JP2657704B2 - Concentrated composition for color developer and processing method using the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a concentrated composition for a color developing solution of a silver halide color photographic light-sensitive material and a developing method using the same. The present invention relates to a concentrated composition having excellent properties, a concentrated composition of a color developing solution capable of obtaining stable photographic performance even in the process of preparing a color developing solution using the concentrated composition, and a processing method using the same. is there.

(Prior art) As a method of supplying chemicals used in recent color development, each component is not supplied in powder form, but can be easily used only by diluting to a specified concentration before use. In many cases, a liquid concentrated composition (premix) having a fixed composition to be a color developing solution is supplied and used.

Such a concentrated composition has a shorter time required for preparing a color developing solution than a method of preparing it at the processing site from the beginning, and is convenient for workability and labor saving that requires less labor. If the concentrate composition is particularly liquid, the above advantages are greater than when it is solid. However, on the other hand, it has a drawback that storage stability is poor and a storable period is short. Generally, such a concentrated solution is 2 to 4 in consideration of storage stability and workability during use.
The concentrated composition group is divided into so-called parts, and these are dissolved together in water to form a usable color developing solution. Among these concentrated composition groups, the part having the above-mentioned storability problem is mainly a part containing a color developing agent as a main component and a part containing a preservative of the color developing agent.

For example, a color developing solution containing hydroxylamine is conventionally known. However, a concentrated solution such as a concentrated composition for a developer containing a high concentration of hydroxylamine has a short storage time, and the storage ratio may be 20 to 30% due to storage. That is, in this concentrated composition, nitrogen oxides such as ammonia are generated and deteriorated by oxidative decomposition of hydroxylamine by air or decomposition considered to be due to a trace amount of metal, which greatly affects photographic characteristics after development processing. In addition, there is a danger that the generated gas increases the internal pressure of the container of the concentrated composition and damages the container.

Furthermore, the part mainly composed of a color developing agent is generally composed of a low pH due to the stability of the color developing agent, but the above-described color developing agent is mainly composed of hydroxylamine because hydroxylamine is easily decomposed at a low pH. It cannot coexist in the part that does. Therefore, it is difficult to reduce the number of components of the concentrated composition group to reduce costs, improve workability, and the like.

Therefore, various methods have been proposed for preventing the decomposition of hydroxylamine. For example, Japanese Patent Publication No. 51-25143,
These are described in JP-A-61-264343, JP-A-55-21084, Research Disclosure Item No. 18844, and the like. In recent years, concentrated compositions using diethylhydroxylamine, a derivative thereof, instead of hydroxylamine have been supplied and used. However, none of them has a sufficient effect of preventing the decomposition over time, and it is impossible to obtain constant photographic characteristics. JP-A-63-5341 discloses a color developing solution containing a preservative of the following general formula (I), but does not disclose any preservation of the preservative itself.

Accordingly, an object of the present invention is to provide a highly concentrated composition for a color developer. More specifically, an object of the present invention is to reduce the decomposition and coloring of components with the passage of time during concentration, and to reduce the effects of composition fluctuations and decomposition products even when diluted and prepared as a color developing solution to obtain stable photographic performance. And
It is an object of the present invention to provide a concentrated composition for a color developer which improves the working environment.

(Means for Solving the Problems) The above object has been achieved by the following method. That is, an aqueous concentrated composition containing at least one compound represented by the following general formula (I) and an aromatic primary amine color developing agent and having a concentration ratio of 2 to 50 times the final use concentration is used. This can be achieved by a concentrated composition for a color developing solution of a silver halide color photographic light-sensitive material, characterized in that the composition is at least a part of the constituent components.

General formula (I) (Wherein L represents an alkylene group which may be substituted;
Is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, or an alkyl-substituted group. R represents a hydrogen atom or an optionally substituted alkyl group; The stability of the aqueous concentrated composition containing the compound represented by the general formula (I) in the concentrated composition of the present invention, unlike hydroxylamine, is remarkably improved at the point where the concentration ratio is twice, and the residual after storage. Of about 90%, without generation of nitrogen compounds as decomposition products, and as a result, the stability of photographic characteristics is significantly improved. Further, in the present invention, the aqueous concentrated composition also serves as a part of a low pH concentrated composition containing a developing agent at the same time. That is, it has very excellent stability that the preservative and the developing agent can be made into one part. This fact is completely different from hydroxylamine and diethylhydroxylamine, which have been widely used as preservatives, and is unexpected.

 Hereinafter, the general formula (I) will be described in detail.

General formula (I) In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene,
Propylene is a preferred example. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an ammonium group which may be alkyl-substituted, and preferred examples thereof include a carboxy group, a sulfo group, a phosphono group, and a hydroxy group. . A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted,
Represents an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, a sulfamoyl group which may be alkyl-substituted, and a carboxy group, a sulfo group, a hydroxy group, a phosphono group, and a carbamoyl group which may be alkyl-substituted. Preferred examples are given. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Group, carboxyethyl group,
Particularly preferred examples include a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. R represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted,
To 5 are preferred. As the substituent, a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group,
An amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, and a sulfamoyl group which may be substituted with alkyl. There may be two or more substituents. R represents a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group,
Preferred examples include a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group, and a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group are particularly preferred examples. be able to. L and R may combine to form a ring.

When the compound of the general formula (I) has an acid group, the acid group may be appropriately added as a salt such as an alkali metal salt or an ammonium salt.

Representative examples of the compounds represented by formula (I) are shown below, but the present invention is not limited to these compounds.

(19) HO-NH-CH 2 CO 2 H (20) HO-NH-CH 2 CH 2 CO 2 H (26) HO-NH-CH 2 CH 2 SO 3 H (28) HO-NH- (CH 2) 3 SO 3 H (29) HO-NH- (CH 2) 4 SO 3 H (30) HO-NH-CH 2 PO 3 H 2 (32) HO-NH-CH 2 CH 2 PO 3 H 2 (33) HO-NH-CH 2 CH 2 OH (34) HO-NH- (CH 2) 3 OH (35) HO-NH-CH 2 - PO ₂ H ₂ (46) HONHCH ₂ CH (PO ₃ H ₂ ) ₂ The compound represented by the general formula (I) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction). West German Patent No. 1,159,634,
"Inorganica Chimika Acta" (Inorganica Chi
mica Acta), 93, (1984) 101-108, etc., and specific methods are described below.

Synthesis Example Synthesis of Exemplified Compound (7) In a 200 ml aqueous solution of hydroxylamine hydrochloride (20 g), sodium hydroxide (11.5 g) and sodium chloroethanesulfonate (9) were added.
Add 6g, keep at 60 ℃ 40m of aqueous solution of 23g of sodium hydroxide
l was added slowly over 1 hour. 3 hours at 60 ° C
, The reaction mixture is concentrated under reduced pressure,
Heated to ° C. Filter the insolubles and add 500 ml of methanol to the filtrate.
Was added to give the desired product (exemplified compound (7)) as monosodium salt crystals. 41 g (yield 53%) Synthesis of Exemplified Compound (11) To a hydrochloric acid aqueous solution of 7.2 g of hydroxylamine hydrochloride and 18.0 g of phosphorous acid was added 32.6 g of formalin, and the mixture was heated under reflux for 2 hours. The resulting crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of Exemplified Compound (11).

The amount of the aqueous concentrated composition solution of the compound of the above general formula (I) to be added is preferably 0.05 to 2.5 mol per 1 and more preferably 0.1 to 1.5 mol. Also, 2
More than one species may be used. Further can be used in combination with various preservatives described in JP-A-63-146041,
Among them, when the concentration ratio is 2 to 50, particularly 10 to 40, the alkanolamines represented by the following general formulas (A), (BI) and (B-II) and the aromatic polyhydroxy compound are used in combination for preservation. This is particularly preferred in that the stability of the agent itself is increased and the stain is small even when used in the development processing.

General formula (A) (Wherein, R ₁₁ is a hydroxyalkyl group having 2 to 6 carbon atoms;
₁₂ and R ₁₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula Wherein n is an integer of 1 to 6, X and X 'are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 2 to 6 carbon atoms.
Represents a hydroxyalkyl group. Preferred specific examples of the compound represented by the general formula (A) are as follows.

(A-1) Ethanolamine (A-2) Diethanolamine (A-3) Triethanolamine (A-4) Di-isopropanolamine (A-5) 2-Methylaminoethanol (A-6) 2-Ethylaminoethanol (A-7) 2-dimethylaminoethanol (A-8) 2-diethylaminoethanol (A-9) 1-diethylamino-2-propanol (A-10) 3-diethylamino-1-propanol (A-11) 3- Dimethylamino-1-propanol (A-12) isopropylaminoethanol (A-13) 3-amino-1-propanol (A-14) 2-amino-2-methyl-1,3-propanediol (A-15) Ethylenediaminetetraisopropanol (A-16) benzyldiethanolamine (A-17) 2-amino-2- (hydroxymeth Le) -1,
3-propanediol (A-18) 1,3-diaminopropanol (A-19) 1,3-bis (2-hydroxyethylmethylamino) -propanol These compounds represented by the general formula (A) are It is preferable to prepare the color developing solution so that the effect of the object of the invention is in the range of 3 g to 100 g per color developing solution, and more preferably in the range of 6 g to 50 g.

General formula (BI) General formula (B-II) Wherein R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom,
Halogen atom, a sulfonic acid group, an alkyl group having a carbon number of 1 to 7, -OR _18, -COOR _19, Or, it represents a phenyl group. R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₁₅ represents -OH or a hydrogen atom, R ₁₄ is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR ₁₈ , -COOR ₁₉ , Or a phenyl group.

The alkyl group represented by R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ includes those having a substituent, for example, a methyl group, an ethyl group,
iso-propyl group, n-propyl group, t-butyl group, n
-Butyl group, hydroxymethyl group, hydroxyethyl group, methyl carboxylic acid group, benzyl group, etc., and the alkyl group represented by R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ is the same as the above, and further octyl And the like.

Examples of the phenyl group represented by R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Specific examples of the chelating agent of the present invention are shown below, but are not limited thereto.

(BI-1) 4-isopropyl-1,2-dihydroxybenzene (BI-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (BI-3) 1,2,3- Trihydroxybenzene-5-carboxylic acid (BI-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (BI-5) 1,2,3-trihydroxybenzene-5-carboxy −
n-butyl ester (BI-6) 5-t-butyl-1,2,3-trihydroxybenzene (BI-7) 1,2-dihydroxybenzene-3,4,6-trisulfonic acid ( B-II-1) 2,3-Dihydroxynaphthalene-6-sulfonic acid (B-II-2) 2,3,8-Trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2,3-dihydroxy Naphthalene-6-carboxylic acid (B-II-4) 2,3-dihydroxy-8-isopropyl-naphthalene (B-II-5) 2,3-dihydroxy-8-chloro-naphthalene-6
Sulfonic acid Among the above compounds, particularly preferred compounds used in the present invention include 1,2-dihydroxybenzene-3,5-
Examples thereof include disulfonic acid, which can also be used as an alkali metal salt such as a sodium salt and a potassium salt (a specific exemplified compound (B-I-2)).

In the present invention, the compounds represented by the aforementioned general formulas (BI) and (BI)
The compound represented by I) is 5 mg to 15 g per color developing solution.
, And more preferably 15 mg to 10 g, and still more preferably 25 mg to 7 g.

The concentration ratio of the concentrated composition used in the present invention, which comprises an aqueous concentrated solution containing the compound represented by the general formula (I) as at least a part of the constituent components, is set to 2 in order to obtain the color developing solution 1. It is a level that dilutes to 50 times, the concentration ratio is preferably 10 to 50 times, more preferably 15 to 50 times,
Particularly preferably, it is 20 to 50 times. In the present invention, when the concentration ratio of the concentrated composition solution containing the compound of the general formula (I) is less than 2, the compound represented by the general formula (I) during storage is significantly decomposed by oxidation or the like, and the residual ratio is extremely low. . If the concentration ratio is too small, the volume of the concentrated solution necessary for producing a unit volume of the developing solution becomes large, and it becomes difficult to handle in use such as transportation. Further, if the concentration ratio exceeds 50 times, the solubility of the concentrate itself during production may be reduced, or the precipitate may be formed at a low temperature, and the concentration ratio needs to be in the above range. .

In the present invention, the ratio of the water and the preservative in the aqueous concentrated composition liquid is represented by weight ratio, and is usually 1: 1 to 50: 1, preferably 1: 1 to 20: 1, and more preferably 1: 1. 1 to 10: 1.

The concentrated composition may be decomposed into two or more parts, and in the present invention, the concentrated composition for a color developing solution means a concentrated composition group when divided into such parts. Therefore, when constituting a color developer from the concentrated composition of the present invention, this concentrated composition group is mixed,
Made by diluting with water.

Generally, other necessary components are also concentrated, and the concentrated composition of the color developing solution is composed of 3 to 4 parts in total. The contents are generally divided into the main components of (developer), (preservative, alkaline agent, fluorescent whitening agent) and (alkali agent, chelating agent). (Benzyl alcohol, benzyl alcohol solvent) part, separate the above components into two or more parts, replace the main component with another part, and optimize the combination according to the purpose and application Usually, it is composed into

The color developer obtained from the concentrated composition of the present invention is the same as a normal color developer except for the above-mentioned points.

Known compounds can be used for each of the main components,
Specific examples thereof include color developing agents, various buffers, chelating agents, development accelerators, antifoggants, fluorescent brighteners, surfactants, and inorganic agents described on page 7 and thereafter of JP-A-63-146041. Halogen salts and the like. If necessary, an antifoaming agent, a fungicide, a solvent such as polyethylene glycol or methanol may be added to the concentrated composition.

Containers for storing these concentrated compositions may be those commonly used such as polyethylene, polypropylene, polystyrene, polyvinyl, vinyl chloride, and glass, but are preferably European Patent 0250219A and JP-A-63-17453.
It is more desirable to use a container using a material having low oxygen permeability as described in JP-A-63-125143, from the viewpoint of the stability of the concentrated composition. The storage temperature is preferably from 0 to 10C.

The concentrated composition for a color developing solution of the present invention is diluted into a color developing solution, and after processing a silver halide color light-sensitive material with the above color developing solution, bleaching, bleach-fixing, and a desilvering step such as fixing are performed. It is common to carry out a washing and / or stabilizing treatment.

The bleaching solution, bleach-fixing solution and fixing solution used in the desilvering step are generally composed of a concentrated composition of 1 to 3 parts, like the color developing solution. As the main component, any known compounds can be used. For example, bleaching agents, bleaching accelerators, rehalogenating agents, pH buffering agents, fixing agents described on page 10 or later of JP-A-63-146041 can be used. , Preservatives, and the like. The details described in the patent regarding the washing and / or stabilizing step also apply to the treatment in the present invention.

The method of the present invention can be applied to any processing step using a color developer. For example, the present invention can be applied to processing of color paper, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, color reversal film, etc., but is particularly preferably applied to color paper and color reversal paper.

Further details of the color light-sensitive material used in the present invention,
For example, it is described on pages 13 to 26 of JP-A-63-146041.

(Examples) Specific examples of the present invention will be described below, but the present invention is not limited to these embodiments.

Reference Example 1 A multilayer color printing paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene as a color photosensitive material. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7) were dissolved by adding 27.2 cc of ethyl acetate and 5.7 g of the solvent (Solv-1), and the solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

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

 The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY ) 0.77 Color image stabilizer (Cpd-1) 0.18 Solvent (Solv-1) 0.23 Color image stabilizer (Cpd-7) 0.03 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average and 0.39 μm emulsion (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion is AgBr
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.22 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.42 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv) −5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 μm average and 0.45 μm average grain size (Ag mole ratio), fluctuation in grain size distribution) Coefficients are 0.09 and 0.11, AgBr for each emulsion
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Next, each part of the concentrated composition of the color developing solution shown below was prepared.

Put the above part (A) solution in a polyethylene container,
Vent the air at the top of the container and seal it tightly.
It was aged at 40 ° C. for 6 weeks. The preservative concentration (%) after 6 weeks was determined by analyzing the concentration of the preservative in the liquid before and after the lapse of time by high performance liquid chromatography (HPLC).

Further, 50 ml and 50 ml of the parts (A), (B) and (C) before the aging were respectively collected in the amounts shown in Table 1, mixed, and added with water to 1 to adjust the pH to 10.05. The photosensitive material described above was exposed to light through an optical wedge using a color developing solution adjusted using the method described above, and processed in the following steps.

On the other hand, only the part (A) was stored under the aging conditions shown above, and the parts (B) and (C) used the liquid immediately after preparation without aging, and these were mixed and diluted at the same ratio as described above to develop the color. A solution was prepared and the treatment was performed in the same manner.

Changes in photographic performance before and after the aging of Part (A) were measured with a blue light for the change in photographic performance. The minimum change in yellow density (ΔDmin) and the change in yellow gradation (Δγ)
I asked for it.

ΔDmin = [Dmin of the aged part (A) solution] − [Dmin of the part (A) solution before aging] Δγ = [part (A) solution before aging of the part (A) solution after aging] Density at the same exposure amount obtained in the same manner as above)
-[Exposure to give a yellow density of 0.5 in solution (A) before aging + concentration of exposure at logE = 0.3] Further, each solution prepared in concentrated composition part (A) was subjected to-
It was stored at 5 ° C. for 2 weeks, and the concentrated composition liquid was visually observed for any precipitate. The evaluation was performed as follows.

These results are summarized in Table 1.

Step Temperature Time color developing 38 ° C. 45 seconds blix 35 ° C. 45 seconds rinsing (1) 35 ℃ 20 seconds rinsing (2) 35 ℃ 20 seconds rinsing (3) 35 ℃ 20 seconds Drying 80 ° C. 60 seconds Bleach-fixing solution Water 600 ml ammonium thiosulfate solution (700 g / l) 100 ml ammonium sulfite 45 g iron (III) ammonium ethylenediaminetetraacetate 3.0 g ethylenediaminetetraacetic acid 3.0 g ammonium bromide 30 g nitric acid (67%) 27 g Add water 1000 ml pH 5.80 washing solution ion exchange water (calcium and magnesium each less than 3ppm) From the results in Table 1, it can be seen from the general formula (I) used in the present invention.
When the concentration ratio of the preservative of the concentrated composition exceeds 2 times, the preservative residual ratio is remarkably improved, and the liquid is aged over time with a liquid having the same concentration ratio as the comparative preservative, diethylhydroxylamine. The stability of the preservative is high, especially when the concentration ratio is 2 times or more, a high preservative retention ratio is stably exhibited, and therefore, the stability of the concentrated composition solution becomes good, which indicates that the treatment No. 1-6 This is apparent from a comparison between 1-15 and Nos. 1-1 to 1-5.

If the concentration rate of the preservative of the formula (I) is too low, the stability of the preservative is low, and the fluctuation of the photographic performance becomes slightly large (processing Nos. 1-6 and 1-11). On the other hand, when the concentration ratio is high, the residual ratio of the preservative is high, and the fluctuation in photographic performance is small and good. However, crystallization tends to start, and a decrease in the stability of the solution was observed (Process No. 1). -10, 1-15).

In addition, the combined use with alkanolamines and aromatic polyhydroxy compounds can further improve the stability of the preservative, and can be applied to treatment Nos. 1-9, 1-14 and Nos. 1-16, 1-17, No. 1−
It is clear from comparison with 18, 1-19.

Further, the diethylhydroxylamine used for comparison had a greater coloration (brown to dark brown) and a more pronounced odor in the temporal composition of the concentrated composition as compared with the preservative of the present invention having the same concentration rate. However, it was also observed or confirmed that the preservative of the present invention had a low degree of coloring and hardly any odor.

Example 1 Each part of the concentrated composition of the color developing solution shown below was prepared.

100 ml, 50 ml, and 50 ml of each of the prepared parts (A), (B) and (C) were collected, mixed, and added with water to adjust the pH to 10.1 with a color developer prepared with potassium hydroxide. The sample prepared in Reference Example 1 was exposed to light using an optical wedge and processed.

Subsequently, the part (B) solution was placed in a vinyl chloride container, sealed, sealed and stored under the same aging conditions as in Reference Example 1, and then used, and the other parts (A) and (C) were used. The treatment was performed in the same manner as above using a new solution that had not been aged.

The sample thus obtained was subjected to density measurement, and the minimum density change (ΔDmin) and gradation change (Δγ) of the yellow color image were obtained in the same manner as in Reference Example 1.

 Table 2 shows the results.

From the above table, it can be seen that even in a system containing a developing agent and a preservative in the concentrated composition part (B) of the present example, the concentrated solution containing the preservative of the general formula (I) of the present invention has a remarkably excellent concentrated composition. It is evident from the comparison with the preservative, diethylhydroxylamine, which is used for comparison, that it shows the stability of the product and that the fluctuation in photographic performance is small.

(Effect of the Invention) An alkyl-substituted hydroxylamine having a specific substituent in the alkyl group is used as a preservative of a color developer, and the concentrated composition for a color developer of the present invention containing the preservative is a conventional hydroxylamine-containing concentrate. The stability over time is remarkably superior to those containing an amine-based preservative. A processing solution is prepared using this concentrated composition, and when the processing is performed, stable processing with little fluctuation in photographic performance (minimum density, gradation and sensitivity) can be performed, and a color photographic material with stable finish quality can be provided. be able to.

Claims (2)

(57) [Claims] An aqueous concentrate containing at least one compound represented by the following general formula (I) and an aromatic primary amine color developing agent, and having a concentration ratio of 2 to 50 times the final use concentration. A concentrated composition for a color developing solution of a silver halide color photographic light-sensitive material, characterized in that the composition comprises at least a part of a constituent component. General formula (I) (Wherein L represents an alkylene group which may be substituted;
Is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, or an alkyl-substituted group. R represents a hydrogen atom or an optionally substituted alkyl group; ) 2. A color developing solution which is retained as the concentrated composition for a color developing solution according to claim 1, and is used to prepare a color developing solution. A processing method comprising subjecting a photosensitive material to color development processing.