JPH0463342A - Color developing composition - Google Patents

Abstract

PURPOSE:To lessen the formation of tar and the coloration of liquid even if a high-concn. developing agent is incorporated into the above compsn. by specifying the compsn. of a color developer. CONSTITUTION:This color developing compsn. is formed by incorporating >=8.0g/l arom. primary amine color developing agent, at least one kind of the compds. expressed by formula I, at least one kind of the compds. expressed by formula II, and at least one kind of the compds. expressed by formulas III, IV and V in this compsn. In the formulas, R denotes 4 to 16C alkyl group or alkenyl group; M denotes hydrogen or cation species; R1, R2 denote hydrogen, alkyl group, etc.; L denotes an alkylene group, phenylene group, etc.; L1 to L10 denote an alkylene group; R11 to R18 denote a hydrogen atom, hydroxy group, etc.; R21 denotes an alkyl group; R31 to R34 denote hydrogen, halogen, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to the composition of a color developer used in the color development process of silver halide color photographic light-sensitive materials, and more specifically relates to the composition of a color developer used in the color development process of silver halide color photographic light-sensitive materials. This invention relates to a developing composition.

(Prior Art) In recent years, in the processing of silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials), research has been underway to reduce the amount of replenishment liquid from the viewpoint of environmental conservation. In order to achieve this low replenishment process, particularly for low replenishment of color developer, it is necessary to make the color developer replenisher more concentrated. Furthermore, in low replenishment processing, the color developer is easily fatigued, so it is an important issue to improve the stability of the color developer and its replenisher.

Color developer replenisher generally has a lower pH than color developer.
is high and the concentration of developing agent is also high. Under such conditions,
When a color developer replenisher is used over time, the developing agent deteriorates, causing coloring of the solution and generation of tar. This may contaminate the processing machine, and replenishing the color developer replenisher may deteriorate the finished quality of the photosensitive material.

In the case of continuous processing with low replenishment, in addition to the above-mentioned deterioration of the replenisher, the color developer itself also tends to deteriorate, making the above-mentioned problem of deterioration of the finished quality of the photosensitive material even more serious.

Various preservatives have been developed to improve the stability of these color developers. For example, International Publication Patent WO
No. 3,710,360 describes specifying sulfite concentrations and using hydroxylamine derivatives and specific chelating agents.

However, in the case of a developing composition with a high concentration of developing agent, such as a color developer replenisher, the accumulation of deterioration products tends to increase.
The reality is that the finished quality of photosensitive materials cannot be fully guaranteed.

Further, the higher fatty acids described in the present invention are known from the viewpoint of preventing precipitation of developing agents, and for example, in JP-A No. 53-69035,
The issue describes the effect of preventing crystallization in a color developer replenisher system containing hydroxylamine. However, regarding the deterioration of the Micolor developer, it cannot be inferred that the above-mentioned problem is related to the combination of a hydroxylamine having a substituent and the chelating agent according to the present invention.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a color silver halide color photographic light-sensitive material that is stable with little generation of tar or coloration of the liquid even if it contains a high concentration of developing agent. An object of the present invention is to provide a color developing composition for use in a developer.

(Means for Solving the Problems) The above problems of the present invention were achieved by using the following color developing composition.

8.0 g/l or more of an aromatic primary amine color developing agent, at least one compound represented by the following general formula (A), and at least one compound represented by the following general formula (B). A color developing composition comprising at least one compound represented by the following general formulas (1), (n) and (I[l).

General formula (A) -COOM In the formula, R represents an alkyl group or alkenyl group having 4 to 16 carbon atoms, and M represents a hydrogen atom or a cation species.

General formula (B) 0-N-R In the formula, R3 and R2 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or a heterocyclic group, provided that R1 and R1 are simultaneously R7 and R2, which are not hydrogen atoms, may be linked to each other to form a petero ring with a nitrogen atom.

General formula (1) % formula % In the formula, L is an alkylene group, a cycloalkylene group, a phenylene group, Ls-○-Ls OLs or -L6
Z Lb-, where Z is N Lq Rl
s, -N L, -N-Lq RIb
L drop RIM>N RIq or -N-L, 0-
Represents N-.

Rls RI.

L, or Ll. each represents an alkylene group.

R11 to R7 are each a hydrogen atom, a hydroxy group, a carboxylic acid group (including its salt), or a phosphonic acid group (
(including salts thereof), provided that at least two of R1 to RI4 are carboxylic acid groups (including salts thereof)
or a phosphonic acid group (including its salts).

General formula (II)・ P○, R2 HO-C-R□ 0sHt In the formula, R1 represents an alkyl group.

General formula (nT) H 1?33 In the formula, Rll to R34 are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group, or R.

It represents a phenyl group, and R1+ to R3g may be the same or different. Also, Ro to R3,
each represents a hydrogen atom or an alkyl group, provided that
When R,ll represents a hydroxy group or a hydrogen atom,
R33 is a halogen atom, a sulfonic acid group, an alkyl group,
In 0R3S, -COORsss, Ro and R33 may be linked to each other to form a naphthalene ring, or the naphthalene ring may have an atom or group as defined above represented by R31 to Ro.

First, general formula (A) will be explained in detail.

As a substituent in general formula (A), a hydroxy group,
They are a carboxy group and a sulfo group. Alkyl and alkenyl groups are straight-chain or branched alkyl and alkenyl groups having 4 to 16 carbon atoms. Preferably, they are unsubstituted alkyl groups and alkenyl groups. The number of carbon atoms is preferably 6 to 15, more preferably 10 to 15.

M represents a hydrogen atom or a cation species, and the cation species include alkali metals (e.g. lithium, sodium,
potassium), ammonium.

Preferred are hydrogen atoms and alkali metals.

Specific examples of the compound represented by the general formula (A) are listed below, but the present invention is not limited to these compounds.

These compounds represented by the general formula (A) can be used in developer solution 11
The range is from 1X10-'' to 10g, preferably from 5X10-'' to 5g.

Further, the compounds represented by the general formula (A) may be added at the time of preparing the developer, or may be added in the required amount as a roughening solution, and the timing of their addition,
There are no particular restrictions on the addition method.

Note that higher fatty acids with a large number of carbon atoms, for example, those with carbon atoms of 15 or more, may foam during the preparation or processing of color developing solutions. This problem can be solved while maintaining the effect of As an antifoaming agent, for example, JP-A-49-
No. 62127, No. 49-62128, Special Publication No. 51-3
No. 7538, West German Publication No. 1936676, Japanese Patent Publication No. 1973
Compounds described in No. 23436 and the like can be used.

The compounds represented by the general formula (A) of the present invention may be used in combination of two or more.

Next, general formula (B) will be explained in more detail.

Substituents for R1 and R2 include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroquine group, an alkyl-substituted ammonio group (for example, a trimethylammonio group), and an alkyl-substituted amino group. (e.g. dimethylamino group), carbamoyl group which may be substituted with alkyl (e.g. N-methylcarbamoyl, N-propylcarbamoyl group), sulfamoyl group which may be substituted with alkyl (e.g. N-methylsulfamoyl, N- ethylsulfamoyl group), an optionally substituted alkylsulfonyl group (e.g., methanesulfonyl, 2-carboxyethylsulfonyl group), acylamino group (e.g., acetylamino group), alkylsulfonyltomino group (e.g., methanesulfonylamino group), Arylsulfonylamino group (e.g. benzenesulfonylamino group), alkoxycarbonyl group (e.g. ethoxycarbonyl group), arylsulfonyl! (eg benzenesulfonyl group), nitro group, cyano group, halogen atom (eg chlorine, bromine).

The ring structure of the nitrogen-containing heterocycle is a 5- or 6-membered ring, composed of carbon atoms, hydrogen atoms, halogen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.
Examples of these nitrogen-containing heterocycles include piperidyl, pyrrolidyl, N-methylpiperazyl, morpholyl, indolinyl, and benztriazolyl groups.

In the present invention, R1 and R2 are preferably unsubstituted or substituted alkyl groups or alkenyl groups, and the number of carbon atoms is preferably from 1 to 10, particularly preferably from 1 to 5.

Preferred substituents for R2 and Rt are a hydroxy group, an alkoxy group, a carboxy group, a sulfo group, and a phosphono group,
Particularly preferred are a carboxy group, a sulfo group, and a phosphono group.

Specific examples of the compound represented by the general formula (B) are listed below, but the compounds of the present invention are not limited thereto.

(B (B-73) (B-74) ■ HONHCHzCHtN (CHz)z (B (B (B (B (B 6 days) (B (B-70) (B-75) ■ HONHC82C) ICH!N( CH3)5(B (B H -C The amount of the compound represented by formula (B) added to the color developing solution is 5X10-' to 5X10-' mol/l. Preferably, 2X10-! to 5X10-' mol/l. It is desirable to add it at a concentration of 1 x 10-1 mol/p.

Moreover, two or more types of compounds represented by the general formula (B) can also be used in combination. These compounds may be added directly when preparing a color developing solution, or a concentrated solution may be prepared and then added in the required amount.

Next, general formula (1) of the present invention will be explained.

-C In formula (1), the alkylene group has 1 to 5 carbon atoms.
is an alkylene group. It preferably has 1 to 3 carbon atoms, and methylene, ethylene, and propylene groups are preferred. The cycloalkylene group is preferably a cyclohexylene group.

Specific examples of the compound represented by the general formula (1) are listed below, but the present invention is not limited to these compounds.

N-1F Ethylenediaminetetraphosphonic acid [I [I diethylenetriaminepentaacetic acid 3] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid propylenediaminetetraacetic acid triethylenetetraminehexaacetic acid cyclohexanediaminetetraacetic acid 1.2-diaminopropanetetraic acid 2] acid [■ [■ [I] 1 13-diaminopropan-2-ol-tetraacetic acid ethyl ether diamine tetraacetic acid glycol ether diamine tetraacetic acid 11] ethylenediaminetetrapropion 9] 8] acid Phenyldiaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt (1-14) Ethylenediaminetetraacetic acid tetra1
2] [■ (Trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-) Sodium acetate salt Propylenediaminetetraacetic acid sodium salt Salt Ethylenediaminetetramethylenephosphonic acid cyclohexanediaminetetraacetic acid sodium salt (1-21) Diethylenetriaminepentamethylenephosphonic acid cyclohexanediaminetetramethylenephosphonic acid Ethylenediamine orthohydroxyphenylacetic acid 15] 18] 16] 19] 23] [I [■ [I [ 1-20) [■ [I (1-24) N,N'-bis(2-hydroquinobenzyl)ethylenediamine-N,N' diacetic acid The compound represented by the general formula (I) of the present invention is a color developer. It is used in a range of 0.1 to 20 g per 11. Preferably, it is in the range of 0.3 to 15 g. Moreover, two or more types of these compounds can also be used in combination.

Next, general formula (II) will be explained.

The argyl group in general formula (It) has 1 to 5 carbon atoms.
is a straight chain or branched alkyl group, which may be substituted. The substituent has the same meaning as the one substituent explained in general formula (B), but preferably a hydroxyl group, a carboxyne group, a sulfo group, a phosphono group, and a lower alkokino group having 1 to 4 carbon atoms.

Specific examples of the compound represented by the -11R formula (II) are listed below, but the compounds of the present invention are not limited thereto.

The compound represented by the general formula (II) of the present invention is used in an amount of I x 10-'' to 10 g per 1 p of the developer. Preferably, it is in a range of I x 10-' to 5 g. Can also be used together.

Next, general formula (III) will be explained.

In the general formula (I(1)), the alkyl group is a linear or branched unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, and examples of the substituent include a hydroxo group, a carboxy group,
Alkoxycarbonyl groups (e.g. methoxycarbonyl,
butoxycarbonyl group), aryl group (e.g. phenyl group) are preferable, and the phenyl group may be a phenyl group having a substituent, such as 2-hydroxyphenyl, 4
-aminophenyl group and the like.

Specific examples of the compound represented by the general formula (II[) will be listed below, but the present invention is not limited to these compounds.

(I[l-1) 4-isopropyl-12-dihydroxybenzene (I[l-2) 1.2-dihydroxybenzene-
35-Disulfonic acid (1-3> 1.2.3-trihydroxybenzene-5-carboxylic acid (III-4) 1 2.3-)dihydroxybenzene-5-carboxymethyl ester (I[1-5) 1 .2.3-trihydroxybenzene-5-carboxy-n-butyl ester <ll-6> 5-t-butyl-1,2,3-trihydroxybenzene (III-711, 2-dihydroxybenzene-35,
6-) Disulfonic acid (■-8) 1,2-dihydroxybenzene-6chloro-
3,5-disulfonic acid (III-9) 1,2-dihydroxybenzene-
34,5,6-tetrasulfonic acid (m-10) 2.3-dihydroquinaphthalene 6-sulfonic acid (III-11) 2. 3. 8-1-lyhydroxynaphthalene-6-sulfonic acid (Ill-12) 2. 3-dihydroquinaphthalene 6-carboxylic acid (Iff-13) 2. 3-dihydroxo-8~
Isopropyl-naphthalene (III-14) 2. 3-dihydroxy-8-
Chloronaphthalene-6-sulfonic acid In the above compound, carboxylic acid and sulfonic acid also include alkaline earth salts such as sodium salt and potassium salt,
can be used.

The compound represented by the general formula (III) of the present invention can be used in an amount of 5.times.10-' to 15 g per 11 of the developer. Preferably from 1.5X10-2
0g, more preferably 2.5XIO-" to 7g. Also, two or more types can be used in combination.

At least one of the compounds represented by the above general formulas (1), (II) and (III) is contained in the color developer together with the compounds represented by the general formulas (A) and (B). Accordingly, the stability of the color developer can be further improved.

In the present invention, the compounds represented by the general formulas (1), (n) and (III) are combined, and the compounds represented by the general formula (
By using the compound represented by A) and general formula (B), the effect can be further enhanced. Among these combinations, the general formulas (1) and (■), the general formulas (1) and (■), the general formulas (1), (It), and (III) are particularly preferable.

The color developing composition according to the present invention is particularly suitable for tank liquid (
When used not only as a mother liquor (mother liquor) but also as a so-called replenisher, it is particularly preferable in that tar formation and coloring can be suppressed. Furthermore, the effects of the present invention are particularly noticeable when the color developing composition is a color developing replenisher having a pH of 10.8 or higher and a carbonate concentration of 25 g/l or higher.

The color developing composition used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl N- (β−
(methanesulfonamido)ethyl]-aniline D-7N-<2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl N-β-
Ethoxyethylaniline 1)-11,4-amino-3-methyl-N-ethylN-
β-Butoxyethylaniline D-124-amino-3-ethoxycarbonylamino-
N-Ethyl-N-β-methoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl N-Cβ-(methanesulfonamido)ethylcoaniline (Exemplary Compound D
-6).

Further, salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates may be used with these p-phenylenediamine derivatives. In the present invention, the amount of the aromatic primary amine developing agent used is preferably 8 to 8 per p of the developer.
A concentration of about 25g, more preferably 10 to about 15g.

In practicing the present invention, it is preferred to use a developing composition that is substantially free of Hensyl alcohol. Here, "substantially not containing" preferably means 2 wl/
l. Below, more preferably 0. Benzyl alcohol concentration below 5 wd/l'l and most preferably no hensyl alcohol.

More preferably, the developing composition used in the present invention does not substantially contain sulfite ions.

The sulfite ion functions as a preservative for the developing agent (17), and at the same time has a silver halide dissolving action and reacts with the oxidized developing agent to reduce the dye formation efficiency. This effect is one of the causes of increased variation in photographic properties during processing.
This is because it is estimated that there is one. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10 -' mol/l or less, and most preferably no sulfite ion at all. However, in the present invention, a small amount of sulfite ion is excluded, which is used to prevent oxidation of a processing side kit in which the developing agent is subjected to SVa before being mixed into a solution for use.

The developing composition used in the present invention preferably contains substantially no sulfite ions, and more preferably substantially no hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties. Here, "substantially not containing hydroxylamine" preferably means 5.0 x 10-' mol/l.
1 degree of hydroxylamine, most preferably no hydroxylamine at all.

The developing composition used in the present invention uses compounds represented by the general formulas (A) and (B) of the present invention in place of the hydroxylamine and sulfite ion, and further contains a known organic preservative. can be used.

The term "organic preservative" as used herein refers to any organic compound that, when added to a processing solution for a color photographic light-sensitive material, reduces the rate of deterioration of an aromatic primary amine color developing agent. That is, they are organic compounds that have the function of preventing the oxidation of color developing agents by air, among others, hydroxams A2,
Hydrazines, hydrazides, phenols, α-hydroquine ketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and fused amines are particularly effective organic preservatives. These are JP-A Nos. 63-4235, 63-30845, 63-21647, and 6
No. 3-44655, No. 63-53551, No. 63-4
No. 3140, No. 63-56654, No. 63-5834
No. 6, No. 63-43138, No. 63-146041, No. 63-44657, No. 63-44656, U.S. Pat. No. 143020, Special Publication Showa 4B-3049
It is disclosed in No. 6, etc.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in No. 349 may be contained as necessary.

In particular, it is preferable to add alkanolamines such as triethanolamine or hydrazine derivatives.

Examples of amines include cyclic amines described in JP-A-63-239447, amines as described in JP-A-63-128340, and other patent applications JP-A-63-971.
Examples include amines such as those described in No. 3 and No. 63-11300.

The color developing composition used in the present invention, especially when used as a replenisher for low replenishment, preferably has a high pH in order to maintain the pH in the tank. , the pH is preferably 10°8 or higher, more preferably 1
0.8 to 13 is preferred.

In the present invention, as described above, when the color developing composition is used particularly as a replenisher for low replenishment, it is desirable to contain, for example, 20 g or more of carbonate in order to maintain the pH in the tank. In order to bring out the effects of the present invention, it is preferable to contain 25 g/l or more.Furthermore, in order to maintain the above pH, various buffering agents can be used, but other buffering agents include: Phosphoric acid, borate, tetraborate, hydroxybenzoate, glinol salt, N,N-dimethylglycine salt, leuson salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyric acid Salt, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used.

Specific examples of these buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Other salts include trisodium phosphate, tripotassium phosphate, trisodium phosphate,
Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate,
Sodium 0-hydroxybutyric C1 fomanate (sodium salicylate), Potassium 0-hydroxybenzoate, Sodium 5-sulfo-2-hydroquine benzoate (Sodium 5-sulfosalicylate), Potassium 5-sulfo-2-hydroxobenzoate (5- Examples include potassium sulfosalicylate). However, the present invention is not limited to these compounds.

The total amount of the buffer added to the color developing composition including carbonate is preferably 0.1 mol/l or more, particularly 0.1 mol/l to 0.4 mol/l. It is particularly preferable.

In addition, general 24), (II) and (III) are used as anti-settling agents for calcium and magnesium in color developing compositions, or to improve the stability of color developing solutions.
In addition to the above, various chelating agents can be used. for example,
Nitrilotriacetic acid, N, N.

N-1-rimethylenephosphonic acid, 2-phosphonobutane-
Examples include 1,2,4-tricarboxylic acid.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developing composition. For example, it is about 0.1 g to 10 g per 11.

If necessary, any development accelerator can be added to the color developing composition.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
'l-5987, 3B-7826, 44-12
No. 380, No. 45-9019 and U.S. Patent No. 3.81
3,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-Sho 50
= Quaternary ammonium salts shown in Japanese Patent Publication No. 437726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2.494
．． No. 903, No. 3.128.182, No. 4,230.
No. 796, No. 3,253.919, Special Publication No. 41-11
No. 431, U.S. Patent No. 2482.546, U.S. Patent No. 2.59
Amine compounds described in 6.926 and 3.582.346, etc., Japanese Patent Publication No. 37-16088, 42-2
5201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3.532,501, etc., and other 1-phenyl-3-birapritone etc., imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidrohenzimitasole, 5-nitroisoindazole, 5methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole. , 2-thiazolylmethyl-
Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing composition that can be used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent whitening agent, 4.
4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0.05 to 5 g/l, preferably 0.1 g to 4/l, and various surfactants such as alkyl sulfonic acids, arylsulfonic acids, and aromatic carboxylic acids may be added as necessary. Also good.

Further, if necessary, water-soluble polymers such as homopolymers or copolymers thereof having hydroxy, pyrrolidone, amide, oxyethylene groups, or anionic dissociative groups can be used.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited to these.

Example】 A color developing composition having the composition shown below was prepared.

water 80
0d General formula (1) - (■) (See Table 1) Triethanolamine 15g Sodium chloride 1.0g Potassium bromide
0.020g potassium carbonate
28g General formula (A)
(See Table 1) N-ethyl-N-(β-methane
10.0g Sulfonamidoethyl)-3 Monomethyl-4-aminoaniline General formula (B) (See Table 1) Sodium sulfite 0.1g Optical brightener 01
HITEX-4, 3, 0g manufactured by Sumitomo Chemical) pH (25°C) 10.
90 (pH adjustment is done with potassium hydroxide or sulfuric acid aqueous solution) Each of the prepared color developing compositions was placed in a glass beaker and strained so that the aperture ratio defined below was 0.05. It was stored for 7 days at ℃.

However, stirring was given for 30 minutes x 2 times/day.

Opening ratio Ccffi-') = Volume of color developing composition (, ff1) The entire volume of each color developing composition stored under the above conditions was transferred to Ichito paper (Toyo Roshi, 5A) with a diameter of 90 m. , separated using a Buchner funnel, and evaluated by conducting a sensory test based on the amount of floating matter and precipitate separated on the paper, and also by observing the state of the color developing composition after storage under the above conditions. However, the △ marks are at the very limits of practicality.

The results obtained are summarized in Table 1.

From the results in Table 1, the general formula (
A), (B) and -Color developing compositions (from floors 7 onwards) using at least one of the ship stock (1) to (pl) are more effective than comparative color developing compositions (positive numbers 1 to 6). It can be seen that even when stored under high temperature conditions, the liquid does not become cloudy and no suspended matter is generated, indicating that it has excellent stability.

Example 2 A color developing composition was prepared by changing the composition to the following formulation.

water 80
〇-General formulas (1) to (III) See Table 2 Triethanolamine 17g Potassium carbonate See Table 2-Ship storage (A)
See Table 2 N-ethyl-N-β
-(Methane 12.3g Sulfonamidoethyl)-3 Methyl-4-aminoaniline General formula (B) See Table 2 Sodium gnitite 0.2g Optical brightener (
WHITEX-4, 0.2g manufactured by Sumitomo Chemical) (Adjust the pH using potassium hydroxide or sulfuric acid aqueous solution) These prepared color developing compositions were stored in a polyethylene container, and the aperture ratio was adjusted to 0. 01Cam-') and stored at 40°C for 7 days. During this time 6
Stirring was given for 0 minutes x 1 time/day.

After the above test was completed, the color developing composition was subjected to a sensory test according to the method described in Example 1.

These results are summarized in Table 2.

From the results in Table 2, it can be seen that the color developing composition (floor 35 and above) that satisfies the constituent requirements of the present invention is different from the comparative color developing composition (
It is clear that they exhibit superior stability under storage conditions at higher temperatures than those of Grades 31 to 34).

Further, the potassium carbonate concentration of the color developing composition is 25 g/l.
It can be seen that when the potassium carbonate concentration is 25 g/l or more and the pH is 10.8 or more, it is worse in the comparative example than when the pH is 10.8 or less (Nn32
, l & 33), according to the structure of the present invention, the liquid condition does not deteriorate even when the potassium carbonate concentration is 25 g/l or more and the pH is 10.8 or more (m37 compared to floor 35.36). Recognize.

Example 3 The color developing agent N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline in the color developing composition Level 31 of Example 1 was used as an exemplary compound of the color developing agent. Listed D-4, D-5, D-9, D
-12 and D-5/D-6 = 1/l (molar ratio) in equal molar proportions, and the stability of the color developing composition was investigated under the same conditions as described in Example 2.

As a result, the same results as those for floors 35 to 45 of Example 2 were obtained, and it was confirmed that excellent stability was exhibited.

Example 4 Fog prevention 11 was applied to the m39 color developing composition of Example 2.
6-nidropenzimidazole as lXl0-”g
/l plus (1-2 of the compound represented by -Funezo (1)
Stability evaluation was carried out under the same conditions as in Example 2 by replacing 3 with the same number of grams of nitrilotriacetic acid and adding 1 g/l of polyvinyl alcohol-polyacrylic acid block copolymer (2:1 weight ratio). Results similar to those of N1135-45 in Example 2 were obtained, and it was confirmed that it exhibited excellent stability.

(Effects of the Invention) A color developing composition for use in color development of silver halide color photographic materials contains 8.0 g or more of an aromatic primary amine color developing agent, Also, if it contains at least one of the aliphatic carboxylic acid or its salt, the hydroxolamine derivative, and the chelate represented by (1) to (III) of the present invention, there will be no coloration and no floating matter will be generated. It is possible to provide a highly concentrated color developing composition with excellent stability.

1゜ Procedural amendment 1990 1

Claims (2)

[Claims] (1) Aromatic primary amine color developing agent 8.0g/l
The above, at least one compound represented by the following general formula (A), at least one compound represented by the following general formula (B), and the following general formulas (I), (II), and (III) A color developing composition comprising at least one compound represented by: General formula (A) R-COOM (In the formula, R represents an alkyl group or alkenyl group having 4 to 16 carbon atoms, and M represents a hydrogen atom or a cation species.) General formula (B) ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (In the formula, R_1 and R_2 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or a heterocyclic group. However, R_1 and R_2 must be hydrogen atoms at the same time. (R_1 and R_2 may be linked together to form a heterocycle with the nitrogen atom.) General formula (I) ▲ Numerical formula, chemical formula, table, etc. are available▼ (In the formula, L is an alkylene group, cycloalkylene group, phenylene group, -L_5-O-L_5-O-L_5- or -L_6-Z-L_6-, where Z is -N-L
＿７－R＿１＿５、▲There are mathematical formulas, chemical formulas, tables, etc.▼
, Represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. L_1 or L_1_
Each 0 represents an alkylene group. R_1_1 to R_1_8 each represent a hydrogen atom, a hydroxy group, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts). However, at least two of R_1_1 to R_1_4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof)
It is. ) General formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_12 represents an alkyl group. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_3_1 to R_3_4 are hydrogen atoms, halogen atoms, sulfonic acid groups, alkyl groups, -OR, respectively)
_3_5, -COOR_3_6, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or represents a phenyl group, and R_3_1 to R_3_4 may be the same or different. Further, R_3_5 to R_3_2 each represent a hydrogen atom or an alkyl group. However, when R_3_1 represents a hydroxy group or a hydrogen atom, R_3_3 is a halogen atom, a sulfonic acid group, an alkyl group, -OR_3
_5, -COOR_3_6, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or represents a phenyl group. Furthermore, R_3_2 and R_3_3 may be linked to each other to form a naphthalene ring, and the naphthalene ring may have the above-defined atoms or groups represented by R_3_1 to R_3_4. ) (2) The color developing composition according to claim 1, wherein the color developing composition contains carbonate in an amount of 25 g/l or more and has a pH of 10.8 or more.