JPH0146866B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to liquid developer concentrate compositions for use in color photography and methods for their preparation. More particularly, the present invention relates to liquid developer concentrates that are formulated into more concentrated compositions and diluted with water to obtain color developer baths ready for use in color photography. Generally, the developer solution used for color photography is
It consists of an aqueous solution containing various components along with a p-phenylenediamine developer which is oxidized by exposed silver halide and reacts with a coupling agent to form a dye. Components of this type usually include antioxidants and alkalinizing agents and various additional components, such as buffers, anti-calcium agents.
[For example, U.S. Pat. No. 2,656,273, U.S. Pat. No. 3,462,269,
French Patent No. 3201246, French Patent No. 3214654, French Patent No. 3994730, French Patent No. 2251036 and
1975 Research Day Closure
Disclosure) 13410], fluorescent brighteners (e.g.
Research Disclosure 17643-V, 1978), as well as other known development control agents, such as those described in Research Disclosure 17643 (1978), especially
Includes regulators listed in Chapter XI. Essential ingredients include the aforementioned antioxidant compounds and benzyl alcohol, which is commonly used as a development accelerator in developers for color paper films (such as those described in U.S. Pat. No. 2,304,925). . The PH of the ready-to-use developer solution is adjusted by mixing a plurality of concentrated compositions (preferably water-containing liquid compositions) with water, one of which is acidic (e.g. a p-phenylenediamine compound). ) and the other is basic. normal PH
The value is usually between 10 and 11.50, depending on the film (positive, negative, photographic paper and reversal film) and developer used. The production of aqueous solutions of p-phenylenediamine developers and additional components from concentrated compositions that are readily miscible with water and stable under various storage conditions is important to the color photoprocessing chemistry market ( As far as p-phenylenediamine compounds are concerned, stability issues are of particular importance). Only one part of the developer solution itself
Since it is not possible to make one concentrated composition (due to solubility and stability issues), it is best to separate the developer into various component groups, prepare them, and mix them in water to produce a ready-to-use bath. It has become a common practice in this field. Such components or compositions generally include one or more components of the developer bath in liquid or solid state. The following two points are important requirements for these compositions. Firstly, the composition must be in as small a quantity as possible, and secondly, it must be stable to various conditions of transport and storage. A third desired requirement of the composition is that it be liquid and easily miscible in water without prolonged stirring. It is particularly desirable in the market to formulate a developer into a manufactured concentrated composition that satisfies the first and second requirements above as well as the third requirement. Many experimental studies have been carried out in the past, but results as satisfactory as desired have not been achieved. A developer composition is described, for example, in U.S. Pat. No. 3,615,572, which consists of four compositions: p--
The composition comprises a first composition comprising a phenylenediamine developer, a second composition comprising hydroxylamine sulfate, a third composition comprising an alkali and a buffer, and a fourth composition comprising benzyl alcohol. Developers prepared as multiple concentrated compositions are
It is further described, for example, in US Pat. No. 3,814,606. Such developers include a first concentrated composition containing benzyl alcohol, diethylene glycol, hydroxylamine hydrochloride and water, a second concentrated composition containing an alkali and a buffer in water, a dry powder containing sulfites or in an acidic aqueous solution. and a third concentrated composition comprising a color developer. All of these prepared developers have at least one of the following drawbacks: a) The number of concentrated compositions is too high; b) The concentrated compositions are not easily miscible with water; c) Colored p-phenylenediamine When containing the compound, the concentrated composition is not very stable under all storage conditions on the market. Prepared developer compositions consisting of two components are described, for example, in inter alia US Pat. No. 3,574,619. Compositions of this type usually include water, benzyl alcohol, ethylene glycol, silver halide,
The first composition includes a p-phenylenediamine developer and a sulfite, and the second composition includes a hydrous alkali. However, this developer composition suffers from problems such as a) formation of turbidity during the addition of benzyl alcohol to an aqueous solution of color developer and sulfite, and b) deterioration of the developer when the composition is stored at high temperatures. It has its drawbacks. A primary object of the present invention is to provide a method for preparing color photographic developers as multiple liquid concentrate compositions that are stable and rapidly miscible in water. It is an object of the present invention, inter alia, to provide a method for preparing color photographic developers as minimally liquid concentrated compositions that are stable and rapidly miscible with water. Furthermore, it is an object of the present invention to provide a developer formulated as a multi-liquid concentrate composition that is stable and readily miscible with water. A special object of the invention is to
It is an object to provide a developer formulated as a composition of minimal, preferably two, liquid concentrates that is stable and rapidly miscible with water. According to the invention, the above objects can be achieved by preparing the entire or major part of the color photographic developer as at least two liquid concentrate compositions, the first of which is substantially a p-phenylenediamine color developer dissolved in a substantially water-free organic solvent to form a substantially water-free solution, the second composition consisting essentially of an aqueous alkaline solution. According to the present invention, in fact, any ready-to-use developer containing a p-phenylenediamine compound and other components known in the literature can be developed as a small number of concentrated compositions that are stable and rapidly miscible with water. It was found that it was possible to produce a drug. The developer usually contains a p-phenylenediamine compound, the exact chemical structure of which depends on the film to be developed. For example (as seen on the market), a developer bath for color positive film has 2-
Amino-5-diethylaminotoluene hydrochloride (commonly referred to as CD2) is used, and 4-amino-N-
Ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate (generally referred to as CD3) is used in the developing bath for color negative films, and 4-amino-3-methyl -N-ethyl-N-(β-hydroxyethyl)-aniline sulfate (commonly referred to as CD4)
is used. The antioxidants contained in the developer and mixed at least in part with the concentrated composition containing the p-phenylenediamine compound include all antioxidants known in the literature and specifically used for this purpose, e.g. Alkali metal sulfites and pyrosulfites and any sulfur compounds capable of giving rise to sulfite ions in aqueous solution, hydrazine and hydroxylamine salts, such as hydroxylamine sulfates and hydrochlorides, ascorbic acid, stereoisomers of ascorbic acid and dia Stereoisomers and their sugar derivatives, glycine, hydroxyacetone (compounds similar to those described in U.S. Pat. No. 3,615,503: commonly known as "acetol"), carbohydrazides, phenylhydrazides salts, such as phenylhydrazine sulfonic acid, phenoxyphenylhydrazine sulfonic acid, as well as compounds used primarily for different purposes, such as those commonly used as black-and-white developers (as antioxidant compounds due to their reducing properties). can also be used),
Sulfuric acid-p-methylaminophenol (methol)
and other substituted p-aminophenols, hydroquinone compounds and phenidones [LFA Mason, Photographic Processing Chemistry, Focal Press, p. 36 ( (1966)]. Some rules have been established in this field during the use of antioxidants of this type. It is mainly p
- Hydroxyamine compounds (if used) must not be included in the same concentrated (water-containing) composition containing phenylenediamine compounds (due to stability issues) and hydroxylamine compounds must not be used together with sulfite compounds. (due to problems with photosensitivity measurements). The first effect of the present invention is that hydroxylamine can be incorporated into a solution containing a p-phenylenediamine compound that contains almost no water, without causing any particular harmful effects. The effect is that the hydroxylamine itself is mixed with the sulfite and does not produce the significant harmful effects seen previously (the sulfite is first dissolved in an organic solvent and then sequentially mixed with the p-phenylenediamine compound). and hydroxylamine compounds are advantageously added under reduced pressure to absorb the SO ₂ formed). Furthermore, ascorbic acid and acetol are particularly effective when used in the water-free concentrated solutions of the invention, even when used in very low concentrations (ascorbic acid 0.015-5 g/t, especially 0.15-1.5 g/t). 1t
and acetol (0.3-10 g), it has been found that sulfites can be usefully substituted as antioxidants for use with p-phenylenediamine compounds. Mixtures of p-phenylenediamine compounds with hydroxylamine and ascorbic acid and/or acetol have been found to be particularly useful in obtaining highly stable concentrated compositions according to the invention. Also, of course, if hydroxylamine is deemed necessary but should be avoided in combination with the p-phenylenediamine compound in the same concentrated composition, it may be used in water with the alkaline aqueous composition according to the invention. In the concentrated organic composition to be mixed, sulfites (or ascorbic acid or other antioxidants) can be added together with the p-phenylenediamine compound, and the third concentrated composition (in an organic solvent or in water, especially The hydroxylamine may be present in an organic solvent (which may contain additional components of the developer). In fact, it has been found very easy to mix various developer components, both inorganic and organic, with water for the purposes of the present invention. For the purposes of the present invention, the organic solvent selected must be neutral and readily and completely miscible with water in all proportions. Additionally, it is important that no products react with the developing composition or any components of the photographic film to produce products that have deleterious effects on the photograph. The organic solvent selected must also dissolve the p-phenylenediamine acid addition salt and other salts in the absence of water. Among various known organic solvents such as ethylene glycol, methanol, dioxane, ethylene glycol monomethyl ether, formamide, dimethylformamide, methyl sulfoxide and acetonitrile, those well known as non-toxic substances in color photography were selected. Preferred organic solvents are therefore selected from the class of dihydric alcohols (e.g. ethylene glycol or trimethylene glycol), polyhydric alcohols (e.g. glycerin) and polyoxyethyl glycols (e.g. diethylene glycol or triethylene glycol) or mixtures thereof. can do. Such solvents are indeed capable of dissolving the acid addition salt of the p-phenylenediamine compound and some additional components of the developer in amounts sufficient for the purposes of the present invention and do not exhibit any harmful properties. . For the purposes of this invention, the solution in the selected organic solvent must be a substantially water-free solution, with a total percentage of water being 5% of the total volume of the solution.
Must not exceed. Experiments have shown that concentrated organic compositions containing p-phenylenediamine compounds according to the invention are not stable at certain storage conditions (conditions commonly found in the market) when their water content is higher than 5% of the total volume of the solution. It was proven by. As a result of this storage stability, concentrated compositions darken and precipitate, degrading the performance of the finished developer bath and producing significant amounts of oily material that is insoluble in such a bath ready for use. Therefore, the composition should contain as little water as possible. The maximum amount is 5%
However, it is advantageous if water is present in an amount of less than 3%. Therefore, the present invention provides a liquid composition in which the first concentrated composition is substantially free of water and contains a p-phenylenediamine compound dissolved in an organic solvent, and the second composition is a liquid composition containing at least an alkaline water-containing compound. The present invention relates to a color photographic developer prepared as a stable, water-mixing, multi-concentrate composition characterized in that it comprises two liquid concentrate compositions. The present invention
Furthermore, with respect to the above-mentioned prepared developer, wherein the substantially water-free liquid composition comprising a p-phenylenediamine compound also comprises an antioxidant, such an antioxidant may in particular be a sulphite (ion-releasing) compound, or a hydroxylamine compound, or an ascorbic acid compound or acetol, or a mixture of two or more thereof, especially a mixture of hydroxylamine and a sulfite, or a mixture of hydroxylamine and ascorbic acid or acetol. In particular, the present invention preferably comprises a compound selected from p-phenylenediamine compounds, hydroxylamine compounds, benzyl alcohol and sulfite compounds, ascorbic acid compounds, acetol-type compounds, especially ascorbic acid, and is substantially free of water. It relates to said developer prepared as only two concentrated compositions, including liquid concentrated compositions. Furthermore, the present invention particularly provides three concentrated compositions comprising the first and second liquid compositions described above and a third liquid composition comprising a hydroxylamine compound dissolved in water or preferably an organic solvent. The present invention relates to the prepared developer. The organic solvent used for the purposes of the invention is advantageously selected from the class of dihydric alcohols, polyhydric alcohols and polyoxyethylene glycols or mixtures thereof, more preferably ethylene glycol. Second, the present invention relates to a method for preparing a color photographic developer as a concentrated composition by dissolving the components of the color developer in a plurality of liquid compositions. One of the compositions is obtained by dissolving it in a substantially water-free liquid composition. p used in the prepared color photographic developer of the present invention
- A liquid concentrate composition of a phenylenediamine compound is characterized in that the p-phenylenediamine compound is contained in an organic solution that is substantially free of water but is miscible with water. In a particular embodiment, the solution may contain one or more compounds selected from among hydroxylamine compounds, sulfite compounds, ascorbic acid compounds and acetol compounds as described above. Particularly and in an advantageous embodiment, the concentrate composition comprises benzyl alcohol. p-phenylenediamine compound, hydroxylamine compound,
Further advantageous are compositions comprising benzyl alcohol compounds and compounds selected from sulphite, ascorbic acid and acetol type compounds, especially ascorbic acid. Next, the present invention will be explained in detail based on examples.
The present invention is not limited to this. Example 1 Color paper developer components were formulated as the following liquid concentrate composition required to make ready-to-use developer replenisher 1: Composition A Ethylene glycol 50 ml Hydroxylamine hydrochloride 2.75 g Pyro Potassium sulfite 1g CD3 7g Optiblank AC,
Fluorescent brightener sold by Sigma in Italy] 2.5 g benzyl alcohol 18.3 ml Ingredients were added in the above order until the volume reached 77 ml.
Slowly and completely dissolved in ethylene glycol. Composition B Water 30 ml 35% KOH 7 ml Diethylene triaminopentaacetic acid 1.6 g Potassium pyrosulfite 1.45 g Potassium carbonate 32 g Example 2 The developer components for color photographic paper are as follows: It was formulated as a liquid concentrate composition as follows: Composition A Ethylene glycol 42 ml Benzyl alcohol 18.3 ml Hydroxylamine hydrochloride 2.75 g Sodium pyrosulfite 0.9 g CD3 7 g Optiblank AC 2.5 g Ingredients in the order given above, in a volume of 67.5 ml was gradually dissolved in ethylene glycol until completely dissolved. Composition B Same composition as described in Example 1. Example 3 Color paper developer components were formulated as the following liquid concentrate composition required to make ready-to-use developer replenisher 1: Composition A Ethylene glycol 30 ml Glycerin 5 ml Sodium pyrosulfite 0.9 g Benzyl alcohol 18.3ml Hydroxylamine hydrochloride 2.75g Optiblank AC 2.5g CD3 7g Add the ingredients in the above order until the volume reaches 58ml.
gradually in ethylene glycol and glycerin,
Completely dissolved. Composition B Same composition as described in Example 1. Examples 4 to 8 Color paper developer components were formulated as two liquid concentrate compositions necessary to make ready-to-use developer replenisher 1, the first of which was an ethylene Composition A was the same as Example 2, except that instead of 42 ml of glycol, the following solvent was used:

Table Composition B of each example was the same as Composition B of Example 2. Example 9 Color paper developer components were formulated as two liquid concentrate compositions required to make ready-to-use developer replenisher 1: Composition A 20 ml of ethylene glycol and sodium sulfite.
Add a mixture of 1.2 g of hydroxylamine hydrochloride to a solution of 2.75 g of hydroxylamine hydrochloride in 20 ml of ethylene glycol, stir until a clear solution is obtained, and add the ingredients below in the order listed until the final volume is 65 ml. Gradually, completely dissolve and prepare: Benzyl Alcohol 18.3 ml Optiblank AC 2.5 g CD3 7 g Composition B Same composition as described in Example 1. Example 10 Color paper developer components were formulated into two liquid concentrate compositions required to make ready-to-use developer replenisher 1: Composition A Ethylene Glycol 42ml Optiblank AC 2.5g Benzyl alcohol 18.3 ml Sodium pyrosulfite 0.9 g CD3 7 g Hydroxylamine hydrochloride 2.75 g Ingredients were dissolved in the order listed slowly and completely until a final solution of 67.5 ml was obtained. Composition B Water 24 ml 35% KOH 8 ml Diethylenetriaminopentaacetic acid 1.6 g Diaminopropanoltetraacetic acid 1.5 g Potassium pyrosulfite 1.45 g Potassium carbonate 32 g Example 11 Developer components for color photographic paper were added to developer replenisher 1, which can be used immediately. Formulated as two liquid concentrate compositions required to make: Composition A Ethylene Glycol 42ml Optiblank AC 2.5g Benzyl Alcohol 18.3ml Ascorbic Acid 0.05g CD3 7g Hydroxylamine Hydrochloride 2.75g Ingredients listed in order was gradually and completely dissolved in ethylene glycol until a final solution of 67.5 ml was obtained. Composition B Water 24ml 35% KOH 8.8ml Diethylenetriaminopentaacetic acid 1.6g Diaminopropanoltetraacetic acid 1.5g Potassium pyrosulfite 2g Potassium carbonate 32g Example 12 The composition of Example 11 except that the first composition uses only 0.028g ascorbic acid. The color paper developer components were formulated as two liquid concentrate compositions, one the same as Composition B of Example 11, and the second composition the same as Composition B of Example 11. The amounts of both compositions were sufficient to produce a ready-to-use developer replenisher 1. Examples 13 to 18 Color photographic paper developer components were formulated as two liquid concentrate compositions, except that the first composition used the following compounds in place of ascorbic acid: Example 11
Composition A was the same as:

TABLE The second composition was in all examples the same as composition B of Example 11, and the amounts of both compositions in each example were sufficient to produce a ready-to-use developer replenisher 1. Example 19 Color paper developer components were formulated into three liquid concentrate compositions required to produce ready-to-use developer replenisher 1: Composition A Ethylene glycol 20.5 ml Hydroxylamine hydrochloride 2.75 g Optiblank AC 2.5g The final volume was 25ml. Composition B Ethylene glycol 28ml Benzyl alcohol 18.3ml Sodium pyrosulfite 0.9g CD3 7g Final volume was 50ml. Composition C Same composition as composition B of Example 10. Example 20 Color paper developer components were formulated as three liquid concentrate compositions required to obtain ready-to-use developer replenisher 1: Composition A Ethylene glycol 10 ml Hydroxylamine hydrochloride 2.75 g Final The capacity was 11.8ml. Composition B Ethylene glycol 42ml Optiblank AC 2.5g Benzyl alcohol 18.3ml Sodium pyrosulfite 0.9g CD3 7g The final volume was 67ml. Composition C Same composition as composition B of Example 10. Example 21 Color photographic negative developer components were formulated into two liquid concentrate compositions necessary to produce a ready-to-use developer replenisher 1. Composition A Ethylene glycol 70ml Hydroxylamine hydrochloride 1.5g Sodium pyrosulfite 5g CD4 5.3g The ingredients were slowly and completely dissolved in ethylene glycol in the order listed to give a final solution of 76ml. Composition B Water 56ml Diethylenetriaminopentaacetic acid 2.57g Potassium carbonate 35g Sodium sulfite 4.7g Potassium bromide 1.1g Potassium chloride 0.3g Potassium carbonate 3.8g Examples 22 to 26 Developer components for color photographic negatives were prepared in the same manner as in Example 21. Formulated as two liquid concentrate compositions, the first composition was the same as Composition A of Example 21, except that instead of 50 ml of ethylene glycol and 1 g of sodium pyrosulfite, the following materials were used:

[Table] The second composition was the same as composition B of Example 21. The amounts of both compositions in each example are such that a ready-to-use developer replenisher 1 can be produced. Example 27 Color photographic negative developer components were formulated as two liquid concentrate compositions in quantities to produce ready-to-use developer replenisher 1: Composition A Ethylene glycol 50 ml Ascorbic acid 0.1 g CD4 5.3 g Hydroxylamine Hydrochloride 3g The ingredients were slowly and completely dissolved in ethylene glycol in the order listed to a final volume of 56ml. Composition B Same composition as Composition B of Example 21. Example 28 A ready-to-use developer replenisher 1 for color photographic paper was prepared in the following manner: A quantity of a liquid concentrate composition containing developer components was added to
While constantly stirring at a constant speed, they were added sequentially to 800 ml of water necessary to obtain developer replenisher 1 that could be used immediately, and the time required to obtain a clear solution between each addition was measured. : Liquid concentrate compositions of Examples 1 to 18 using water at three different temperatures, namely 20°C, 30°C and 40°C, with volumes comparable to those of commercially available color photographic paper developer liquid concentrate compositions. The tests were repeated using the same amount of developer replenisher 1, the amount of which in all cases resulted in a ready-to-use developer replenisher 1. It has been found that the mixing times for the concentrated compositions of the present invention are generally better than the mixing times for similar known compositions. In the following, data according to examples of the invention are presented in detail in comparison with known compositions existing on the photographic market.

【table】

TABLE The liquid concentrate compositions of Examples 1 to 27 were used to prepare developer replenisher solutions. Such developer was used to replenish the operating solution contained in the processing agent tank, thereby developing color photographic paper. Such an operating solution consists of 80% of the same concentrated composition used to obtain the developer replenisher and the required amount of inorganic antifoggant (in the case of color paper developers)
KBr0.6g, for color negative developer
0.48 g of KBr and 0.02 g of KI) in water (to 1). Example 29 For color photographic paper, the liquid concentrate compositions of Examples 1 to 18 and then the alkaline liquid concentrate composition B of each example and 0.6 g of KBr were poured into a predetermined amount of water to a final volume of 1. A ready-to-use photographic developer solution was obtained. Samples of 3M color print photographic paper were exposed and processed in the following order. Development 3 minutes 30 seconds at 32.8°C Bleach-fixing 1 minute 30 seconds at 32.8°C Washing 3 minutes 30 seconds at 32.8°C Drying at 100°C The photographic results using 40.4 ml of composition B, fresh and stored A) are shown in the table below.

【table】

[Table] Example 30 The liquid concentrate compositions of Examples 19 and 20 were added by 20%
Immediate use for color photographic paper by pouring successively 20% less volume of each liquid concentrate composition and 0.6 g of KBr into the specified volume of water to a final volume of 1. A liquid photographic developing solution was prepared. Samples of 3M Color Print Photographic Paper were exposed and processed in the same order as Example 29. The following were prepared from the same liquid concentrate composition, but
The results are shown using a developer solution compared to a developer solution held at high temperature for a certain period of time.

[Table] Example 31 Liquid concentrate compositions A of Examples 21 to 27 were added in a 20% smaller volume, and then each liquid concentrate composition B was added in turn.
A ready-to-use photographic developer solution for color photographic negatives was prepared by pouring 0.4 g of KBr and 0.02 g of KI into a predetermined volume of water to a final volume of 1 in a 20% smaller volume. 3M Color Negative, Color Photographic Negative samples were exposed and processed in the following order: Development 3 minutes 15 seconds at 38°C Bleaching 6 minutes 30 seconds at 38°C Washing 3 minutes 15 seconds at 38°C Fixing 6 minutes at 38°C minutes 30 seconds Washing 3 minutes 15 seconds at 38°C Stabilization 1 minute 30 seconds at 38°C The following was prepared from the same liquid concentrate composition:
The results are shown using a developer solution compared to a developer solution held at high temperature for a certain period of time.

TABLE The amount of solid components present in the concentrated developer compositions according to the invention is as high as possible depending on their nature and the nature and amount of the organic solvent used to dissolve them. Advantageously, the amount is from 5 to 50 g, more preferably from 15 to 30 g per 100 ml of solution. The proportions of the various ingredients in the concentrate composition itself are those conventional in the art, unless otherwise stated in the specification. For example, this is true in the case of sulfite compounds, which have p-
0.05 to 2.0 per mole of phenylenediamine developer
It can be added in molar amounts, in particular from 0.10 to 0.5 molar (calculated as sulphite ions).

Claims (1)

[Claims] 1. The first concentrated composition is substantially free of water and has p.
- a liquid composition comprising a phenylenediamine compound dissolved in an organic solvent, the second composition being an alkaline water-containing composition; A color photographic developer prepared as a composition. 2 the first concentrated composition is substantially free of water;
The liquid composition of claim 1, which is a liquid composition containing a p-phenylenediamine compound and an antioxidant dissolved in an organic solvent, prepared as a plurality of concentrated compositions so as to be rapidly miscible with water. Color photographic developer. 3. Prepared as a plurality of concentrated compositions so as to be rapidly miscible with water according to claim 1 or 2, wherein the first concentrated composition contains a sulfite compound as an antioxidant. Color photographic developer. 4. Claim 1, wherein the first concentrated composition comprises a hydroxylamine compound as an antioxidant.
A color photographic developer according to items 1 to 3, prepared as a plurality of concentrated compositions so as to be rapidly miscible with water. 5. The color photographic developer according to claim 1, wherein the first concentrated composition contains an ascorbic acid compound as an antioxidant. 6. Claims 1 to 5, which contain a sulfite compound both in the first liquid composition that does not substantially contain water and in the second water-containing liquid composition. Color photographic developer. 7. Claims 1 to 6 include a third liquid concentrate composition containing a hydroxylamine compound.
The color photographic developer according to item 1. 8. A color photographic developer according to claim 6 or 7, wherein the third liquid concentrated composition comprises a hydroxylamine compound dissolved in an organic solvent substantially free of water. 9. A color photographic developer according to any one of claims 1 to 5, which is prepared simply as a two-part liquid concentrated composition. 10. The color photographic developer according to claim 9, which contains ascorbic acid in the first liquid concentrated composition substantially free of water and contains a sulfite compound in the second liquid concentrated composition. . 11. The color photographic developer according to any one of claims 1 to 10, wherein the organic solvent is selected from the group consisting of dihydric alcohols, polyhydric alcohols, polyoxyethylene glycols, or mixtures thereof. 12. The color photographic developer according to claim 11, wherein the organic solvent is ethylene glycol. 13. The color photograph according to Claims 1 to 12-1, wherein the p-phenylenediamine compound is 4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine. developer. 14 Claim 1, wherein the p-phenylenediamine compound is associated with benzyl alcohol in the same liquid concentrate composition substantially free of water.
The color photographic developer according to items 1 to 13. 15 One of the compositions is obtained by dissolving the p-phenylenediamine compound in an organic solvent to form a liquid composition substantially free of water, wherein the first concentrated composition is characterized in that the first concentrated composition is water-free. A plurality of liquid compositions comprising at least two liquid concentrate compositions, the second composition being an alkaline water-containing composition. A method for preparing a color photographic developer prepared as a concentrated composition of seeds.