JPH0658521B2 - Color developer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color developer composition used for developing a silver halide color photographic light-sensitive material such as a color negative film or color paper.

[Prior Art] Various preservatives and chelating agents have been studied in order to improve the stability of color developers. For example, as preservatives, there are JP-A Nos. 52-49828 and 59-1.
60142, 56-47038, and U.S. Pat.
Aromatic polyhydroxy compounds described in 3746544 and the like, hydroxycarbonyl compounds described in US Pat. No. 3615503 and British Patent No. 1306176, α-aminocarbonyl compounds described in JP-A Nos. 52-143020 and 53-89425, Alkanolamines described in JP-A-54-3532, JP-A-57-44148 and JP-A-57-5374.
Examples thereof include metal salts described in No. 9 and the like. Further, as the chelating agent, Japanese Patent Publication Nos. 48-30496 and 44
Aminopolycarboxylic acids described in JP-A-30232, JP-A-56-97347, JP-B-56-39359, and organic phosphonic acids described in West German Patent No. 2227639;
No. 2-102726, No. 53-42730, No. 54-
121127, 55-126241 and 55-.
Phosphonocarboxylic acids described in JP-A-695956, and others, JP-A-58-195845 and JP-A-58-203440.
And compounds described in JP-A-53-40900.

Among these various compounds, hydroxylamine has been conventionally used to prevent the oxidation of the developing agent.
If these are used, there is a problem that the color developability is lowered.

Further, in the case where benzyl alcohol, which is a commonly added component to the developer, is not contained, the appearance of a color developer which is more deteriorated with time and has excellent stability is desired.

[Problems to be solved by the invention]

Therefore, it is an object of the present invention to provide a color developer composition having excellent stability over time without adversely affecting the photographic characteristics of the developing agent and the photosensitive material to be developed.

[Means for solving problems]

The present invention, among the numerous hydroxyamine compounds,
It is said that the above problems can be effectively solved by using an amine compound having a hydroxyl group at the terminal of the alkylene group and at least one special group having an ether or thioether bond in the alkylene group in the molecule. It was made based on the knowledge.

That is, the present invention is a color developer composition containing an aromatic primary amine color developing agent and an amine compound represented by the following general formula [I].

(In the formula, R ¹ and R ² are alkylene groups having 2 to 4 carbon atoms,
R ³ and R ⁴ represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a group represented by —R ² —X—R ¹ —OH, and R ³ and R ⁴ may form a ring. X represents an oxygen atom or a sulfur atom. As the aromatic primary amine color developing agent used in the present invention, various known compounds can be used. Of these, p-
One or a mixture of two or more phenylenediamine derivatives is preferable, and specific examples include the following.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [N -Ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 N-ethyl-N- (β- Methanesulfonamidoethyl) -3-methyl-4-aminoaniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4 -Amino-3-methyl-N-ethyl-N-methoxyethylalinine D-10 4-amino-3-methyl-N-ethyl-N-
β-ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-
β-Butoxyethylaniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is a concentration of about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per developing solution.

The specific alkanolamine compound used in combination with the developing agent is a compound represented by the general formula [I]. In the formula [I], an alkyl group having 1 to 6 carbon atoms such as an ethyl group, an isopropyl group and a butyl group, and a hydroxyalkyl group such as a 2-hydroxyethyl group and a 2-hydroxy group. Examples thereof include those having 2 to 6 carbon atoms such as -1-methylethyl group and 4-hydroxybutyl group. Further, the ring formed by R ³ and R ⁴ together includes a 5- to 8-membered ring. Among these, in the present invention, R ¹ and R ² in the formula [I] are preferably ethylene or propylene, most preferably ethylene, and R ³ and R ⁴ are an alkyl group, a hydroxyalkyl group or —R ²
A group represented by —X—R ¹ —OH is preferable, a group represented by —R ² —X—R ¹ —OH is most preferable, and X is preferably an oxygen atom.

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

A-1 NC ₂ H ₄ OC ₂ H ₄ OH) ₃ A-2 H ₂ NC ₂ H ₄ OC ₂ H ₄ OH A-3 NC ₂ H ₄ SC ₂ H ₄ OH) ₃ A-4 (C ₂ H _{5 2} NC ₂ H ₄ OC ₂ H ₄ OH A-5 (HOC ₂ H _{4 2} NC ₂ H ₄ OC ₂ H ₄ OH A-6 HOC ₂ H ₄ -NC ₂ H ₄ OC ₂ H ₄ OH) ₂ A-7 HNC ₂ H ₄ SC ₂ H ₄ OH) ₂ A-8 N (CH _{2 3} OCH _{2 2} OH) ₃ A-11 (HOC ₂ H _{4 2} NCH _{2 4} OCH _{2 3} CH A-12 HOCH _{2 3} NC ₂ H ₄ OC ₂ H ₄ OH) ₂ The compound of the general formula [I] used in the present invention is disclosed in JP-B-57-
It is easily produced by the method described in No. 8096 or a method analogous thereto.

The amine compound represented by the general formula [I] is added in an amount of 0.01 g to 50 g, preferably 1 g to 1 g, per color developing solution.
It is good to use 20 g.

The color developer composition of the present invention must contain the above-mentioned two components, and the balance is composed of water or water containing an organic solvent such as diethylene glycol, but the optional additives described below are added. You can

Hydroxylamines It is preferable to use together one or a mixture of two or more conventionally used hydroxylamines in order to improve the stability of the color developing solution. Specifically, the following are exemplified. Of these, the alkyl group of N, N-dialkylhydroxyamine may be substituted with a hydroxy group or a lower alkoxy group.

_{H 2 NOH, CH 3 NHOH,} CH 3 CH 2 NHOH, (CH 3) 2 NOH, (CH 3 CH 2) 2 NOH, (C
H ₃ OCH ₂ CH ₂ ) ₂ NOH, The hydroxyamines include hydrochloric acid, sulfuric acid, nitric acid, acetic acid,
It may form a salt with various acids such as oxalic acid. Preferred hydroxylamines are N, N-dialkyl substituents, which alkyl groups may be further substituted.

These hydroxyamines are used per color developing solution.
It is recommended to use 0.01 g to 20 g, preferably 0.1 g to 10 g, more preferably 1 g to 8 g. Preservatives It is preferable to contain sulfite salts such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts. The addition amount of these is 0 g to 2
It is 0 g / preferably 0 g to 5 g /, and a smaller amount is preferable if the stability of the color developer is maintained.

Other preservatives include hydroxyacetones described in U.S. Pat. No. 3,615,503 and British Patent No. 1306176;
Α described in 2-143020 and 53-89425
-Aminocarbonyl compounds, various metals described in JP-A-57-44148 and 57-53749, various sugars described in JP-A-52-102727, 52-27
Hydroxamic acids described in No. 638, 59-16014
No. 1, α, α′-dicarbonyl compound, 59-1
Salicylic acids described in No. 80588, alkanolamines described in No. 54-3532, poly (alkyleneimines) described in No. 56-94349, No. 56-75647.
The gluconic acid derivative described in the above publication can be added if necessary. Two or more kinds of these preservatives may be used in combination, if necessary.

Buffering agent The pH of the color developing solution is preferably pH 9 to 12, more preferably 9 to 11.0. In order to maintain the pH, it is preferable to use various buffering agents.

Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy salt. Phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,
3-Propanediol salt, valine salt, proline salt, trishydrocyaminomethane salt, lysine salt and the like can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent solubility and buffer capacity in a high pH range of pH 9.0 or higher, and even when added to a color developing solution, they have excellent photographic performance. It is particularly preferable to use these buffers, since they have the advantages of being free from adverse effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, potassium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), Sodium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol / mol or more, particularly preferably 0.1 mol / -0.4 mol /.

Chelating Agent Various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, organic oxide compounds are preferable, for example, aminopolycarboxylic acids described in JP-B-48-30496 and 44-30232, JP-A-56-97347.
Organic phosphonic acids described in Japanese Patent Publication No. 56-39359 and West German Patent No. 2227639, JP-A-52-102726.
No. 53-42730, No. 54-12127,
Phosphonocarboxylic acids described in JP-A-55-126241 and JP-A-55-69556, and others, JP-A-58-19.
No. 5845, No. 58-203440 and Japanese Patent Publication No. 53-
Examples thereof include compounds described in No. 40900.
Specific examples are shown below, but the present invention is not limited thereto.

-Nitrilotriacetic acid-Ethylenediaminetetraacetic acid-Diethylenetriaminepentaacetic acid-Triethylenetetraminehexaacetic acid-N, N, N-trimethylenephosphonic acid-Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid-1,3 -Diamino-2-propanol-4acetic acid-transcyclohexanediaminetetraacetic acid-nitrilotripropionic acid- 1,2-diaminopropanetetraacetic acid-hydroxyethyliminodiacetic acid-glycoletherdiaminetetraacetic acid-hydroxyethylenediaminetriacetic acid-ethylenediaminetetraacetic acid -Ethylenediamine ortho-hydroxyphenylacetic acid-2-phosphonobutane-1,2,4-tricarboxylic acid-1-hydroxyethylidene-1,1-diphosphonic acid-N, N'-bis (2-hydroxybenzyl) ethylenedia Emissions -N, N'-diacetic acid These chelating agents may be used in combination of two or more thereof, if desired.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
The amount is about 0.1 to 10 g.

Development Accelerator An optional development accelerator can be added to the color developing solution, if necessary. However, it contains substantially no benzyl alcohol,
The addition amount thereof is 0.5 ml / l or less per color developing solution, and preferably it is not contained at all. Other development accelerators include JP-B-37-16088, JP-B-37-5987, JP-B-38-7826 and JP-B-44-12.
380, 45-90019 and U.S. Pat. No. 3813247.
Compounds represented by JP-A-52-
49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137.
No. 726, Japanese Patent Publication No. 44-30074, and Japanese Patent Laid-Open No. 56-1.
56826 and 52-43429, and the like, quaternary ammonium salts, p-aminophenols described in U.S. Pat. Nos. 2610122 and 4119462, U.S. Pat. Nos. 2,494,903, 3128182, and 4230796. Issue No. 325
3919, Japanese Patent Publication No. 41-11431, U.S. Pat. No. 248254.
No. 6, No. 2596926, No. 3582346, etc., amine compounds, JP-B-37-16088;
No. 201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-114
31, 42-23883 and U.S. Pat. No. 3,352,501.
No. 1 and other polyalkylene oxides
-Phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Antifoggant In the present invention, an optional antifoggant can be added to the color developing solution, if necessary. As the antifoggant, alkali metal halides such as potassium bromide, sodium chloride and potassium iodide and organic antifoggants can be used.
Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoinzole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole and hydroxyazaindolizine, and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, and thiosalicylic acid. It is possible to use mercapto-substituted aromatic compounds such as Particularly preferred are nitrogen-containing heterocyclic compounds. These antifoggants may be eluted from the color light-sensitive material during processing and accumulated in the color developing solution.

Optical Brightening Agent The color developing solution of the present invention preferably contains an optical brightening agent. Fluorescent brighteners include 4,4'-diamino-
2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g / preferably 0.1 g to 4 g / p.

Surfactant Various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added, if necessary.

The color developer of the present invention is used at a processing temperature of 20 to 50 ° C, preferably 30 to 40 ° C. The treatment is carried out for 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Also, it is preferable that the replenishing amount is small, but 20 to 60 per 1 m ^{2 of} the light-sensitive material.
It is 0 m1 and preferably 50 to 300 m1. More preferably, it is desirable to set it to 100 m1 to 200 m1.

The color developing solution of the present invention can be applied to any processing of general silver halide color light-sensitive materials such as color negative films, color papers, color positive films, color reversal films, and especially for developing color papers. It is preferably used.

First, for color paper, the silver bromide content is 10 mol%
Examples thereof include those containing the above silver chlorobromide. Further, in order to obtain an emulsion having sufficient sensitivity without increasing fog, the silver bromide content is preferably 20 mol% or more, but when rapidity is particularly required, 10 mol% or less or 5 mol% or less May be used. In particular, an emulsion of 1 mol% or less close to pure silver chloride is preferable because a rapid phenomenon is possible.

Further, the color negative film or the color reversal film may be a photographic emulsion layer containing any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 2 to 25 mol% of silver iodide.

By using tabular grains in the above silver halide photographic emulsion, improvement in sensitivity including improvement in color sensitization efficiency by a sensitizing dye, improvement in relation between sensitivity and graininess, improvement in sharpness, improvement in development progress, Improvement of covering power and improvement of crossover can be achieved.

Here, the tabular silver halide grains have a diameter / thickness ratio of 5 or more, for example, more than 8 or 5 or more and 8 or less.

The light-sensitive material which is the object of the present invention can contain various aller couplers. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Typical examples of useful color couplers include naphthol or phenol compounds and pyrazolone. Alternatively, there are pyrazoloazole compounds and closed or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (December 1978) VII-D.
No. 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent coupler substituted with a coupling-off group is more preferable than a four-equivalent coupler having a hydrogen atom at the coupling active position, because the coated silver amount can be reduced. Further, a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler is an oil protect type acylacetamide coupler.
Specific examples thereof include U.S. Pat.Nos. 2,407,210 and 2,875,057.
And No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and US Pat.Nos. 3,408,194, 3,447,928, and 3,933,50 are used.
No. 1 and No. 4,022,620, etc., and oxygen atom desorption type yellow couplers or Japanese Examined Patent Publication No. 58-1073.
9, US Pat. Nos. 4,401,752, 4,326,024, RD
18053 (April 1979), British Patent No. 1,425,020,
(West German Application Publication Nos. 2,219,917, 2,261,361, and
Typical examples thereof include nitrogen atom releasing yellow couplers described in 2,329,587 and 2,433,812. α-pivaloyl acetanilide type couplers are excellent in fastness of color forming dyes, especially light fastness, while α
-The benzoylacetanilide type coupler provides a high color density.

The magenta coupler is an oil-protected type, indazolone type or cyanoacetyl type, preferably 5
-Pyrazoloazole type couplers such as pyrazolone type and prazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye.
No. 2,311,082, No. 2,343,703, No. 2,600,788, No. 2,908,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015. As a leaving group of a 2-equivalent 5-pyrazolone-based coupler, US Pat.
The nitrogen atom leaving group described in 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
1,432 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (1984, 1984).
And the pyrazolotetrazoles and Research Disclosure 2 described in JP-A-60-33552.
4230 (June 1984) and JP-A-60-43.
And the pyrazolopyrazoles described in No. 659.
The imidazo [1,2-,] described in U.S. Pat. No. 4,500,630 in view of low yellow sub-absorption of a coloring dye and light fastness.
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 are particularly preferred.

Cyan couplers include oil-protected naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, and 4,
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in Nos. 228,233 and 4,296,200. Further, specific examples of the phenol-based couplers include U.S. Patent Nos. 2,369,929, 2,801,171, and 2,772,162.
No. 2,895,826 and the like. Humidity and temperature robust cyan couplers are preferably used in the present invention, typical examples of which are U.S. Pat.
Phenol cyan coupler having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in 002, U.S. Pat.Nos. 2,772,162, 3,758,308, and 4,
126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and European Patent 121,365 and the like, 2,5-diacylamino-substituted phenol couplers and U.S. Pat.Nos. 3,446,622 and 4,333,999.
Nos. 4,451,559 and 4,427,767, and the like, and phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. Japanese Patent Application Nos. 59-93605 and 59-264277.
Nos. 59-268135 and 59-268135, cyan couplers in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc. are also excellent in the fastness of a color image and can be preferably used in the present invention.

In order to correct the unnecessary absorption in the short wavelength region which the dyes produced from the magenta and cyan couplers have, it is preferable to use a color coupler together with the color negative photosensitive material for photographing. Yellow colored magenta couplers described in U.S. Pat.No. 4,163,670 and JP-B-57-39413 or U.S. Pat.Nos. 4,004,929, 4,138,258 and British Patent 1,
Typical examples are magenta colored cyan couplers described in JP-A No. 146,368 and the like.

Furthermore, antioxidants, color-enhancing agents, ultraviolet absorbers, cyan, magenta and / or yellow dye image fading inhibitors, color mixing inhibitors, stain inhibitors, antifoggants, spectral sensitizers, dyes, hardeners. , A surface active agent, an antistatic agent, a development accelerator and a desilvering accelerator can be added.

In the developer of the present invention, photosensitive materials having various known layer constitutions are processed. Among these, preferable layer constitutions include the following, and as the support, a flexible support such as plastic film, paper, cloth or the like usually used for photographic light-sensitive materials or glass, pottery, metal. And the like. Among them, it is preferable to use a baryta paper or polyethylene laminated polyethylene support containing a white pigment (for example, titanium oxide) in the polyethylene support. These are, for example, Research Disclosure
clozure) Nos. 17643, pages 23-27 and No. 187
16 specifically described on pages 648 to 650 are exemplified.

(I) Support-BL-MC-GL-MC-RL-PC
(2) -PC (1) (ii) Support-BL-MC-RL-MC-GL-PC
(2) -PC (1) (iii) Support-RL-MC-GL-MC-BL-PC
(2) -PC (1) (iv) Support-RL-MC-BL-MC-GL-PC
(2) -PC (1) (v) Support-BL (2) -BL (1) -MC-GL (2) -G
L (1) -MC-RL (2) -RL (1) -PC (2) -PC (1) where PC (1) and PC (2) are non-photosensitive layers, MC is an intermediate layer,
BL indicates a blue emulsion layer, GL indicates a green-sensitive emulsion layer, and RL indicates a red-sensitive emulsion layer.

Processing Method After developing the photosensitive material with the developer of the present invention, the photosensitive material is processed by a usual method. A specific processing method including the developing step is shown below. It should be noted that these are typical steps and are not limited to these.

A. Coloring phenomenon-bleach-fixing-washing-drying B. Coloring phenomenon-bleach-fixing-washing-stabilization-drying C.I. Coloring phenomenon-washing-bleach-fixing-washing-drying D. Coloring phenomenon-bleaching-fixing-washing-stabilization-drying E. Coloring phenomenon-bleaching-fixing-washing-drying F. Coloring phenomenon-washing-bleaching-fixing-washing-drying G. Coloring phenomenon-bleaching-bleach-fixing-washing-stabilization-drying H. Coloring phenomenon-bleaching-bleach-fixing-washing-drying I. Color development phenomenon-bleaching-bleach-fixing-fixing-washing-stabilization-
Dry J. Coloring phenomenon-bleaching-bleach-fixing-fixing-washing-drying In the above steps, when the preceding step of the stabilizing step is the washing step, the washing step can be deleted and the stabilization step can be directly carried out.

Bleaching solution, bleach-fixing solution, fixing solution As a bleaching agent used in a bleaching solution or a bleach-fixing solution, a ferric ion complex is a chelate of ferric ion with aminopolycarboxylic acid, aminopolyphosphonic acid or salts thereof. It is a complex with an agent. The aminopolycarboxylic acid salt or aminopolyphosphonic acid salt is a salt of aminopolycarboxylic acid or aminopolyphosphonic acid with an alkali metal, ammonium, or a water-soluble amine. The alkali metal is sodium, potassium, lithium or the like, and the water-soluble amine is an alkylamine such as methylamine, diethylamine, triethylamine or butylamine,
A ring-type amine such as cyclohexylamine, aniline,
aryl amines such as m-toluidine, and pyridine,
Heterocyclic amines such as morpholine and piperidine.

Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or salts thereof are ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt 1,2-diaminopropanetetraacetic acid 1, 2-Diaminopropane tetraacetic acid disodium salt 1,3-Diaminopropane tetraacetic acid 1,3-Diaminopropane tetraacetic acid diammonium salt Nitrilotriacetic acid Nitrilotriacetic acid trisodium salt 1,3-Diaminopropanol-N, N, N ′, N ′-
Tetramethylenephosphonic acid Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1,3-Propylenediamine-N, N, N', N'-tetramethylenephosphonic acid, etc., but of course It is not limited to these exemplified compounds.

The ferric ion complex salt may be used in the form of a complex salt, or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and amino acid. The ferric ion complex salt may be formed in the solution by using a chelating agent such as polycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one or more ferric salts may be used. Furthermore, one or more chelating agents may be used. Further, in any case, the chelating agent may be used in an amount more than that for forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.1 to 1 mol / in a bleaching solution of a color photographic light-sensitive material for photographing such as a color negative film.
, Preferably 0.2-0.4 mol / mol, and in the bleach-fix solution, it is preferably 0.05-0.5 mol / mol, and more preferably
It is 0.1 to 0.3 mol /. Further, in a bleaching solution or a bleach-fixing solution of a color photographic light-sensitive material for printing such as Aller's paper, 0.03 to 0.3 mol / preferably 0.05.
~ 0.2 mol /.

Further, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent 1,290,8.
12, No. 2,059,988, JP-A-53-32736,
53-57831, 37418 and 53-65.
No. 732, No. 53-72623, No. 53-95630
No. 53-95631, No. 53-104232,
53-124424, 53-141623, 53-28426, Research Disclosure N
Compounds having a mercapto group or a disulfide group described in JP-A No. 17129 (July 1978);
Thiazolidine derivatives as described in 0-140129; JP-B-45-8506 and JP-A-52-208.
32, 53-32735, U.S. Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715,
Iodides described in JP-A-58-16235; West German Patent No.
Polyethylene oxides described in 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434, 49-5
No. 9644, No. 53-94927, No. 54-3572
No. 7, No. 55-26506 and No. 58-16394.
Examples thereof include compounds described in No. 0, iodine, bromine ion and the like. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect,
Especially U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95630 are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, iodide). Ammonium) rehalogenating agents can be included. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Addition of one or more inorganic acids, organic acids and their alkali metal or ammonium salts having pH buffering ability such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc., or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can do.

The bleach-fixing solution of the present invention or the fixing agent used in the fixing solution is
Known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a thioether compound such as octanediol and a water-soluble silver halide dissolving agent such as thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-51-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

The amount of the fixing agent per unit is preferably 0.3 to 2 mol, and particularly 0.8 to 1.5 in the processing of color photographic light-sensitive materials for photographing.
In the case of processing a color photographic light-sensitive material for printing, the range is 0.5 to 1 mol.

The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 10, more preferably from 5 to 9. When the pH is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

A bleach-fixing solution or a fixing solution is a preservative such as sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.),
Metabisulfite (eg potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.)
Etc. containing a sulfite ion releasing compound.

Washing and stabilizing After the desilvering process (bleach-fixing or fixing), washing and / or
Alternatively, processing such as stabilization is performed. Various compounds can be used for various purposes in the washing and stabilizing steps. For example, it is known to add a bactericidal agent or a fungicide to prevent the generation of various bacteria, molds and algae. For example, Journal of Antibacterial and Antifungal Agents (J.Antiba
ct.Antifung.Agents) vol.11, No.5, p207 ~ 2
23 (1983) and the compounds described in Hiroshi Horiguchi, "The Chemistry of Antibacterial and Antifungal Agents"), or JP-A-57.
-8543, JP-A-57-58143, and JP-A-57.
-97530, JP-A-58-105145, JP-A-58-134636, JP-A-59-91440, JP-A-59-126533, and JP-A-59-184344.
JP-A-59-185336, JP-A-60-239.
750, JP-A-60-239751, JP-A-60-
247241, JP-A-60-260952, JP-A-61-2149, JP-A-61-28947, JP-A-61-28945, Japanese Patent Application No. 59-158475, Japanese Patent Application No. 60-105487. The compounds described in the specification and methods of using the same can be applied.

In particular, isothiazolone derivatives (2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-
Isothiazolin-3-one etc.), sulfanilamide derivative (sulfanilamide etc.) and benzotriazole derivative (benzotriazole, 5-methyl-benzotriazole, 5-chloro-benzothiazole etc.)
Is useful.

It is known to add various chelating agents for the purpose of improving the image stability after processing. For example, inorganic phosphoric acid, organic carboxylic acid, aminopolycarboxylic acid and organic phosphonic acid are useful, and they are disclosed in JP-A-57-8543 and JP-A-57-543.
197540, JP 58-14834, JP 5
8-134636, JP-A-59-126533, JP-A-59-184343, JP-A-59-184344.
JP-A-59-184345 and JP-A-59-185.
336, JP-A-60-135942, JP-A-60-
238832, JP-A-60-239748, JP-A-60-239749, JP-A-60-239750,
JP-A-60-239751, JP-A-60-24245
No. 8, JP-A-60-262161, JP-A-61-40
47, JP-A 61-4050, JP-A 61-405.
No. 1, JP-A-61-4052, JP-A-61-4053
No. 61-40542, 61-28942
And the method of use described in JP-A No. 61-28945.

In particular, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and ethylenediaminetetramethylphosphonic acid are useful.

A metal compound may be used in combination with these chelating agents. For example, a bismuth compound (JP-A-58-13)
4636), Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb,
Ti, Sn, Zn, Zr compounds (JP-A-59-184344)
No.), Mg, Al, Sr compounds (JP-A-59-185336).
No.), Bi, Ca, Mg, Al are particularly useful.

Further, in order to effectively carry out washing with water, a surfactant is used (JP-A-57-197540), or a method of contacting with an ion exchange resin for the purpose of removing a component having an adverse effect (JP-A-57-1975). 60-220345), a method of reverse osmosis treatment (JP-A-60-241053), activated carbon, a clay substance, a polyamide polymer compound, a polyurethane polymer compound, a phenol resin, an epoxy resin, a polymer having a hydrazide group. Compound, polymer compound containing polytetrafluoroethylene, method of contacting with monohydric or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer (JP-A-60-263151), electrodialysis A treatment method (Japanese Patent Laid-Open No. 61-28949) can be applied.

Further, it can be applied as a method for preventing the generation of bacteria and mold such as a method of irradiating ultraviolet rays or passing a magnetic field. Further, in the case of continuing the treatment, JP-A-60-233651 and JP-A-6-233651.
0-235133, 60-263941, 61
-4048, 61-4049, 61-4055.
No. 61-4056, 61-4057, 61
The methods of No. -4058 and No. 61-4060 can be applied.

In addition to the above-mentioned additives, a fluorescent whitening agent, a hardener, etc. may be added to the washing and stabilizing baths.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment in order to improve the image storability.

As the various additives, the same or different target compounds may be used in combination of two or more depending on the purpose. From the viewpoint of the physical properties (e.g., stickiness) of the emulsion film of the processed light-sensitive material, it is preferable that the addition amount be the minimum amount necessary for achieving the purpose.

It is preferable that the washing or stabilizing step is performed in a multi-stage countercurrent flow of two or more tanks to reduce the amount of replenisher. The amount of replenisher is
0 for the carry-in amount of the pre-bath per unit area of the photosensitive material.
It is preferably 1 to 50 times, more preferably 3 to 30 times.

The washing or stabilization treatment time of the present invention depends on the type of sensitive material,
The time is 20 seconds to 2 minutes, and more preferably 20 seconds to 1 minute 30 seconds, although it varies depending on the treatment conditions.

The washing or stabilization treatment temperature of the present invention is 20 to 45.
℃, preferably 25 ℃ ~ 40 ℃, more preferably 30 ~ 35 ℃.

In order to enhance the effect of washing out components in the film in washing or stabilizing treatment, it is preferable to circulate and stir the liquid,
In particular, it is preferable to use a method in which the surface of the emulsion film of the light-sensitive material is exposed to a strong liquid flow (eg, gas agitation, liquid spraying, etc.).

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring and the like may be provided in each treatment bath.

〔The invention's effect〕

The present invention provides an excellent color developing solution which is stable for a long period of time. In particular, excellent developing characteristics and stability are ensured even when benzyl alcohol is not contained.

Next, the present invention will be described with reference to examples.

Example 1 Various emulsion layers were coated on a paper support laminated on both sides with polyethylene to prepare a multilayer color photographic paper. The emulsion coating solution used here was prepared as follows.

Yellow coupler (a) 19.1 g and color image stabilizer (b) 4.4 g
Ethyl acetate (27.2 ml) and solvent (c) (7.9 ml) were added to and dissolved, and this solution was emulsified and dispersed in 185 ml of 10% gelatin aqueous solution containing 10 ml of 8% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (silver bromide 1.0 mol%, Ag
90 g of a blue-sensitive emulsion was prepared by adding the blue-sensitive sensitizing dye shown below to 5.0 × 10 ⁻⁴ mol per mol of silver chlorobromide (containing 70 g / kg). Mix and dissolve the emulsified dispersion and emulsion,
The gelatin concentration was adjusted so as to have the composition shown in Table B, and the coating solution for the first layer was prepared.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer (Addition of 5.0 × 10 ⁻⁴ mol per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol added per mol of silver halide) (7.0 × 10 ^-5 mol added per mol of silver halide) Red-sensitive emulsion layer (Addition of 0.9 × 10 ⁻⁴ mol per mol of silver halide) The following dye was used as the anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion layer: Structural formulas of compounds such as couplers used in this example are as follows.

The color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

Treatment process Temperature Time Color development (35 ° C) 45 seconds Bleach fixing (35 ° C) 45 seconds Rinse 1 (35 ° C) 20 seconds Rinse 2 (35 ° C) 20 seconds Rinse 3 (35 ° C) 20 seconds Dry (80 ° C) 60 The processing solutions used for each second are as follows.

A part of the color developing solution obtained as described above is heated to 40 ° C.
After being left for 20 days in the above, it was treated again in the above treatment step.

Developer used immediately after preparation (hereinafter referred to as fresh liquid)
Table 1 shows the photographic characteristics of the light-sensitive material obtained by developing the light-sensitive material with the developer after the aging and after the aging.

The photographic characteristics are represented by Dmin at yellow density, sensitivity and gradation. Here, the sensitivity is a constant exposure amount (100 CMS)
Is expressed as the density value of, and the gradation is logE from the point where the density is 0.5.
The change in density up to the density point on the high exposure side of 0.3 is expressed by.

From the results of Table-1, according to the developer of the present invention, there is almost no change in photographic characteristics even after the passage of time, and stable performance is obtained, whereas when sodium sulfite or triethanolamine is used, Fog will increase over time,
It can be seen that the gradation changes.

Example 2 As described in Table C, double-sided polyethylene laminated paper treated with corona discharge was coated with the first layer (bottom layer) to the seventh layer (top layer) to prepare a sample.

The coating liquid for the first layer was prepared as follows. That is, to 200 g of the yellow coupler shown in the table, 93.9 g of the anti-fading agent, 10 g of the high boiling point solvent (p) and 5 g of (q),
6 ml of a mixture containing 600 ml of ethyl acetate as an auxiliary solvent
After heating to 0 ° C., a solvent was added, and 330 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont)
Was mixed with 3,300 ml of a 5% gelatin aqueous solution containing and was emulsified using a colloid mill to prepare a coupler dispersion.
From this dispersion, ethyl acetate was distilled off under reduced pressure, and a sensitizing dye for blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole were added to Emulsion 1,
A coating solution was prepared by adding 400 g (including 96.7 g as Ag and 170 g of gelatin), and further adding 2,600 g of 10% gelatin aqueous solution. The coating solutions for the second to seventh layers are
It was produced according to the first layer.

Green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-
9,9 '-(2,2-Dimethyl-1,3-propano) thiadicarbocyanine iodide The following substances were used as stabilizers for each emulsion layer.

1-methyl-2-mercapto-5-acetylamino-
1,3,4-Triazole The following substances were used as anti-irradiation dyes.

4- (3-Salbox-5-hydroxy-4- (3-
(3-Carboxy-5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl) benzenesulfonate-
Di-potassium salt N, N '(4,8-dihydroxy-9,10-dioxo-3,7-disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt Also hard 1,2-bis (vinylsulfonyl) ethane was used as a film agent.

The couplers used are as follows.

Yellow coupler Magenta coupler Cyan coupler [C-1; C-2 = 50: 50 mixture (molar ratio)] The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

Processing time Temperature Color development 3 minutes 30 seconds 33 ° C. Bleach-fixing 1 minute 30 seconds 33 ° C. Rinse 3 minutes 30 ° C. (3 tank cascade) Drying 1 minute 80 ° C. The processing solutions used are as follows.

In the same manner as in Example 1, the light-sensitive material was processed with a fresh solution and an aged developer, and the magenta color of the processed light-sensitive material was changed.
Table 2 shows the change values of each photographic performance when Dmin, sensitivity, and gradation were obtained and the photographic characteristics with a fresh liquid were used as a reference.

From Table-2, according to the present invention, particularly in the combined use system with hydroxylamines, and further in the system containing no benzyl alcohol, the photographic performance is remarkably stabilized (No. 12, 13, 14, 15, 19, 20, 21, 2
2) I understand. On the other hand, it can be seen that when hydroxylamines are used alone, the photographic characteristics change greatly with time.

Example 3 Table 3 shows the results of analysis by liquid chromatography of the residual amounts of the color developing agents in the color developing solutions No. 1 to No. 8 left at 40 ° C. for 20 days in Example 1.

From these results, it is well understood that the color developer composition of the present invention is excellent in the stability of the color developing agent.

Example 4 As the amine compound represented by the general formula [I], A-
Example 2 except that 2, A-4, A-6 or A-7 was used
When the same treatment as in Example 2 was performed, the same excellent effect as in Example 2 was obtained.

Claims (3)

[Claims] 1. A color developer composition comprising an aromatic primary amine color developing agent and an amine compound represented by the following general formula [I]. (In the formula, R ¹ and R ² are alkylene groups having 2 to 4 carbon atoms,
R ³ and R ⁴ represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a group represented by —R ² —X—R ¹ —OH, and R ³ and R ⁴ may form a ring. X represents an oxygen atom or a sulfur atom. ) 2. A composition according to claim 1 wherein the color developer composition is substantially free of benzyl alcohol. 3. The composition according to claim 1, wherein hydroxyamines are used in combination.