JPS61264343A - Developing agent composition for color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a compsn. comprised of a part-agent contg. a p- phenylenediamine type color developing agent stably storable for a long period in a concd. state without evolving any harmful gas, superior in dissolution performance, and also in photographic characteristics, such as fog resistance and max. density, by incorporating said part agent with an org. solvent, and adjusting to a pH of 5-8. CONSTITUTION:The developing compsn. is composed of >=2 kinds of part-agents and can be made practicable by mixing them with water, and the part-agent containing a p-phenylenediamine type color developing agent in incorporated with an org. solvent and its pH is adjusted to 5-8. As the p-phenylenediamine type color developing agent, primary phenylenediamines and their derivs. are useful, and above all, preferable ones are aromatic primary amines each having at least one water-soluble amino group, and especially, compds. represented by the formula shown on the right.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a developer composition for a silver halide color photographic light-sensitive material, and more specifically to a developer composition for fogging, maximum density and v!
Related to a developer composition for a color photographic light-sensitive material composed of a parts agent containing a para-phenylenediamine color developing agent with improved solubility in a four-liquid state (Prior art) Photographic processing solutions include those that are used after weighing and blending various necessary components, and those that are purchased and used as pre-mixed photographic processing agents that already contain the necessary amounts of each necessary component.

Among the above-mentioned pre-mixed photographic processing agents, powder processing agents and liquid processing agents are known.In the case of powder processing agents, they must be dissolved in a certain amount of water before use. In the case of liquid processing agents, if they are concentrated, they are generally diluted with water to a certain amount before use, but if they are not concentrated, they are diluted with water. It can be used as is without addition. Although such pre-prepared photographic processing agents have many advantages in that there is little variation in the quality of the processing solution during preparation and they can be easily used, some of the photographic processing agents contain redox reactions. Many of the components react easily with each other, so they are generally made into kits containing one or more components (hereinafter referred to as parts agents), and when used, these components are mixed with a certain amount of water. It is used after being dissolved.

The above-mentioned kit parts are individually placed in internal containers such as bottles and bags, and then put together in an external packaging (
It is sold as one unit or in a cardboard box (for example, a cardboard box). Recently, in order to prevent the processing solution from deteriorating during processing, a replenishment process is performed to supplement the missing components, and a fixed amount of the replenishment solution is supplied to the processing tank per processed area of the photographic material. In this case, this is generally carried out using an automatic supply pump, and a replenishment solution for dissolving the kit-formed agent is raised to a replenishment tank by means of a bong 1 and is automatically supplied from there.

A photographic processing agent in which the above-mentioned parts are made into a kit is used after being dissolved, diluted, and mixed to a certain amount, but the photographic processing agent has the following drawbacks.

In other words, reducing agents contained in photographic processing agents, such as developing agents, are extremely unstable in a solution state even if they are divided into kits as parts. This tendency is remarkable in the case of main drugs.

For example, Japanese Patent Publication No. 45-37957 describes a method for stabilizing a liquid parts agent containing a paraphenylenediamine color developing agent as described above.
A method is described in which a certain amount of sulfite is added to an acidic aqueous solution containing a paraphenylenediamine color developing agent, and US Pat. No. 3,574,619 describes
A method is described in which benzyl alcohol, ethylene glycol, and sulfite are added to an acidic aqueous solution containing a para-phenylene diamine color developing agent, and Japanese Patent Publication No. 55-21084 describes a method for adding and containing a p-phenylene diamine color developing agent. A method of incorporating sulfite into a solution composition in which the main drug is dissolved in an organic solvent is described. However, in the conventionally known method as described above, sulfite rapidly decomposes and sulfur dioxide is generated, which is not only unfavorable for the working environment, but also causes oxidation of the color developing agent when the 1llf of sulfite decreases significantly. Decomposition proceeds rapidly.

In addition, there have been cases in which parts containing a color developing agent obtained by the method described above are dissolved in water and then other parts containing an alkaline agent are added, or when parts containing an alkaline agent are added. When adding a color developing agent after dissolving it in water, there is a problem in that precipitation, tar, etc. are generated unless the above addition is carried out gradually with sufficient stirring.

As a means to solve such problems, for example, JP-A No. 51-26543 discloses a method of stabilizing by using a phosphate of para-phenylenediamine without using sulfites; Publication No. 47-24323 discloses a method in which an aqueous solution containing a paraphenylenediamine color developing agent and a certain amount of sulfite is sealed in a container mainly made of an organic polymeric material having a low air permeability coefficient;
Furthermore, JP-A-59-216439 discloses a method for stabilizing an aqueous solution containing an N-hydroxyalkyl-substituted paraphenylenediamine color developing agent and a sulfite by adjusting the PIi to 6 to 8. Are known. However, the improvement in solubility when preparing a developing processing solution is not sufficient, especially in the above-mentioned Japanese Patent Application Laid-Open No. 59-210439.
The method described in the publication has the disadvantage that it is not possible to produce a concentrated part agent because the solubility of the color developing agent is extremely low.

(Problems to be Solved by the Invention) Therefore, the object of the present invention is to be able to be stored in a concentrated manner stably for a long period of time, not to generate harmful gases, to have excellent solubility, and to prevent fogging, maximum concentration, etc. It is an object of the present invention to provide a developer composition for a color photographic light-sensitive material, which is composed of a parts agent containing a paraphenylenediamine color developing agent having excellent photographic properties.

(Means for Solving the Problems) According to the present invention, the above-mentioned object of the present invention is to create a composition that is composed of two or more parts and that can be used by mixing with water. In the developer composition for color photographic light-sensitive materials, the parts agent containing the para-phenylenediamine color developing agent contains an organic solvent, and the developer composition for color photographic light-sensitive materials is 5 to 8. I found out that I can get it.

The developer composition for color photographic light-sensitive materials of the present invention (hereinafter referred to as the developer composition of the present invention) is composed of two or more types of parts, but basically includes a paraphenylenediamine color developing agent. The para-phenylene diamine color developing agent contained in the parts agent of the present invention, which is composed of the parts agent containing 22iI and the alkaline agent, includes primary phenylene diamines and their An aromatic primary amine color developing agent having at least one water-soluble amino group;
Particularly preferred is a compound represented by the following general formula (A).

One-piece type [A] Rs-N-R.

N.H.

In the formula, R1 represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group is a straight chain or branched chain having 1 to 5 carbon atoms.
represents an alkyl group, which may have a substituent. R
3 and R3 represent a hydrogen atom, an alkyl group, or an aryl group, but these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. and at least one of R1 and R8 is a hydroxyl group,
an alkyl group substituted with a water-soluble group in a carboxylic acid group, sulfonic acid group, amine group, sulfonamide group ring, or ÷EH,)
−O+F−1<,. This alkyl group may further have a substituent.

In addition, R4 represents a hydrogen atom or an alkyl group, and this alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and q and r represent integers of 1 to 5.

Next, typical examples of the compound represented by the general formula [A] will be listed, but the invention is not limited thereto. For example, 4-amino-N, N-diethylaniline, 3-methyl-
4-amine N, N-diethylaniline, 4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino/-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline/3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamideethyl-4
-Amino-N, N-diethylaniline, 3-methoxy-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-
β-methoxyetheraniline, 3-7cetamido 4-
Amino-N, N-diethylaniline, 4-amino-N,
N-dimethylaniline, N-ethyl-N-β-[β-(
β-methoxyethoxy)ethoxy]ethyl-3-meth)
L'-4-amine aniline, N-engineering N-β (β-
Mention may be made of methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof, such as sulfates, hydrochlorides, sulfites, P-)luenesulfonates, and the like.

Next, the above-mentioned balamino color developing agent in the parts agent according to the present invention is 10 to 500 f, but especially the parts agent 11
A concentrated liquid parts agent containing 901 or more of the above-mentioned color-forming active agents is preferred.

That is, the parts agent having the concentration of para-phenylene diamine color developing material as described above is prepared by dissolving each part agent and 1
li41! This provides a developer composition suitable for containing 1 to 12 t of paraphenylenediamine color developing main system per 11 parts of the developing solution prepared by M. Hit 60? It is preferable to use a part agent suitable for providing a developer composition suitable for preparing a concentrated low-replenishment replenisher containing the above paraphenylenediamine color developing agent.

The parts agent according to the present invention is characterized in that it contains an organic solvent in addition to the above-mentioned paraphenylenediamine color developing agent. Thyl ether, formaldehyde, dimethylformamide, methyl sulfoxide, acetonitrile used in the present invention.

Alkanolamines, hydroxyaminocarboxylic acids, etc. are mentioned, and particularly preferred organic solvents include dihydric alcohols (e.g. ethylene glycol or trimethylene glycol), polyhydric alcohols (e.g. glycerin), polyoxyethylene glycol (e.g. t td diethylene glycol, triethylene glycol or hapolyethylene glycol), alkanolamines (e.g. ethanolamine, jetanolamine and derivatives thereof or triethanolamine), aromatic alcohols (e.g. benzyl alcohol). can.

Such organic solvents are used at a rate of 1v to 950g per 1ft of the parts material according to the present invention.

In addition, the parts agent of the present invention includes, as antioxidants, sulfites and pyrosulfites of alkali metals, any sulfur compound capable of producing sulfite ions in an aqueous solution, hydrazine and hydroxylamine salts, such as hydroxylamine sulfate and hydrochloric acid. salts, ascorbic acid, stereoisomers and diastereoimers of ascorbic acid and their sugar derivatives, glycine, hydroxyacetone (US Pat. No. 3.
No. 615,503, a compound similar to gono (commonly known as 1-acetol'),
Carbohydrazide, phenylhydrazide salt, e.g. evaphenylhydrazine sulfonic acid, phenoxyphenylhydrazine sulfonic acid, hydroxyurea, tetronimide, 2
- Anilinoethanol, aromatic secondary alcohols, hydroxamic acids, bentosematahahexoses, pyrogallol 1,3-dimethyl ether, as well as compounds used primarily for different purposes, such as those commonly used as black-and-white developers (reducing 1-p-methylaminophenol (methol) and other filtrate p-
Amine phenols, hydroquinone compounds and phenidone (L.F.A. Mason (L. de A.Jiio)
ssh), Photographic Grossing Chemistry
ng chemistry), 7 Ocal Keyaki Press (
Focel press, p. 35 (1966)], but sulfites are most preferably used.

According to the present invention, the above-mentioned antioxidant is 0Ω1 mole to 5ρ per mole of paraphenylenediamine color developing agent.
It can be used in a molar ratio, preferably 15 mol per mol of the above-mentioned developing agent, particularly preferably in the range of 2.0 mol to 5.0 mol.

The parts agent containing each of the above components according to the present invention has a pH of 5 to
It is used after being adjusted to 8. The preparation of such parts is carried out by using alkaline agents or acids. As the alkali agent, alkali gold lI4 or ammonium hydroxide or carbonate is generally used, and as the acid, acetic acid or sulfuric acid is generally used.

Further, the parts agent according to the present invention preferably contains 6% or more of water based on the total volume of the parts agent.

That is, 6 to the total volume of the parts agent according to the present invention.
% or more of water, it is possible to improve the solubility when dissolving the developer composition to prepare a processing solution or when preparing a concentrated replenisher, so that tar etc. can be prevented during preparation. No generation occurs, and favorable photographic properties can be obtained.

As mentioned above, the developer composition of the present invention is basically composed of two types: a parts agent containing a paraphenylenediamine color developing agent and a parts agent containing an alkaline agent.
It can be composed of two or more types of parts as needed.

As for the above-mentioned alkaline agent, the same type as the alkaline agent used in the above-mentioned adjustment (1) can be applied. Examples of these alkaline agents include carbonates (e.g., potassium carbonate, sodium carbonate, etc.), borates (e.g., borax,
sodium borate, potassium borate, etc.), phosphates (e.g., sodium phosphate, potassium phosphate, etc.), organic amines (e.g., ethylenediamine, polyethyleneimine,
trimethylamine, etc.), silicates (e.g. silicic acid 6 to 6
It is possible to add and contain photographic additives.

Examples include fluorescent bleaches, surfactants, alkali metal halides, such as potassium bromide, development regulators such as citrazic acid, and chelating agents such as phosphates such as polyphosphates, nitrile, etc. Aminopolycarboxylic acids such as triphosphoric acid, 1,3-diamino-2-propatoltetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, oxycarboxylic acids such as citric acid and glyconic acid, and polyhydroxy compounds such as Tyrone 1 -Hydroxyetheridene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), etc., a development accelerator such as a thioether compound, etc. may be contained. It also contains antifoggants and development inhibitors such as tetrazaindene derivatives.
;can. Each of these additives can be incorporated into other parts, including parts containing paraphenylenediamine color developing agent.

Next, the silver halide used in the silver halide emulsion layer of the silver halide color photographic window used in the present invention includes silver chloride,
Any of those used in ordinary silver halide photographic emulsions, such as silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [1oo] planes to [111) planes can be used. Further, the crystal structure 4 of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of the cut type which forms the latent image primarily on the surface, or of the type which forms the latent image inside the grains. These silver halide grains can be prepared by known methods commonly used in the art. This silver halide is generally dispersed in gelatin, but on the other side of gelatin, polymers such as polyvinyl alcohol are also used instead of gelatin or mixed with gelatin. A silver halide emulsion in which silver halide is dispersed in a suitable binder can be chemically sensitized. They can be done by any conventional method. Namely, active gelatin, noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines,
Chemical sensitization can be carried out using chemical sensitizers such as reduction sensitizers such as tin monochloride alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using a cyanine dye such as zeromethine dye, monomethine dye, dimethine dye, trimethine dye, or an optical sensitizer such as merocyanine color patch alone. Alternatively, in combination (for example, known 2-equivalent and 4-equivalent couplers can be used. As the yellow coupler, open chain ketomethene couplers can be used. Type yellow couplers are advantageous.

■A specific example of a yellow coupler that can be obtained is US Patent No. 2.8.
No. 75,057, @3,265,506, No. 3.
No. 277.155, No. 3,408,194, No. 3
．． No. 415,652, No. 3,447,928, No. 3,664,841, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 48-29432, No. 48-66834
No. 49-10736, No. 49-122335,
It is described in No. 50-28834, No. 50-132926, and No. 53-145024.

As the magenta coupler, compounds such as pyrazolone type, pyrazolotriazole type, pyrazolinopenzimidazole type, indashilon thread, and cyanoacetyl type are used. Specific examples of magenta couplers that can be used include U.S. Pat.
No. 600,788, No. 3.061,432, No. 3
,062. ．． No. 653, No. 3,127,269, No. 3,311,476, No. 3,419,391,
No. 3,519,429, No. 3,558,319, No. 3,684,514, - No. 3,888,680
British Patent No. 1,247,493, British Patent No. 1,534
, No. 349, West German Patent Application (OLS) 2.156, 11
1, Belgian Patent No. 769,116, Belgian Patent No. 792,
No. 525, Special Publication No. 1984-60479, % Kai No. 49-2
No. 9639, No. 49-111,631, No. 49-12
No. 9538, No. 50-13041, No. 50-1229
No. 35, No. 51-20826, No. 52-58533, No. 52-80027, Japanese Patent Application No. 52-98876,
It is described in No. 52-101247, No. 52-104437, etc.

As a colored magenta coupler as a masking coupler, a compound in which an arylazo group is substituted at the active site of a colorless magenta coupler is generally used.
For example, U.S. Patent No. 2,801°171, U.S. Patent No. 2,98
No. 3,608, No. 3, 005.

No. 712, No. 3,684,514, British Patent No. 93
7.621, JP-A-49-123625, JP-A-49-123625
Examples include compounds described in No. 131448 and the like.

In addition, there are colored magenta couplers of the type described in U.S. Pat. No. 3,419,391 in which the dye is leached into the processing bath by reaction with the oxidation products of the color developing agent. can.

Phenol or naphthol derivatives are generally used as cyan couplers. Specific examples include U.S. Pat. No. 2,423,730, U.S. Pat. No. 2,474.293, U.S. Pat.

No. 826, No. 3,476.563, No. 3,737
゜316, same No. 3,758,308, same No. 3,83
No. 9゜044, No. 3,998,642, Japanese Unexamined Patent Publication No. 1973
-37425, 50-10135, 50-25
No. 228, No. 50-112038, No. 50-1174
No. 22, No. 50-130441, No. 51-21828
No. 5218315, No. 53-52423, No. 5
It is described in No. 3-105226, No. 53-109630, etc.

As a colored cyan coupler as a masking coupler, a compound in which an arylazo group is substituted at the active site of a colorless cyan coupler is used, such as U.S. Pat. No. 2,521,908, U.S. Pat. No. 3,034,892, British Patent No. 1,255,111, Japanese Unexamined Patent Publication No. 48-22
Examples include compounds described in No. 028 and the like.

Furthermore, U.S. Patent No. 3,476.563 and Japanese Patent Application Laid-open No. 1987-1
Colored cyan couplers of the type in which the dye flows out into the processing bath by reaction with the oxidation product of a color developing agent, such as those described in No. 0135 and No. 50-123341, can also be used.

Further, in order to improve photographic properties, a so-called combining coupler, which forms a colorless dye, may be included.

In addition, the silver halide color photographic light-sensitive material according to the present invention may contain other layers depending on the purpose, such as a photosensitive layer and/or other constituent layers (for example, an intermediate layer, a subbing layer, a filter layer, a protective layer, an image-receiving layer, etc.). A variety of photographic additives may be included.

For example, stabilizers and anti-capri agents such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salt polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, acryloyl-based, albodiimide-based, maleimide-based, Hardeners such as methanesulfonic acid esters and triazine; gradation adjusters such as 8I14 metals (e.g. rhodium and ruthenium) or cadmium and thallium; development accelerators such as benzyl alcohol and polyoxyethylene compounds; chroman image stabilizers such as those based on the image stabilizers such as those based on claman, bisphenol, and phosphite; and lubricants such as waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids.

In addition, anionic, cationic, and nonionic surfactants can be used as coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. Alternatively, various species of both sexes can be used. The mordant is an N-guanylhydrazone compound.

Quaternary onium salt compounds and the like are effective. The antistatic agent is diacetyl cellulose and styrene perfluoroalkyl rhidium maleate co-electrolyte.

An alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid is effective.

Examples of the color turbidity inhibitor include polymers containing vinylpyrrolidone monomers, polymers containing vinylimidazole monomers, and the like.

Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers.

It is also possible to use colloidal silicon oxide. Also, acrylic ester is used as a latex added to improve film properties.

Examples include copolymers of vinyl esters and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

The silver halide color photographic light-sensitive material of the present invention can be produced by coating a silver halide emulsion layer and other constituent layers containing various photographic additives as described above on a support. Manufactured. Advantageously used supports include, for example, loose 42 paper, polyethylene-covered paper, polyproporin synthetic paper, glass polycellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, and the like. These supports are appropriately selected depending on the intended use of each silver halide photographic material.

These supports are subjected to undercoat processing if necessary.

After exposure, the above-mentioned silver halide color photographic light-sensitive material can be developed by a commonly used known method.

Example 1゜ Color paper samples were first prepared as follows.

2-(1-benzyl-2,4-dioquimidazolidin-3-yl)-2-bivalyl 2'-chloro-
After dissolving 5'-(4-(2,4-di-t-pentylphenoxy)butanamide) acetanilide in dibutyl phthalate and protecting and dispersing it in an aqueous gelatin solution,
It was mixed with silver chlorobromide emulsion and coated. The coating amounts of the coupler and silver used at this time were 24 to 100cm for the coupler and 0.85cm for silver. On this, a gelatin intermediate layer containing dioctylhydroquinone is provided, and on top of this, as a coverr, 3-(2-chloro-5-(1-(octadecyl)succinimide]anilino)-1-(2,4,6- )
Dichlorophenyl)-5-pyrazolone was dissolved in dibutyl 7-thalerate, protected and dispersed in an aqueous gelatin solution, mixed with a green-sensitive silver chlorobromide emulsion, and then coated and dried. The amount of coupler used at this time was 4 per 100
9■, silver was 0.8711q. On top of this layer, a gelatin solution of dioctylhydroquinone is applied as a color turbidity prevention layer, and on top of this layer, 2 as a coupler is applied.
-(2-(2,4-di-t-pentylphenoxy)butanamide)-4,6-dichloro-5-methylphenol was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, and then red-sensitive mass bromide After mixing with silver emulsion, it was coated and dried.

The coating amount of the coupler used at this time was 30 capes per 100 mm, and the amount of silver was 0.75 capes.

Materials for color developer replenisher compositions prepared above and composed of the following parts for color paper No. 11-6
was created according to the following.

Parts agent (A) Parts agent (B) Parts agent (C) Fields were adjusted with 2N sodium hydroxide or sulfuric acid as described in Table 1 below.

Parts agent (D) Potassium carbonate 25. Of Potassium Hydroxide (48.5ch) 9. Add 50 d of water. Put the above parts agent (C) in a plastic bottle and store it at 60℃ for 2 months, then add parts agents (A) to (D) to 800 d of water.
6 types of color developer replenishers were prepared by sequentially dissolving them with water and finishing with water to form 11. At that time, the generation of tar, etc. when adding the parts agent (D) to the % was observed, and the results are shown in Table 1 below.

Next, take 800 μm of each color developer replenisher, add a starter with the following composition, add water to make 1 μ,
Soak the rice with 5% potassium hydroxide or 18N sulfuric acid.
02, and six types of color developing solutions were prepared.

(Starter) Using these six types of color developing solutions, the above-mentioned color paper samples, which had been subjected to regular exposure using a conventional method, were processed according to the following processing steps.

(Processing process) (Processing source #) (Processing time) 1. Color development 38.0℃ 3 minutes 15 seconds 2. Bleach fixing 38.0℃ 1 minute 30 seconds 3. Stabilization 32.0℃ 2 minutes 4. Drying drying
70.0° C. 3 minutes The bleach-fix solution and stabilizing solution used in the above processing steps have the following formulation.

(Bleach-fix solution) Ethylenediaminetetraacetic acid iron II) ammonium 5 (
H'ethylenediaminetetraacetic acid 5v Ammonium sulfite 10f Ammonium thiosulfate (72.5%) 100m/Aqueous ammonia (28th) Finished to 1st base with 10d water, and adjusted ■ to 7.5 with acetic acid and aqueous ammonia.

(Stabilizing liquid) 2-methyl-4-isothiazolin-3-one 0.0
111-Hydroxyethylidene-1,1-diphosphonic acid 1.51 Water was used to finish the first base, and the gate was adjusted to 0.7 using ammonia water.

After developing the color paper sample, Sakura PDA-65
Fog (stain) and maximum fIk degree (Dma·X) were measured using an m-degree meter, and the obtained results are shown in Table 1 below.

(Table-1) Parts agents according to the present invention with parts agent fields of 5 to 8 (C)
When color paper is developed using a developer replenisher composition composed of It was also found that the stability was good.

Example 2 A color developer replenisher composition for color paper was prepared according to the following formulation.

Parts agent (A) Parts agent (B) Parts agent (C) Next, only the water child of the parts agent (A) was changed as shown in Table 2 below to make a color developing auxiliary agent for color paper. Compositions I@7 to I@11 were created.

After putting the above five types of parts agents in a plastic bottle and storing it at 60℃ for 2 months, add parts agents (A) to (C) to 800ml of water in order, and finally add 1 li of water to 1 ri. Five types of color developing solutions were prepared. And especially parts agent (C
) was observed for the generation of tar etc., and the results are shown in Table 2 below.

In addition, Example 1 was prepared using the color developing solution prepared as described above.
Color paper produced in the same manner as in Example 1 was developed and the results obtained are shown in Table 2 below (Table 2). ) to 6%
In the case of a developer replenisher composition containing water as described above, not only does it have good solubility during preparation, does not generate tar, but also produces little fog after storage, and provides a sufficiently high maximum density. , was found to be extremely stable.

Example 3 First, a color negative sample was prepared as follows.

An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer are all formed thereon. The coating was applied so that the amount of silver was 100 - 70 cm. The above emulsion layer is made of silver iodobromide with a silver iodide mole content of about 4.5%, and the blue-sensitive silver halide emulsion layer contains a-(4-nitrophenoxy)-a as a yellow coupler. -piparyl-5-[γ-(2,4-di-t-aminophenoxy)butyramide-2-chloroacetanilide,
1 m of green-sensitive silver halide emulsion contains 1-(2,4,6-trichlorophenyl)-3-( as a mi/ta coupler.
[a-'(2,4-di-1-amylphenoxy)-acetamide]benzamide)-3-pyrazolone and 1-(
2,4,6-)lichlorophenyl)-3-([a-(2
, 4-di-t-amylphenol)-acetamido]peszamide)-4-(4-methoxyphenylazo)-5
- Virazolone was used as a cyan coupler in the red-sensitive silver halide emulsion layer, and 1-hydroxy-N-(a-(2
, 4-t-amylphenoxy)butyl)-2-naphthamide, and additives such as a sensitizing dye, a hardening agent, and a spreading agent were added to each emulsion layer. A color film sample was prepared in this manner.

Next, a developer replenisher composition composed of parts having the following composition was prepared.

Parts agent (A) Parts agent (B) Hydroxylamine sulfate 3.0? Add water and 15-parts agent (C
) According to the formulation listed in Table 3.

After putting the above parts agents (C) (six types listed in Table 3) into a plastic bottle and storing them at 60°C for 2 months, add parts agents (A) to (C) sequentially to water. 800sE
A color developer replenisher was prepared by dissolving the color developer in 11 and finally adding 11 with water. In particular, we observed the generation of tar etc. when adding parts agent (C), and the obtained results are shown in the table below.
4.

Next, add 800 ttt of each of the above color developer replenishers.
After adding a starter having the following composition, 48.
5. Sodium hydroxide or 18N sulfuric acid
A color developing solution of 0.1 Kv14*L, e vn was prepared.

(Starter) Potassium carbonate 2.5f Potassium bicarbonate 1.5 to Sodium bromide 1.3t Potassium iodide 0.002r (Add water
20-Next, the above color negative sample was subjected to main beauty exposure according to a conventional method, and developed using the above six types of color developing solutions according to the following processing steps.

(Processing process) (Processing temperature) (Processing time) 1, Color development 38.0℃ 3 minutes 15 seconds 2, #
4 White 38.0°C 3 minutes 15 seconds 3, fixation 38.0°C 4 minutes 4° 1st stabilization 32.0°C 2 minutes 5,
Second stabilization 32.0℃ 2 minutes 6
, drying at 70° C. for 5 minutes The formulations of the bleaching solution, fixing solution, first stabilizing solution, and second stabilizing solution used in the above processing steps are as follows.

(bleach solution) (Adjust to F[5,8 using acid.

(Fixing I) Thio-te, ammonium (72,5-thi solution) 25
0m anhydrous sodium sulfite 18? Sodium metabisulfite 3. Of ethylenediaminetetraacetic acid disodium 2. Or sodium carbonate 10. Or add water and lf
i (first stabilizing liquid) 2-methyl-4-inteazolin-3-one 0.01r 1-hydroxyethylidene-1,1-diphosphonic acid 1.51 IK finish with water, and 7 ml with ammonia water vI4 to .0
It was extravagant.

(2 stabilizing solution) r Formalin (37% solution) 4d
(Refinish with water.

The capri (stain) and maximum density (Dmax) of the processed color negative samples were measured using a Sakura PDA-65 densitometer, and the results are shown in Table 4 below.

(Table-3) (Table-4) As shown in the table above, a developer replenisher obtained from a parts agent (C) according to the present invention containing ethylene glycol in a parts agent containing a paraphenylenediamine color developing agent. The composition has low stain and excellent maximum density. Furthermore, it can be seen that when the parts agent (C) according to the present invention containing an organic solvent is used, the solubility during the preparation of the present salvage solution is good and the stability is also excellent. It was also found that N117, a sample containing 1.5 mol or more of sulfite per 1 mol of paraphenylenediamine color development material, had excellent photographic properties.

(Effects of the Invention) By adding and containing an organic solvent to a part agent containing a paraphenylenediamine color developing agent and adjusting the particle size to 5 to 8, it is possible to improve the dissolution of the developer composition 14 during adjustment. , photographic properties such as fog, maximum density can also be improved.

Claims (3)

[Claims] (1) In a developer composition for a color photographic light-sensitive material that is composed of two or more types of parts agents and is adjusted to be usable by mixing with water, the parts agent contains a paraphenylenediamine color developing agent. 1. A developer composition for a color photographic material, characterized in that it contains an organic solvent and has a pH of 5 to 8. (2) The developer composition for a color photographic light-sensitive material according to claim 1, wherein the part agent containing the paraphenylenediamine color developing agent contains an antioxidant. (3) A developer for a color photographic light-sensitive material according to claim 1 or 2, wherein the part agent containing a paraphenylenediamine color developing agent contains at least 6% water. Composition.