JP2003050450A - Color developing concentrated composition and photographic processing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color developing concentrated composition that suppresses deterioration of the liquid composition due to storage at a high temperature, prevents interfacial precipitation in a processing tank when used as a replenisher solution and prevents contamination of a processed photosensitive material and to provide a photographic processing method using the composition. SOLUTION: (1) The color developing concentrated composition has pH 9-14 and comprises >=0.10 mol/l color developing agent, a chelate having a specified structure, at least one alkali agent, an antioxidant and a water-soluble organic solvent, and (2) the composition contains at least one of compounds (group A) whose pKa is 9.0 to <11.0 and at least one of compounds (group B) whose pKa is 11.0 to <13.0 in a (group A) to (group B) molar concentration ratio of >=1.2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a concentrated color-development composition and a method for processing a silver halide color photographic light-sensitive material (hereinafter also referred to as light-sensitive material or light-sensitive material) using the same. Of a color developing concentrated composition and a photographic material using the same, in which deterioration of the liquid component due to storage of the composition is improved, interface precipitation in the processing tank is prevented when used as a replenishing solution, and contamination of the processed light-sensitive material is improved. Regarding processing method.

[0002]

BACKGROUND OF THE INVENTION Color developing compositions are used to process color photographic materials such as color photographic films and papers that provide the desired images. Such a composition is
Generally, it contains a color developing agent, such as 4-amino-3-methyl-N- (2-methanesulfonamidoethyl) aniline, as a reducing agent and reacts with a color-forming coupler to produce the desired dye. U.S. Pat. No. 4,892,80
No. 4, No. 4,876, 174, No. 5, 354, 646
And No. 5,660,974 describe various color developing compositions.

A "color development replenishing solution" is added to the color developing solution in the processing tank in order to replenish the processing solution components which are consumed during the reaction or are brought out by the material to be processed. Such replenishment is designed to maintain uniform development and stability of the color developing agent.

Color developers are usually supplied to users in the form of three or more "parts" (or solutions) which are mixed just before use. Separation often comes in multiple parts to maintain the chemical activity and solubility of the components, otherwise they deteriorate when stored together under alkaline conditions for long periods without separation. Or they will react with each other. For example, one part contains a color developing agent, another part contains a material for maintaining alkalinity, and another part contains an optical brightener or the like. A uniform color developer can usually be obtained by mixing all parts with water.

In the photographic industry, the preparation of color developers, especially
There is a desire to reduce the number of parts used to prepare the replenisher. ready to use type solution,
Concentrates or powder formulations and the like are commercially available in the art. For example, European Patent Application Publication No. 079314.
No. 1 describes a two part color developing composition that can be supplied in either solid or liquid form.

In order to provide optimum processing performance, it is generally known that the concentrations of processing liquid components in photographic processing tanks must be maintained within certain ranges. The most important solvent in such photographic processing is water. Solubility in water is important for both inorganic and organic salts.

Although the ready-to-use type solution is convenient to use, it contains a large amount of water because all the components have the intended concentrations, and the cost for manufacturing, transportation and storage is high.

Therefore, in the photographic industry, manufacturers and users provide photographic processing compositions (including color developing compositions) in concentrated form so that large amounts of water need not be expensive to transport or store. And tend to be usable in smaller containers. Further, the photographic industry does not require the various components to be mixed (thus reducing mixing errors) and is ready to use (eg, known as an "auto replenishment" processor) out of the container. Request.

When comparing liquid concentrates with solid mixtures (eg powders and tablets), liquid concentrates are convenient to use, but packaging costs are high compared to powders. On the other hand, although the powder can be highly concentrated, it is difficult to supply a stable powder for each photographic drug composition. In addition, powders have the problems of dust, the need for separate packaging, and cumbersome metering or mixing operations, and require much effort and time to dissolve into a homogeneous solution.

Another concentrated form known in the art is, for example, European Patent Application Publication 020437.
2 and 0800111,
It is a drug paste or slurry. These formulations have yet another drawback, namely lack of homogeneity or slow dissolution rate of solid components.

While all of the conventional "multi-part types" used to provide color developing compositions are easy to combine and tend to form homogeneous, single-part compositions, in concentrated form, The interaction and deterioration between the photographic chemicals is large, and the effect on the photographic material to be processed is not preferable because it causes deterioration of the image quality.

Single-part formulations of color developing compositions that overcome the above problems are commercially available, but should they be stirred well before use due to the presence of precipitates (eg in a slurry) or multiple solvent phases? Need to mix. Therefore, a suitable device is needed to stir the multi-phase composition well.

There is an ongoing need in the photographic industry for a homogeneous, concentrated and stable single piece color developing concentrate composition. Such concentrated compositions not only reduce the cost of transporting and storing solutions diluted with large amounts of water,
Eliminating the need to mix multiple parts or agitate the multi-phase composition, providing an attractive product to the user.

As a technique for satisfying this need, Japanese Patent No. 3150131 was previously proposed. This prior proposed technique is homogeneous and has a pH of 7 to 13 and (a) at least 0.06 mol / mol of the color developing agent in the free base form.
L, (b) at least 0.05 mol / L of an antioxidant for the color developing agent, (c) water, (d) molecular weight 50 to
200, with a water to solvent weight ratio of 15:85 to 50:
Provided as a concentrate at a concentration such that it is photographic inactive for the free base form of the color developing agent,
A single color developing concentrate comprising a water-miscible or water-soluble hydroxy-containing, linear organic solvent, and (e) a buffer miscible with the organic solvent.

As another prior proposal technique for satisfying the above needs, Japanese Patent Laid-Open No. 2001-100382 is known. This technique is a one-part product containing at least one color developing substance, at least one antioxidant, at least one water quality adjusting agent, a buffer system, an alkali, and a sulfate ion of 0.1 mol / L or less. (One-par
t) A concentrated color developing solution, which is a multi-phase, especially two-phase, concentrated one.

The above-mentioned two previously proposed techniques are effective for precipitating property at low temperature storage, but have a problem of deterioration of liquid composition due to storage at high temperature. It was found that precipitation occurs, tar is likely to adhere when the light-sensitive material is actually processed, and the white background performance is deteriorated.

[0017]

Therefore, the present invention suppresses the deterioration of the liquid composition due to storage at high temperature, and prevents the precipitation of the interface of the processing tank and the contamination of the processed light-sensitive material when used as a replenisher. Provided are a concentrated developer composition and a photographic processing method using the same.

[0018]

The present invention for solving the above problems has the following constitution. 1. It has a pH of 9 to 14, contains 0.10 mol / L or more of a color developing agent, and has the following general formulas [AI] and [AI]
I], at least one of the compounds represented by [A-III]
A color-developing concentrated composition containing a seed and containing at least one alkali agent, antioxidant, and water-soluble organic solvent.

[0019]

[Chemical 9]

[In the formula, A ₁₁ , A ₁₂ , A ₁₃ and A ₁₄ each represent —CH ₂ OH, —PO ₃ (M ₆ ) ₂ or —COOM _7, and they may be the same or different. Good. M ₆ and M ₇ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. n represents an integer of 1 to 6, B ₁ and B ₂ may be the same or different,
Each represents an alkylene group having 1 to 5 carbon atoms. ]

[0021]

[Chemical 10]

[Wherein, A ₂₁ , A ₂₂ , A ₂₃ and A ₂₄ each represent —CH ₂ OH, —COOM ¹ or —PO ₃ (M ² ) _{2 and} may be the same or different. Good. M ¹ and M ² represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. X ₁ is a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or-
Represents (B ₁₁ O) n ₅ −B ₁₂ −. n ₅ represents an integer of 1 to 6, and B ₁₁
And B ₁₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. n ₁ , n ₂ , n ₃ and n ₄
Represents an integer of 1 or more, and may be the same or different, and at least one is 2 or more. ]

[0023]

[Chemical 11]

[In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents a hydrogen atom, a hydroxyl group, —COOM ₃ , —PO ₃ (M ₄ ) ₂ , —CH ₂ COO
M _5, represents a -CH ₂ OH or a lower alkyl group. However,
At least one of A ₁ , A ₂ , A ₃ and A ₄ is —COO.
_{M 3, -PO 3 (M 4} ) ₂ or -CH ₂ COOM _5. M
₁ , M ₂ , M ₃ , M ₄ and M ₅ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. n ₇ represents an integer of 0 to 2. ] 2. The concentrated color developing composition as described in 1 above, which contains a compound represented by the general formula [AI]. 3. 3. The color developing concentrated composition as described in 1 or 2 above, wherein the antioxidant is a compound represented by the following general formula [I].

[0025]

[Chemical 12]

[In the formula, R represents a hydrogen atom or an alkyl group, L represents an alkylene group, and A represents a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group or an amino group which may be alkyl-substituted. ] 4.9.0 ≦ pKa <11.0 at least one compound (Group A) and at least 11.0 ≦ pKa <13.0 compound (Group B) at least one compound, and the molar concentration thereof The ratio of (A group) / (B group) ≧ 1.2, the concentrated color developing composition according to any one of 1 to 3 above. 5. 5. The color development concentrated composition as described in any one of 1 to 4 above, which contains at least one water-soluble nonionic surfactant represented by the following general formula [II] or [III].

[0027]

[Chemical 13]

In the formula, R ₂ represents an alkyl group having 1 or 2 carbon atoms or a hydrogen atom, and R ₃ represents a hydrogen atom or a hydroxyl group. p is an integer of 0 to 2, q is an integer of 1 to 3, r
Represents an integer of 1 to 3. A may be replaced by any hydrogen atom on the benzene ring. s represents an integer of 0 to 50, t represents an integer of 0 or 1, and u represents an integer of 10 to 150.

[0029]

[Chemical 14]

[In the formula, R is an alkyl group having 4 to 25 carbon atoms which may have a linear or branched substituent,

[0031]

[Chemical 15]

Or represents a hydrogen atom (provided that R ₁₁ and R
₁₂ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 represents an integer of 0 to 4). n ₈ and m each represent 0 or an integer of 1 to 200, but they do not become 0 at the same time. A and B are respectively

[0033]

[Chemical 16]

Represents the same and may be the same or different. However, n ₉ , m ₁ and l ₁ respectively represent 0, 1, 2 or 3, but n ₉ , m ₁ and l ₁ do not become 0 at the same time. D represents a hydrogen atom. ] 6. An imagewise exposed silver halide color photographic light-sensitive material is subjected to color development using a processing solution prepared by diluting the color development concentrated composition described in any one of 1 to 5 above at least 4 times, and then a desilvering step is performed. A method of processing a silver halide color photographic light-sensitive material, comprising:

Deterioration of liquid components due to storage at high temperature, which is a drawback of the two previously proposed techniques (Japanese Patent No. 3150131 and Japanese Patent Laid-Open No. 2001-100382), which have merits as the single (one part) color developing concentrated composition. The present inventor has solved the problems such as precipitation on the interface when a replenisher is prepared after storage, and easy adhesion of tar when the photosensitive material is actually processed and deterioration of white background performance. Succeeded and completed the present invention.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The general formula [A- used in the color developing concentrate composition of the present invention
I], [A-II] or [A-III] will be described.

First, the compound represented by the general formula [AI] will be described. In the formula, A _{11 to} A ₁₄ may be the same or different and each represents —CH ₂ OH, —PO ₃ (M ₆ ) ₂ or —COOM ₇ . M ₆ and M ₇ are each a hydrogen atom, an ammonium group, an alkali metal atom (for example, sodium,
Potassium) or an organic ammonium group (eg, methylammonium group, trimethylammonium group, etc.).
X is or alkylene group which may be substituted having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. B ₁ and B ₂ may be the same or different and each represents an optionally substituted alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group represented by X include ethylene, trimethylene, tetramethylene and the like. Further, examples of the alkylene group represented by B ₁ and B ₂ include methylene, ethylene, trimethylene and the like. Examples of the substituent of the alkylene group represented by X, B ₁ or B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.) and the like.
n represents an integer of 1 to 6, and preferably 1 to 4.

The preferred specific examples of the compounds represented by the above general formula [AI] are shown below, but the invention is not limited thereto.

[0039]

[Chemical 17]

[0040]

[Chemical 18]

The compound represented by the above general formula [AI] can be synthesized by a generally known method. Among these, particularly preferred compounds are (AI-1) and (AI)
-3) and (AI-14).

The compound represented by the general formula [A-II] will be described below. In the formula, A _{21 to} A _{24, which} may be the same or different, each represents —CH ₂ OH, —PO ₃ (M ² ) ₂ or —COOM ¹ . M ¹ and M ² represent a hydrogen atom, an ammonium group, an alkali metal atom (eg sodium, potassium etc.) or an organic ammonium group (eg a methylammonium group, a trimethylammonium group etc.).

X ₁ represents a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or — (B ₁₁ O) n ₅ B ₁₂ —. B ₁₁ and B ₁₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms (including a substituent). n _{1 to} n ₄ each represent an integer of 1 or more, which may be the same or different, and at least one is 2 or more. Examples of the alkylene group represented by X1 include ethylene, trimethylene and tetramethylene. Examples of the alkylene group represented by B ₁₁ and B ₁₂ include methylene, ethylene, trimethylene and the like. Examples of the substituent of the alkylene group represented by X ₁ , B ₁₁ or B ₁₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group). n ₅
Represents an integer of 1 to 6, preferably 1 to 4. Especially preferably, it is 1-2.

Preferred specific examples of the compound represented by the above general formula [A-II] are shown below, but the invention is not limited thereto.

[0045]

[Chemical 19]

[0046]

[Chemical 20]

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

The above (A-II-16) and (A-II-1)
7), (A-II-18), (A-II-19), (A-II
-20) includes both cis forms. The compound represented by the general formula [A-II] can be synthesized by a generally known method. Particularly preferred compounds among the specific examples are (A-II-1), (A-II-2) and (A-II-).
6).

The addition amount of the compounds represented by the above general formulas [AI] and [A-II] is at least a 4-fold dilution,
When used as a color developing replenisher, 0.0 per 1 liter
It is preferably in the range of 01 to 0.1 mol, and more preferably in the range of 0.005 to 0.05 mol.

Next, the compound represented by the above general formula [A-III] will be described. In the general formula [A-III], A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each is a hydrogen atom, a hydroxyl group or —COO.
_{M 3, -PO 3 (M 4} ) 2, -CH 2 COOM 5, -CH 2 O
H or a lower alkyl group (methyl group, ethyl group, isopropyl group, n-propyl group, etc.) is represented. However, A ₁ ,
At least one of A ₂ , A ₃ and A ₄ is —COOM ₃ , —P.
O ₃ (M _{4) 2} or -CH ₂ COOM _5. M ₁ , M ₂ ,
M ₃ , M ₄ and M ₅ each represent a hydrogen atom, a sodium atom, a potassium atom, a lithium atom, an ammonium group, an alkali metal atom or an organic ammonium group, more preferably a hydrogen atom, a sodium atom and a potassium atom. . n ₇ represents an integer of 0 to 2.

Preferred specific examples of the compound represented by the general formula [A-III] are shown below.

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

The compounds represented by the above general formula [A-III] are disclosed in JP-A Nos. 63-267750 and 63-26775.
No. 1, JP-A-2-115172, and JP-A-2-295954.
It can be synthesized by a general synthesis method described in the specification or the like.

The amount of the compound represented by the above-mentioned general formula [A-III] added is at least 4-fold, and when it is used as a color developing replenisher, 0.001 to 1
It is preferably in the range of 0.1 mol, and more preferably in the range of 0.005 to 0.05 mol.

The color developing concentrate compositions of this invention include one or more color developing agents that are well known in the art and that, in their oxidized form, will react with the dye-forming color coupler present in the material being processed. . Such color-developing agents are described in aminophenols, p-phenylenediamines (particularly N, N-dialkyl-p-phenylenediamines), and European Patent Application Publication Nos. 0434097 and 0530921. Well known in the art such as, but not limited to. It is also useful for the color developing agent to have one or more water solubilizing groups known in the art. Details of such materials can be found in Research Disclosure (Rese
arch Disclosure), publication 3895
7, pages 592-639 (September 1996). This document is referred to as "Research Disclosure"
Say.

Preferred color developing agents include N, N-diethyl-p-phenylenediamine sulfate (KODAK color developing agent CD-2), 4-amino-3-methyl-N-.
(2-methanesulfonamidoethyl) aniline sulfate,
4- (N-ethyl-N-β-hydroxyethylamino)
2-methylaniline sulfate (KODAK color developing agent CD-4), p-hydroxyethylethylaminoaminoaniline sulfate, 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesqui Sulfate (KODAK color developing agent CD-3), 4
-(N-Ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate, and those which are obvious to those skilled in the art, include, but are not limited to.

In the present invention, the amount of the color developing agent added is essentially 0.10 mol / L or more, preferably 0.2.
It is 0 mol / L or more.

In order to protect the color developing agent from oxidation, it is preferred to include one or more antioxidants in the color developing composition. Either inorganic or organic antioxidants can be used. Sulfites (eg sodium sulfite, potassium sulfite, sodium bisulfite and potassium metabisulfite), hydroxylamine (and their derivatives), hydrazines, hydrazides, amino acids,
Ascorbic acid (and their derivatives), hydroxamic acids, aminoketones, mono- and polysaccharides,
Many classes of useful antioxidants are known, including, but not limited to, mono and polyamines, quaternary ammonium salts, nitroxy radicals, alcohols and oximes. Further useful as antioxidants are the 1,4-cyclohexadiones. Mixtures of compounds of the same or different classes can also be used if desired.

Particularly useful antioxidants are, for example, US Pat. Nos. 4,892,804, 4,876,174,
Hydroxylamine derivatives as described in Nos. 5,354,646, 5,660,974, and 5,646,327. Many of these antioxidants are mono and dialkyl hydroxylamines having one or more substituents on both alkyl groups or on one alkyl group. Particularly useful alkyl substituents include
Included are sulfo, carboxy, amino, sulfonamide, carbonamido, hydroxy, and other solubilizing groups.

In the present invention, the antioxidant particularly preferably used is the compound represented by the above general formula [I]. This will be described below.

In the above general formula [I], L has 1 carbon atom.
10 represents a linear or branched alkylene group which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene, and propylene are mentioned as preferable examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group and an ammonio group which may be alkyl-substituted, and a carboxyl group, a sulfo group, a phosphono group and a hydroxyl group are preferred examples. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an alkyl-substituted amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, which is a carboxyl group, a sulfo group, a hydroxyl group, or a phosphono group. A group and a carbamoyl group which may be alkyl-substituted are preferred examples. 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, and carboxymethyl group. A group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group can be mentioned as particularly preferable examples.

R represents a hydrogen atom or an alkyl group,
The alkyl group may be substituted, and among them, a linear or branched alkyl group having 1 to 10 carbon atoms that may be substituted is preferable, and an alkyl group having 1 to 5 carbon atoms that may be substituted is preferable. More preferable. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group,
It represents a hydroxyl group, or an amino group which may be alkyl-substituted, an ammonio group, a carbamoyl group or a sulfamoyl group. There may be two or more substituents. Preferred examples of R include a hydrogen atom, 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, and a hydrogen atom and carboxymethyl group. A group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferable examples. L and R may combine to form a ring.

Typical examples of the compounds represented by the general formula [I] are shown below.

[0066]

[Chemical 25]

[0067]

[Chemical formula 26]

[0068]

[Chemical 27]

[0069]

[Chemical 28]

The amount of the compound represented by the general formula [I] added is 3.0 × 10 ⁻⁴ m when it is used as a color developing replenisher.
It is preferably contained in the range of ol / L to 1.0 × 10 ⁻¹ mol / L, and is in the range of 3.0 × 10 ⁻³ mol / L to 5.0 × 10 ⁻² mol / L. Is more preferable.

Suitable water-soluble solvents for the color developing concentrate composition according to the present invention are, for example, carboxylic acid amides and urea derivatives such as dimethylformamide, methylacetamide, dimethylacetamide, N, N'-dimethylurea, tetramethylurea, Methanesulfonamide, dimethylethylene urea, N-acetylglycine, N-valeramide, isovaleramide, N-butylamide, N,
N-dimethylbutyramide, N- (2-hydroxyphenyl) acetamide, N- (2-methoxyphenyl) acetamide, 2-pyrrolidinone, ε-caprolactam,
Acetanilide, benzamide, toluenesulfonamide, phthalimide; aliphatic and cyclic alcohols such as isopropanol, tert. -Butyl alcohol, cyclohexanol, cyclohexanemethanol,
1,4-cyclohexanedimethanol; aliphatic and cyclic polyalcohols such as glycols, polyglycols, polywaxes, trimethyl-1,6-hexanediol, glycerol, 1,1,1-trimethylolpropane, Pentaerythritol, sorbitol; aliphatic and cyclic ketones such as acetone, ethyl methyl ketone, diethyl ketone, tert. -Butyl methyl ketone, diisobutyl ketone, acetylacetone, acetonylacetone, cyclopentanone, acetophenol;
Aliphatic and cyclic carboxylic acid esters, such as trimethoxymethane, methyl acetate, allyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol diacetate, glycerol 1-acetate, glycerol diacetate, methylcyclohexyl acetate, methyl salicylate, phenyl salicylate Aliphatic and cyclic phosphonates,
For example, methylphosphonic acid dimethyl ester, allylphosphonic acid diethyl ester; aliphatic and cyclic oxyalcohols such as 4-hydroxy-4-methyl-2-pentanone, salicylaldehyde; aliphatic and cyclic aldehydes such as acetaldehyde, propanal , Trimethylacetaldehyde, crotonaldehyde, glutaraldehyde, 1,2,5,6-tetrahydrobenzaldehyde, benzaldehyde, benzenepropane, terephthalaldehyde; aliphatic and cyclic oximes such as butanone oxime, cyclohexanone oxime; aliphatic and cyclic amines Classes (primary, secondary or tertiary) such as ethylamine, diethylamine, triethylamine, dipropylamine, pyrrolidine, morpholine, 2-amino-pyriline. Jin, aliphatic and cyclic polyamines (primary, secondary or tertiary), such as ethylene diamine, 1-amino-2-diethylamino ethane,
Methyl-bis (2-methylaminoethyl) -amine, permethyldiethylenetriamine, 1,4-cyclohexanediamine, 1,4-benzenediamine; aliphatic and cyclic hydroxyamines such as ethanolamine, 2
-Methylethylamine, 2-methylaminoethanol,
2- (dimethylamino) ethanol, 2- (2-dimethylaminoethoxy) -ethanol, diethanolamine, N-methyldiethanolamine, triethanolamine, 2- (2-aminoethylamino) ethanol, triisopropanolamine, 2-amino- 2-hydroxymethyl-1,3-propanediol, 1-piperidine ethanol, 2-aminophenol, barbituric acid,
2- (4-aminophenoxy) -ethanol and 5-amino-1-naphthol.

The compound having a buffering capacity used in the concentrated color developing composition of the present invention has a pKa of 9.0 or more and 11.0.
Compounds less than (group A) include, for example:

[0073]       Compound pKa   4-phenol sulfonic acid 9.05   2-Aminoethylsulfonic acid 9.06   Alanine 9.10   4-aminopyridine 9.11.   Histidine 9.18   Serine 9.21   Boric acid 9.23   Ammonia 9.25   Pyrophosphoric acid 9.41   Ethanolamine 9.50   Ephedrine 9.54   Dimethylaminoethylamine 9.55   Hydroxyproline 9.66   2-Amino-2-methyl-1-propanol 9.69   Leucine 9.74

[0074]   Glycine 9.78   Trimethylamine 9.80   Piperazine 9.81   Ethylenediamine 9.93   1-aminopropan-3-ol 9.96   Aspartic acid 10.00   Phenol 10.00   β-alanine 10.24   Carbonic acid 10.33   CAPS (3- (cyclohexylamino)     Propane sulfonic acid 10.40   γ-aminobutyric acid 10.56   n-propylamine 10.57   Methylamine 10.62   Ethylamine 10.63   n-butylamine 10.64

[0075]   sec-Butylamine 10.64   Triethylamine 10.72   Dimethylamine 10.77   Diethylamine 10.93   Hexamethylenediamine 10.93   4-Acetyl-β-mercaptoisoleucine 10.30   1-aminocycloheptanecarboxylic acid 10.46   5-amino-N-phenylsulfonic acid 10.95   4-aminophenol 10.30   5-amino-N-valeic acid 10.77   Caffeine 10.4   Cis-cis-cyclohexanone-1,3,5-     Triamine 10.4   1,3-diamino-1-2-aminothymerp     Lopin 10.38   Dehydroascorbic acid 10.3   α, γ-diaminobutyric acid 10.4

N, N-diethylglycine 10.47 2,5-dihydroxybenzoic acid 10.50 2,3-dimethylcaptopropan-1-ol 10.58 2,4-dimethyl-8-hydroxyquinoline 10.60 ethyl Acetoacetate 10.68 Ethylenediaminetetraacetic acid 10.95 Ethylpyrrolidone 10.43 2,2'-Methylene-bis (4,5-dichlorophenol) 10.65 3-Methylpentane-2,4-dione 10.87 Murexide 10.50 L-proline 10.69 Examples of compounds (County B) having a pKa of 11.0 or more and less than 13.0 include the following.

[0077]   Piperidine 11.12   Phosphoric acid 12.33   Alizarin-3-sulfonic acid 11.01   Ascorbic acid 11.82   Betaine 12.16   t-Butyl hydroxide 12.80   Chrome Az Roll S 11.47   Cornyin 11.0   Cycloacetyl hydrazide 11.17   Diethyl piguanide 11.68   2,3-Dihydroxybenzoic acid 11.78   3,4-Dihydroxybenzoic acid 11.74   Erio Chrome Black T 11.55   Ethylene-N, N-diacetic acid 11.05   3-Ethylpentane-dione-2,4 11.34

[0078]   Glycoascorbic acid 11.58   Glucose 12.43   Glutamide 11.43   Guanyl ethyl urea 11.10   o-Hydroxybenzoic acid 12.38   2-hydroxypyridine 11.62   4-hydroxypyridine 11.09   Methylpiperazine 11.02   Nicotinic acid 11.0   Pyrocatechol 12.08   Pyrogallol 12.63   Resorcinol 12.32   Salicylaldoxime 12.11   Salicylic acid 12.38

[0079]   Spartine 11.76   5-sulfosalicylic acid 12.00   Toluhydroquinone 11.62   Tyrone 12.6   Xanthine 11.68   Sodium silicate     (Na2O · nSiO2n = 0.5 to 4)> 11.0

Needless to say, the present invention is not limited to the above compounds. In order to exert the effect of the present invention more, at least one compound having a pKa of 9.0 or more and less than 11.0 (preferably 9.5 to 10.7), and a pKa of 11.0 or more and less than 13.0 ( Preferably 11.
It suffices that at least one compound of 5-12.7) is included in combination, and any number of compounds may be used in combination.
Further, it may be used in the form of various salts such as Na salt and K salt.

Most preferably, in Group A, carbonic acid (pKa1
0.33), and phosphoric acid (pKa12.3 in group B).
3), salicylic acid (pKa12.38), 5-sulfosalicylic acid (pKa12.00), glucose (pKa1).
2.43). The amount used is not particularly limited,
In order to exert the effect of the present invention better, 0.01 to 1.0 m when one compound is used as a color developing replenisher.
It is more preferably used in the range of ol / L, and particularly preferably 0.03 to 0.5 mol / L.

The pKa values of the exemplified compounds are shown in "Selection of buffer and application of hydrogen ion / metal ion" (DD Perrin, B. Dempsey, translated by Keiichi Tsuji, Kodansha Scientific) and "Lange's Chemistry Handbook "(Lam
ge's Handbook of Chemistr
y, 11th Edition Edited byJ
ohn A. Dean. McCGRAW HILL B
OOK COMPANY, 1973).

In the present invention, the content molar ratio is (group A) /
(County B) ≧ 1.2. As a result, the effects of the present invention, particularly the concentrate storage stability and running performance, are excellent.

In the color developing concentrate composition of the present invention,
It is essential that the pH is 9 to 14, preferably pH.
It is in the range of 11.5 to 13.

Next, the general formula [II] will be described. R ₂ represents an alkyl group having 1 or 2 carbon atoms (for example, a methyl group, a methoxyethyl group, an ethyl group, etc.) or a hydrogen atom, and R ₃ represents a hydrogen atom or a hydroxyl group.
p represents an integer of 0 to 2, q represents an integer of 1 to 3, and r represents an integer of 1 to 3. A may be replaced by any hydrogen atom on the benzene ring. s is 0 to 50, t is an integer of 0 or 1, and u is 1.
It represents an integer of 0 to 150.

Preferred compounds represented by the general formula [II] of the present invention are as follows.

[0087]

[Chemical 29]

[0088]

[Chemical 30]

[0089]

[Chemical 31]

Among the above compounds, those which are particularly preferably used from the effects of the object of the present invention are II-1 and II.
-2, II-4, II-5, II-6, II-8, II
-13 and II-14 are mentioned.

Examples of the water-soluble surfactants preferably used in the present invention include the compounds represented by the above general formula [III], and specific examples include the following compounds, but the invention is not limited thereto. Not a thing.

[0092]

[Chemical 32]

[0093]

[Chemical 33]

The water-soluble surfactant used in the present invention can be contained in the color-development concentration composition by selecting at least one selected from the above examples, but it is also possible to include two or more kinds. When two or more kinds are used together, one kind selected from the above examples and a water-soluble surfactant other than the above may be used together.

The water-soluble surfactant used in the present invention is preferably in the range of 0.01 to 50 g / L when it is used as a color developing replenisher.

The color developing concentrate compositions of this invention comprise an imagewise exposed halogen comprising a support and one or more silver halide emulsion layers containing imagewise distributed developable silver halide emulsion grains. It has the utility of providing color development to silver halide photographic elements. A wide variety of photographic elements containing different types of emulsions (both color negative and color reversal films and papers, and color motion picture films and prints) can be processed using the present invention. These emulsion types are well known in the art (see Research Disclosure).

The present invention is particularly useful for processing high chloride (greater than 70 mole percent chloride, preferably greater than 90 mole percent chloride, based on silver) color photographic paper emulsions. Such color photographic papers can contain any useful amount of silver coated in one or more emulsion layers, and in some embodiments have low silver amounts (ie 0.8 g silver / g).
elements (less than m ² ) are processed using the present invention.

Color development of imagewise exposed silver halide photographic elements is carried out under suitable time and temperature conditions and in suitable processing equipment to produce the desired developed image in the color development processing prepared according to this invention. It is carried out by contacting with liquid. Then one or more of a development stop step, a bleach step, a fixing, a bleach / fix step, in a particular desired order as known in the art.
Additional processing can be performed using conventional procedures including, but not limited to, washing (or rinsing) steps, stabilizing steps and drying steps. Useful processing steps of various processing protocols, including conventional Process C-41 processing for color negative films, Process RA-4 for processing color papers, and Process E-6 for processing color reversal films, and their useful conditions. And materials are well known.

The processing time and temperature for each processing step of the present invention are generally those used in the art. For example, color development generally involves 20-6.
It is carried out at a temperature of 0 ° C. The preferred time for color development is 15
~ 250 seconds. For color paper processing, it is desirable that the color development time is shorter (for example, 45 seconds or less). At least 4 times the color developing concentrate composition of the present invention;
It can be appropriately diluted up to 12 times to prepare a working concentration solution or a replenisher. The dilution ratio is preferably 4 to 10 times, and water is usually used as the diluting liquid. It can be diluted during or before treatment.

In one embodiment of the present invention, the color developing concentrate composition is a photographic bleaching composition, a photographic bleaching / fixing composition,
One agent in a photoprocessing chemical kit that can include one or more other photoprocessing compositions (dry or liquid) including, but not limited to, a photofix composition, a photostabilizing or final rinse composition. It is a formulation. Such additional compositions can be formulated into concentrated or working strength solutions and provided in dry form (eg, powder or tablets).

[0101]

EXAMPLES The present invention will be illustrated below with reference to examples. Example 1 Color development concentrate composition for color paper The color developing concentrate composition of the present invention was prepared as follows.

DEG 400 g PEG4000 100 g Na salt of compound 1-7 0.3 mol CD-3 Stilbene-based optical brightener 15 g polystyrene sulfonic acid 10 g Compound 1 shown in table 1 0.2 mol II-4 compound 10 g K ₂ CO ₃ (A) 2.2 mol Potassium sulfosalicylate (B) 0.4 mol KOH, H ₂ SO _{4 The} pH was adjusted to the value shown in Table 1 and adjusted to 12
Water was added to make up to 00 ml.

The concentrated composition for color development was put in a closed container and stored in a thermostat at 50 ° C. for 2 months, and then the concentrated composition (1200 ml) was diluted with water to 10 L to prepare a replenisher.

This replenisher was placed in a polyethylene container having an opening area ratio of 0.15 cm ⁻¹ and stored at a thermostat of 30 ° C. for 1 month. The degree of precipitation on the container wall after storage and the CD-3 residual ratio, Colorability (450 nm) was evaluated.

Further, an actual running process of the light-sensitive material was carried out by using the replenishing solution after the storage.

The photosensitive material used was QA paper manufactured by Konica Corporation, and the automatic developing machine was a paper developing machine (CL-PP1801EA, E of NPS868SQA system manufactured by Konica Corporation).
B) was used. The processing conditions are shown below.

Process Treatment time Treatment temperature Replenishment amount Color development 22 seconds 39.8 ° C. 80 ml / m ² bleach-fix 22 seconds 37.0 ° C. 200 ml / m ² stable (3 tanks) 22 seconds × 3 38.0 ° C. 248 ml / m ^Two

The bleach-fixing solution is K-28P2R- manufactured by Konica.
02, and K-P3R-01 manufactured by Konica Corporation was used as the stabilizing solution. The starting solution for color development used was a solution prepared by diluting the color development concentrate (900 ml) with water and adding the following composition to a final volume of 15 L.

KHCO ₃ 150 g KCl 60 g Sulfuric acid was added to adjust the pH to 10.25. The running process was carried out for 5 m ^{2 of} color paper per day until the color development replenisher (10 L) was consumed.

At the end of the running process, the wedge-exposed photosensitive material was processed, and the minimum density part (DminY) and the maximum density part (DmaxY) were measured for yellow density. Further, the degree of adhesion of stains to the treated paper at the start of treatment on the last day of the running treatment was evaluated. The results are shown in Table 1.
Shown in.

There is no degree of crystal precipitation of the replenisher ◎ It is on a part of the wall but there is no problem level ○ There is precipitation on a part of the wall and the bottom △ Precipitation of the wall and the bottom is growing × Precipitation on the entire bottom surface Occurrence of XX Degree of dirt adhesion ... At the start of processing, unexposed L size (1
(27 mm × 89 mm) was continuously treated and evaluated by the number of sheets until the stain was not visually observed on the print surface.

[0112]

[Table 1]

EDTA = ethylenediaminetetraacetic acid DTPA = diethylenetriamine pentaacetic acid HEDP = 1-hydroxyethylidene-1,1-diphosphonic acid DETAPH = diethylenetriaminepentaphosphonic acid

From the results shown in Table 1, the combination of the compounds of the present invention, the precipitability after storage at high temperature and the CD-3 residual rate,
It is clear that the running processing performance is excellent.
Further, it is understood that pH is 9.0 or more is essential and 11.5 or more is a more preferable region. Further, it is understood that the compound represented by AI is preferable as the compound. Further, it is understood that the added amount of CD-3 is essentially 0.10 mol / L or more, and more preferably 0.20 mol / L or more.

Example 2 Experiment No. 1 of Example 1 11, N of compound 1-7
The same experiment was conducted except that the salt a was changed to the compound shown in Table 2 and the storage period of the 50 ° C. thermostat was changed to 3 months. The results are shown in Table 2.

[0116]

[Table 2]

DEHA = diethylhydroxylamine HAS = hydroxylamine sulfate DMHA = dimethoxyethylhydroxylamine oxalate

In addition to the constitution of the present invention, it is found that the compound of the general formula [I] is preferably used as the antioxidant.

Example 3 Experiment No. 1 of Example 1 In 11 potassium carbonate (A)
The same experiment was performed except that the addition amount and composition of potassium sulfosalicylate (B) and the composition were changed as shown in Table 3 and the storage period of the 50 ° C. thermostat was changed to 3 months. The results are shown in Table 3.

[0120]

[Table 3]

In order to achieve the effect of the present invention better,
At least one compound of 9.0 ≦ pKa <11.0 (group A) and a compound of 11.0 ≦ pKa <13.0 (B
It can be seen that it is desirable that at least one of the (group) is contained and the contained molar ratio is (A) group / (B) group ≧ 1.2.

Example 4 A similar experiment was conducted, except that the compound II-4 used in Example 1 was changed to the compound shown in Table 4 and the storage period at 50 ° C. thermostat was 3 months. It was The results are shown in Table 4.

[0123]

[Table 4]

It is apparent that the present invention becomes more effective by using the water-soluble nonionic surfactants represented by the general formulas [II] and [III].

[0125]

EFFECT OF THE INVENTION The present invention is a concentrated color developing composition which can prevent deterioration of the liquid composition due to storage at high temperature, prevent precipitation at the processing tank interface and prevent contamination of the processed light-sensitive material when used as a replenisher. It is possible to provide a photographic processing method using.

Claims (6)

[Claims] 1. A dye having a pH of 9 to 14 and containing 0.10 mol / L or more of a color developing agent and having the following general formula [AI]:
A color development concentrated composition containing at least one compound represented by [A-II] or [A-III] and containing at least one alkali agent, antioxidant and water-soluble organic solvent. [Chemical 1] [Wherein A ₁₁ , A ₁₂ , A ₁₃ and A ₁₄ are each —CH ₂ OH, —
It represents PO ₃ (M ₆ ) ₂ or —COOM _7, and may be the same or different. M ₆ and M ₇ are hydrogen atoms,
It represents an ammonium group, an alkali metal atom or an organic ammonium group. X is an alkylene group having 2 to 6 carbon atoms or-(B
₁ O) n-B ₂ - represents a. n represents an integer of 1 to 6, B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ] [Chemical 2] [In the formula, A ₂₁ , A ₂₂ , A ₂₃ and A ₂₄ are —CH ₂ OH and —C, respectively.
Represents OOM ¹ or —PO ₃ (M ² ) ₂ and may be the same or different. M ¹ and M ² represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group.
X ₁ is a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or — (B ₁₁ O) n ₅ —
Represents B ₁₂ −. n ₅ represents an integer of 1 to 6, B ₁₁ and B ₁₂ may be the same or different and each has 1 carbon atom.
Represents the alkylene group of ~ 5. n ₁ , n ₂ , n ₃ and n ₄ represent integers of 1 or more, and may be the same or different, and at least one is 2 or more. ] [Chemical 3] [In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each is a hydrogen atom, a hydroxyl group, —COOM ₃ , —PO ₃ (M ₄ ) ₂ , —CH. ₂ COO
M _5, represents a -CH ₂ OH or a lower alkyl group. However,
At least one of A ₁ , A ₂ , A ₃ and A ₄ is —COO.
_{M 3, -PO 3 (M 4} ) ₂ or -CH ₂ COOM _5. M
₁ , M ₂ , M ₃ , M ₄ and M ₅ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. n ₇ represents an integer of 0 to 2. ] 2. A color-developing concentrated composition according to claim 1, which contains the compound represented by the general formula [AI]. 3. The color developing concentrate composition according to claim 1, wherein the antioxidant is a compound represented by the following general formula [I]. [Chemical 4] [In the formula, R represents a hydrogen atom or an alkyl group, L represents an alkylene group, and A represents a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group or an amino group which may be alkyl-substituted. ] 4. A compound of 9.0 ≦ pKa <11.0 (A
Group) and at least 11.0 ≦ pKa <13.0
4. At least one compound (group B) according to claim 1, wherein the molar concentration ratio is (group A) / (group B) ≧ 1.2. The color development concentrated composition of. 5. The color development concentrated composition according to claim 1, which contains at least one water-soluble nonionic surfactant represented by the following general formula [II] or [III]. [Chemical 5] In the formula, R ₂ represents an alkyl group having 1 or 2 carbon atoms or a hydrogen atom, and R ₃ represents a hydrogen atom or a hydroxyl group.
p represents an integer of 0 to 2, q represents an integer of 1 to 3, and r represents an integer of 1 to 3. A may be replaced by any hydrogen atom on the benzene ring. s is 0 to 50, t is an integer of 0 or 1, and u is 1.
It represents an integer of 0 to 150. [Chemical 6] [Wherein, R is an alkyl group having 4 to 25 carbon atoms and optionally having a linear or branched substituent, Or a hydrogen atom (provided that R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 represents an integer of 0 to 4). n ₈ and m each represent 0 or an integer of 1 to 200, but they do not become 0 at the same time. A and B are respectively And may be the same or different. However,
n ₉ , m ₁ and l ₁ respectively represent 0, 1, 2 or 3, but n ₉ , m ₁ and l ₁ do not become 0 at the same time. D represents a hydrogen atom. ] 6. A silver halide color photographic light-sensitive material imagewise exposed is color-developed using a processing solution prepared by diluting the color-developing concentrated composition according to claim 1 at least 4-fold, A method of processing a silver halide color photographic light-sensitive material, characterized by performing a desilvering process thereafter.