stable (5) Color developing → Bleach-fixing → 1st stability → 2nd stability (6) Color development → Washing (or stable) → Bleach-fixing → Washing (or stable) (7) Color-developing → Stop → Bleach-fixing → Washing (or stable) (8) Color development → Bleaching → Washing → Fixing → Washing → Stable (9) Color developing → Bleaching → Fixing → Washing → Stable (10) Color developing → Bleaching → Washing with a small amount of water → Fixing → 1st stable → 2nd stable (11) Color developing → Bleach → Wash with a small amount of water → Fixing → Wash with a small amount of water → Rinse with water → Stable (12) Color development → Bleach → Fix → Stable (13) Color development → Stop → Bleach → Rinse with small amount of water → Fix → Rinse with small amount of water → Stable → Color development of the present invention Developers are color paper, color film, color positive film, color Di paper, can be applied slide for color reversal films, color reversal films for movie, TV for color reversal film, a color photographic light-sensitive material, such as a 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 is silver bromide,
Any of silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride and the like used in ordinary silver halide light-sensitive materials may be used. 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 normal crystal, twin crystal or other crystal, and any ratio of {100} plane to {111} plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (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, the standard deviation can be easily obtained. The relational expression If the breadth of distribution (%) is defined by
Those having a monodispersity of 20% or less are preferable, 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 silver halide is prepared by seed particles by an acidic method, and further,
It may be grown by an ammonia method having a high growth rate and grown to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and an 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 primary sensitizers.
Tin salts, thiourea dioxide, polyamines, etc .; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and 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, combination of gold sensitizer and sulfur sensitizer, combination of gold sensitizer) Chemically combined with a selenium sensitizer).

The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one hydroxytetrazaindene and at least one nitrogen-containing heterocyclic compound having a mercapto group are contained. You may make it contain 1 type.

The silver halide may be optically sensitized by adding a sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ⁻³ mol per mol of the silver halide in order to impart photosensitivity to a desired wavelength range. Good. Various sensitizing dyes can be used,
Further, each sensitizing dye may be used alone or in combination of two or more.

The light-sensitive material to which the present invention can be applied includes a red-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer, each of which is a coupler, that is, a dye which reacts with an oxidant of a color developing agent. Those containing a compound capable of forming are preferred.

Examples of yellow couplers that can be used include closed ketomethylene compounds, active-point-o-aryl-substituted couplers, active-point-o-acyl-substituted couplers, active-point hydantoin compound-substituted couplers, and active-point urazole compound-substituted so-called 2-equivalent type couplers. Couplers and active-point succinimide compound-substituted couplers, active-point fluorine-substituted couplers, active-point chlorine or bromine-substituted couplers, active-point-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. Pat.Nos. 2,875,057, 3,265,506, 3,408,194, and 3,551,155.
No. 3,582,322, No. 3,725,072, No. 3,891,445
No., West German Patent No. 1,547,868, West German Application Publication No. 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,
No. 425,020, Japanese Patent Publication No. 51-10783, JP-A No. 47-26133, No. 4
8-73147, 51-102636, 50-6341, 50-123342
No. 50, No. 50-130442, No. 51-21827, No. 50-87650, No. 5
2-82424, 52-115219, 58-95346 and the like can be mentioned.

Examples of magenta couplers that can be used include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based 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. Pat.Nos. 2,600,788, 2,983,608, and 3,
062,653, 3,127,269, 3,311,476, and
No. 3,419,391, No. 3,519,429, No. 3,558,319, No. 3,582,322, No. 3,615,506, No. 3,834,908,
No. 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,41
No. 8,959, No. 2,424,467, JP-B-40-6031, JP-A-5
1-20826, 52-58922, 49-129538, 49-74027
No. 50-159336, No. 52-42121, No. 49-74028. Same 5
No. 0-60233, No. 51-26541, No. 53-55122, Japanese Patent Application No. 55-11
Those described in No. 0943 and the like can be mentioned.

Examples of cyan couplers that can be used include phenol-based and naphthol-based 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, 2,434,272 and 2,47.
No. 4,293, No. 2,521,908, No. 2,895,826, No. 3,3
No. 034,892, No. 3,311,476, No. 3,458,315, No. 3
No. 3,476,563, No. 3,583,971, No. 3,591,383, No. 3,767,411, No. 3,772,002, No. 3,933,494,
No. 4,004,929, West German patent application (OLS) No. 2,414,830
No. 2,454,329, JP-A-48-5983, 51-26034
No. 48, No. 5055, No. 51-146827, No. 52-69624, No. 52
No. 90932, No. 58-95346, and Japanese Patent Publication No. 49-11572.

Couplers such as colored magenta or colored cyan couplers and polymer couplers may be used in combination in the silver halide emulsion layer and other photographic constituent layers. 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 amount of the coupler added is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ³ per mol of silver.
^{It is −2 to} 5 × 10 ⁻¹ mol.

The photographic material to which the present invention can be applied may contain various photographic additives. For example, antifoggants, stabilizers, UV absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners described in Research Disclosure magazine 17643. Agents, surfactants, plasticizers, wetting agents and the like can be used.

In the light-sensitive material to which the present invention is applied, hydrophilic colloids used for preparing an emulsion include gelatin, a derivative gelatin, a graft polymer of gelatin and another polymer, albumin, a protein such as casein, a hydroxyethyl cellulose derivative, Any one of cellulose derivatives such as carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl imidazole, and polyacrylamide is included.

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

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 are constituent layers. Can be used in appropriate combination. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

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, U.S. Pat.Nos. 3,297,445 and 3,379,529. , West German patent application (OL
S) No. 2,417,914, JP-A Nos. 52-15271, 53-9116,
Examples thereof include those described in Nos. 59-123838 and 59-127038.

The DIR compound 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. Good.

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 No. 935,454. No., US Patent
3,227,554, 4,095,954, 4,149,886 and the like.

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. In the present invention, U.S. Pat.Nos. 3,652,345, 3,928,041, and 3,95
8,993, 3,961,959, 4,052,213, JP-A-5
3-110529, 54-13333, 55-161237 and the like, when coupled with an oxidant of a color developing agent, a development inhibitor is released, but a compound that does not form a dye. Is also included.

Furthermore, 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, the mother nucleus forms a dye or an unemployed compound. On the other hand, a so-called timing DIR compound in which the released timing group is a compound which releases the development inhibitor by an intramolecular nucleophilic substitution reaction or an elimination reaction may be used.

Further, when reacting with an oxidized product of a color developing agent described in JP-A-58-160954 and JP-A-58-162949, a timing group as described above is present in the coupler mother nucleus which forms a completely diffusible dye. It may be a timing DIR compound attached.

In general, these DIR compounds are preferably 2 × 10 ^{-5 to} 5 × 10 ^-1 mol, and more preferably 1 mol per mol of silver in the emulsion layer.
That is, x10 ^-4 to 1 x 10 ^-1 mol is used.

〔The invention's effect〕

The following effects (a) to (c) can be obtained by the present invention.

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

(B) As described above, in a color developing solution, when it is attempted to obtain a practical preservative by using a preservative, the unfavorable influence on the photographic characteristics and the rapid processability of the preservative and the preservability However, according to the present invention, the photographic characteristics and the rapid processing property (especially, a light-sensitive material having an emulsion layer having a high silver chloride content) can be avoided. The above relationship between () and homeostasis 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, the color developing solution is colored. The filter effect due to is reduced and stable photographic characteristics can be obtained.

(Specific embodiments of the invention)

Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.

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

(Color developer) Potassium sulphite Amount to obtain sulfite ion concentration in Table 1 Sodium chloride 0.3g Potassium carbonate 25.0g Preservative (Table 1) Hydroxylamine derivative of the present invention (Table 1) Chelating agent A 0.6g Color-developing agent [Exemplified compound 1)] 5.0 g Fluorescent whitening agent below 2.0 g Development accelerator (described in Table 1) 3.0 g Potassium hydroxide and water were added to make 1. The pH is 10.1.
It was set to 0.

Chelating agent A Optical brightener Ferric ion in each color developer (No.1-1 to No.1-13)
Add 4 ppm, copper ion 2 ppm and calcium ion 100 ppm (dissolve and add FeCl ₃ , CuSO ₄ · 6H ₂ O and CaCl ₂ respectively), and open ratio 30 cm ² / l at 50 ℃ (for 1 developing solution, It was stored in a glass container having an air contact area of 30 cm ² ).

 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 (quite discoloration) -Almost no change is 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. The polyethylene-coated paper has an average molecular weight of 100,00.
0, density 0.95 polyethylene 200 parts by weight and average molecular weight 200
A mixture of 20 parts by weight of polyethylene with a density of 0.8 and a density of 0.80 was added with 6.8% by weight of anatase type titanium oxide, and a coating layer with a thickness of 0.035 mm was formed on the surface of a high-quality paper with a weight of 170 g / m ² by the extrusion coating method. A coating layer having a thickness of 0.040 mm was provided only on 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 having the following structure per mol of silver halide. Sensitizing dye (I) 2,5-di-t-butylhydroquinone 200 mg / m ² sensitized with 2.5 × 10 ⁻⁴ mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate Further, as a yellow coupler, [Y-1] having the following structure is contained in an amount of 2.0 × 10 ^-1 mol per mol of silver halide, and the amount of silver is 300 mg / m ² .

Second layer: di-t-octylhydroquinone 300 mg / m ² dissolved and dispersed in dibutyl phthalate, ^{2 as} an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'methylphenyl) -5-chloro-benzotriazole, 2-
Mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (1: 1:
1: 1) gelatin layer containing 200 mg / m ² gelatin 1900 mg /
It is applied so that it will be 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 having the following structure per mol of silver halide. Sensitizing dye (II) was sensitized with 2.5 × 10 ⁻⁴ mol of 2,5-di-t-butylhydroquinone dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2: 1 and a magenta coupler as shown below. Containing [M-1] of the structure of 1.5 × 10 ^-1 mol per mol of silver halide, the amount of silver is 230 mg.
/ m ^2, AI dye is applied so that the 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: di-t-octylhydroquinone 30 mg / m ² dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole as an ultraviolet absorber. , 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2-
Mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-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 consisting of a silver chlorobromide emulsion containing 3 mol% of silver bromide, said emulsion containing 500 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: Sensitizing dye (III) was sensitized with 2.5 × 10 ⁻⁵ mol of 2,5-di-t-butylhydroquinone 150 mg / m ² dissolved and dispersed in dibutyl phthalate and a cyan coupler of the following structure [C -1] is 3.5 × 10 per mol of silver halide.
^{-Containing 1} mol, the amount of silver is 280 mg / m ² , and the AI dye is 40 mg / m ² .

Sixth layer: It is a gelatin layer and is coated with gelatin at 900 mg / m ² .

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

After the color paper produced by the above method was exposed, it was treated using the following treatment steps and treatment liquids.

Treatment process (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 [coloring Development tank solution] The above color developing solution (No.1-1 to No.1-13) [Bleaching fixing tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g 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 bring the total volume to 1.

[Stable tank substitute for washing] Orthophenylphenol 0.2g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%
Solution) 2.0 g Ammonia water 3.0 g Water to 1 and ammonia water and sulfuric acid to pH 7.8.

The above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution were filled in an automatic processor, and the color paper sample was processed to measure the maximum density of yellow. The results are shown in Table 1.
Shown in

However, the above-mentioned maximum densities are shown as relative values with the densities of 100 using the developer No. 1-1.

From Table 1, the color developer contains an aldehyde bisulfite addition compound and a compound represented by the general formula [1], and the sulfite ion concentration is 1.5 × 10 ^-2 mol / l or less,
In particular, by setting it to 1.0 × 10 ^-4 or more and 1.0 × 10 ^-2 or less, compared with the color developing solution by the conventional technology, the goodness of the color developing solution is maintained while the photographic characteristics due to the preserving property are bad. It can be seen that the decrease in density is reduced when a light-sensitive material having a high silver chloride content, which is a side effect, is rapidly processed.

Example 2 In the color developer, the preservative, the compound represented by the general formula [1], the hydroxylamine derivative of the present invention and the sulfite ion concentration were set as shown in Table 2, and the number of storage days was 10 days. The same experiment as in Example 1 was performed. The results are shown in Table 2. The maximum density (yellow density) is the developer.
It is shown as a relative value with No. 2-1 as 100.

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

Example 3 An internal latent image type light-sensitive material was prepared by sequentially coating the following layers on a polyethylene-laminated paper support from the support side.

First layer: cyan-forming red-sensitive silver halide emulsion layer 2,4-dichloro-3-methyl- as a cyan coupler
6- [α- (2,4-di-tert-amylphenoxy) butyramide] phenol 90 g, 2,5-di-tert-octylhydroquinone 2 g, tricresyl phosphate 50 g, paraffin 200 g and ethyl acetate 50 g are mixed and dissolved. , A gelatin solution containing sodium dodecylbenzenesulfonate was added and dispersed so that the average particle size was 0.6 μm (prepared by the conversion method according to Example 1 described in US Pat. No. 2,592,250). Internal latent image type halogen. Add silver halide emulsion (AgBr: AgCl = 70: 30), silver amount 400mg / m ² , AI dye
20 mg / m ² and a coupler amount of 360 mg / m ² were applied.

Second layer: Intermediate layer containing 5 g of gray colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate.
100 ml of 2.5% 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) -3- (2-chloro-5-octadecylsuccinimidoanilino) -5-pyrazolone as a magenta coupler 100 g, 2 , 5-ge-t
ert-Octylhydroquinone 5 g, 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 μm. Internal latent image type silver halide emulsion (Ag
Br: AgCl = 60: 40), silver amount 400 mg / m ² , AI dye 20 mg
/ m ² , and the amount of the coupler was 400 mg / m ² .

Fourth layer: yellow filter layer A 2.5% gelatin solution containing 5 g of yellow colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was applied so that the colloidal silver was 200 mg / m ² . .

Fifth layer: yellow-forming blue-sensitive silver halide emulsion layer α- [4- (1-benzyl-
2-Phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-bivalyl-2-chloro-5- [γ- (2,4
-Di-tert-amylphenoxy) butyramide] acetanilide 120 g, 2,5-di-tert-octylhydroquinone 3.5 g, paraffin 200 g, tinuvin (manufactured by Ciba-Geigy) 100 g, dibutyl phthalate 100 g and ethyl acetate 70 ml
Were mixed and dissolved, a gelatin solution containing sodium dodecylbenzene sulfonate was added, and dispersed so that the average grain size was 0.9 μm. An internal latent image type silver halide emulsion (AgBr : AgCl = 80: 20) and add silver
The coating amount was 400 mg / m ² and the coupler amount was 400 mg / m ² .

Sixth layer: protective layer It was applied so that the amount of zetillane was 200 mg / m ² .

It should be noted that all of the above layers contained saponin as a coating aid. As a hardener, 2,4-dichloro-6-hydroxy-s-triazine sodium was added to layers 2, 4 and 6 at 0.02 g per 1 g of gelatin, respectively.

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

Treatment process (38 ℃) Immersion (color developer) 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 Drying 60-80 ℃ 120 The composition of each processing solution is as follows.

(Color developer) Benzyl alcohol 15ml Ethylene glycol 10ml Potassium sulfite Amount that gives the sulfite ion concentration in Table 3 Potassium bromide 1.5g Sodium chloride 0.3g Potassium carbonate 25.0g Preservative, compound represented by general formula [1] And hydroxylamine derivative of the present invention (shown in Table 2) chelating agent A 0.6 g color developing agent (exemplary compound (1) / (3) = molar ratio 1 /
1) 7.5 g Optical brightener (same as in Example 1) 2.0 g Potassium hydroxide and water were added to make 1. The pH is 1
It was set to 0.20.

(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 salt 20 g Pure water was added to 1 and With ammonia water or dilute sulfuric acid
Adjust to pH = 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.

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

Example 4 A compound represented by the general formula [3] or [4] (A-
1) to (A-2), (A-3), (A-4), (A-
5), (A-14), (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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-57-185434 (JP, A) JP-A-58-17439 (JP, A) JP-A-59-135464 (JP, A) JP-A-54- 3532 (JP, A) JP 60-19140 (JP, A) JP 63-4234 (JP, A)

Claims (1)

(57) [Claims] 1. An aldehyde bisulfite addition compound, a compound represented by the following general formula [1], at least one hydroxylamine derivative selected from the following (1) to (4), and 1.5 × per color developing solution. A color developing solution for a silver halide color photographic light-sensitive material, which contains not more than 10 ^-2 mol of sulfite ion and substantially no hydroxylamine. General formula [1] [In the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms.
Is a hydroxyalkyl group, an alkoxy group or an alkoxyalkyl group, R ₂ and R ₃ are each a hydrogen atom or a carbon
~ 6 alkyl group, C2-6 hydroxyalkyl group, alkoxyalkyl group, benzyl group, aryl group or formula In the 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. ]