JPH0582931B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a color developer replenisher for silver halide color photographic light-sensitive materials, and more specifically, the present invention relates to a color developer replenisher for silver halide color photographic light-sensitive materials. In addition, it has been improved from crystal precipitation due to evaporation at the liquid interface of the replenishment tank when stored in a replenishment tank for a long period of time in high temperatures such as tropical regions and deserts, or in dry regions, and can be used in any region of the world. This invention relates to a color developer replenisher that provides stable processing characteristics. [Prior art] Processing of photosensitive materials basically consists of two processes: color development and desilvering.
Desilvering consists of a bleaching and fixing step or a bleach-fixing step. Additional treatment steps such as rinsing and stabilization are added to this area. In color development, the exposed silver halide is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction field of silver halide are eluted into the developer and accumulated. Additionally, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously. As mentioned above, development inhibitors accumulate in color developing solutions when photographic light-sensitive materials are developed, but on the other hand, color developing agents and benzyl alcohol are consumed or accumulated in the photographic light-sensitive materials and taken out. The concentration of the components decreases. Therefore, in a development method in which a large amount of silver halide photographic light-sensitive material is continuously processed using an automatic processor, etc.,
In order to avoid changes in development finish characteristics due to changes in component concentration, a means is required to maintain the components of the color developer within a constant concentration range. As such a method, a method is usually used to replenish the deficient components and dilute the unnecessary increased components.
The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow liquid, methods have been developed to regenerate the developing method using ion exchange resin method or electrodialysis method, concentrated low replenishment method, and another method is to add a regenerant to the overflow liquid and use it again as a replenisher. etc. have been proposed and put into practical use. However, regeneration of the developer is performed by removing bromide, which is an unnecessary accumulated component, and supplementing the insufficient components, but this method (ion exchange resin method and electrodialysis method) is based on the chemical analysis of the developer components. It has the disadvantage that the processing characteristics of the photosensitive material will be impaired unless it is quantified and kept constant, and it requires complicated management, so it is rarely installed in small-scale photo labs or mini-labs that do not have special skills. It's impossible. Furthermore, the initial cost is extremely high. Furthermore, the method of adding a regenerating agent to the overflow solution and reusing it as a replenisher does not require any special skills, but it does require space such as a stock tank, and it also has the disadvantage of being complicated for the photo lab. It is extremely difficult to introduce it into minilabs, etc. However, the concentrated low replenishment method does not particularly require new equipment and is easy to manage, making it extremely suitable for small-scale laboratories such as minilabs. However, this method also has some drawbacks. For example, p-
When using phenylenediamine derivatives, amine bases or free amines tend to precipitate in replenishment tanks and piping (particularly in areas where soft vinyl chloride hoses are used) in cold regions or in winter. With the spread of printing, color development processing is increasingly being performed in various regions around the world.For example, in laboratories in hot or dry regions such as tropical regions and desert regions, replenishment tanks are needed. A new problem has also arisen: crystals form at the tank-to-replenisher interface due to evaporation from the replenisher. In order to eliminate this drawback, techniques for increasing the solubility of p-phenylenediamine derivatives in the developer include adding alkylbenzenesulfonic acid (British Patent No. 669505) and adding methylcellulose (Japanese Patent Publication No. 46-41676). Publication No.). Adding lactose or hydroxypropylcellulose (Japanese Patent Publication No. 50-21250), adding a carboxylic acid derivative or a quaternary ammonium compound having a hydroxyalkyl group (Japanese Patent Application Laid-open No. 70436/1989, -69035) etc. are conventionally known. However, the actual situation is that the technology of adding these compounds to the developer has various drawbacks and has not yet reached a level of practical satisfaction. That is, alkylbenzene sulfonic acid has 100 to 200
Although a series of celluloses improves the solubility of p-phenylenediamine derivatives in a developer solution in a relatively small amount, for example, methyl cellulose, etc., has the opposite effect when added to a developer solution in excess of a certain amount. Furthermore, when the treatment solution is made into a kit, its solubility is extremely poor, requiring a great deal of time and effort in producing the treatment kit. Further, carboxylic acid derivatives and quaternary ammonium compounds have the disadvantage that they are weakly effective against crystal precipitation on the evaporation surface. In addition, the number of minilabs has increased rapidly in recent years, and as of May 1985, the number of minilabs installed in Japan was approximately
It is said that there are 3,000 such facilities, and at least one-third of these are said to have been installed within the past year. This is truly an unprecedented mini-lab boom. Minilabs like this usually have a few employees, and in addition to selling cameras and film, they also provide printing services, so during busy times they can become so busy that they even want to hire a so-called cat's hand. When the replenisher runs out during such busy times, printing operations must be stopped and the replenisher must be dissolved. In recent years, color developer replenishers have become more concentrated and take longer to dissolve.Therefore, in minilabs, there is a strong desire for replenishers to be able to dissolve as quickly and easily as possible, even if they are concentrated. It is. Furthermore, as mentioned above, in recent years, as color developing solutions have become more concentrated and less replenishable, there is a tendency for replenishers to have a higher PH in order to maintain the PH condition of the color developing treatment tank with a small amount of replenishment. Maintaining such a high pH is an extremely difficult problem, and a solution to this problem has been desired in recent years. SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a color developer replenisher for silver halide color photographic materials that does not cause precipitation of amine crystals in replenishment tanks or piping in cold regions or in winter. The second objective is to create a silver halide color that is free from crystal precipitation caused by amines caused by evaporation at the liquid interface in the replenishment tank, even when stored for long periods in high temperature or highly dry areas such as tropical or desert regions. An object of the present invention is to provide a color development replenisher for photographic materials. Furthermore, the third
The object of the present invention is to provide a color developer replenisher for silver halide color photographic materials which can be rapidly dissolved. Furthermore, a fourth object is to provide a color developer replenisher for silver halide color photographic light-sensitive materials that enables maintenance of a high pH. [Means for Solving the Problem] As a result of various studies to achieve the above-mentioned object, the present inventors found that the color developer replenisher contains at least one of an aminocarboxylic acid compound or an aminophosphonic acid compound. , and the surface tension is 20~
It has been found that the above objective can be achieved when the density is 60 dyne/cm. In addition, as a preferable embodiment of the present invention, the color development compensation liquid contains a compound represented by the following general formula []. General formula [] R-O(-A) _o --(-B) _n --C [wherein R is an alkyl group having 4 to 25 carbon atoms which may have a linear or branched substituent or

[Formula] (However, R ₁ and R ₂ 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.) A and B are respectively

[Formula], which may be the same or different (however, n ₁ ,
m ₁ and l ₁ each represent 0, 1, 2 or 3).
C represents a hydrogen atom or _-SO3M (M represents a hydrogen atom, sodium, potassium, ammonium or lithium). n and m each represent 0 or an integer of 1 to 25. ] Furthermore, it is mentioned that the color development replenisher of the present invention contains at least one of the compounds represented by the following general formulas [] to []. General formula []

embedded image In the formula, A ₁ represents a carboxylic acid group, a phosphoric acid group, or a salt thereof, and X represents a hydroxyl group or a salt thereof. B ₁ is a halogen atom, a hydroxyl group,
Represents an alkyl group, a carboxylic acid group, a phosphonic acid group, or a salt of a hydroxyl group, a carboxylic acid group, or a phosphonic acid group. r and l ₂ are 0 and 1 respectively
or 2, n ₂ represents an integer from 1 to 4, m ₂
represents an integer from 0 to 3. General formula []

[Formula] In the formula, R ₃ represents an alkyl acid or an amino group which may have a substituent having 1 to 5 carbon atoms. General formula []

【formula】 General formula []

[Formula] In the formula, R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, -OR ₉ , −
COOR ₁₀ ,

[Formula] Or represents a substituted or unsubstituted phenyl group. Further, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Furthermore, another preferred embodiment of the present invention includes a compound represented by the following general formula [] or []. General formula [] HO(-A) _o3 --(-B) _n3 --H General formula [] N[(--A) _o --(-B) _n --H] In formula ₃ , n, m , A and B have the same meanings as in the general formula [], and n ₃ and m ₃ each represent 0 or an integer from 1 to 600. Furthermore, another preferred embodiment of the present invention is that the color developer replenisher does not substantially contain bromide. As a result of various studies to achieve the above object of the present invention, it was found that using only an aminocarboxylic acid compound or an aminophosphonic acid compound, or simply adjusting the surface tension of the color developer replenisher to 20 to 60 dyne/cm will not work. However, it is not possible to obtain the desired effect of the present invention, and only when these are used in combination,
Surprisingly, it was discovered that the object of the present invention can be achieved, leading to the present invention. The surface tension of the color developer replenisher of the present invention is determined from "Analysis and Testing Methods of Surfactants" (Fumio Kitahara, Shigeo Hayano,
Co-authored by Ichiro Hara, published on March 1, 1982, published by Kodansha Co., Ltd.), etc.). . In the present invention, any method may be used to adjust the surface tension of the color developer replenisher to 20 to 60 dyne/cm, and any method may be used, but surfactants are preferably used. If the surface tension is less than 20 dyne/cm, foaming occurs when the color developing and retouching solution is dissolved, making it impractical, and if it is larger than 60 dyne/cm, the effect of the present invention will not be achieved, so this is also not practical. Therefore, in the present invention, 20~
Used in the range of 60dyne/cm. In particular, when the color development replenisher has a concentration of 25 to 42 dyne/cm, particularly good effects are achieved for the purpose of the present invention. In particular, the present invention exhibits particularly good effects when the compound represented by the general formula [] is used as a surfactant to control the surface tension within this range. Next, preferred representative examples of the compound according to the present invention represented by the general formula [] will be listed. [Exemplary compounds]

【formula】

【formula】

【formula】

【formula】

[ka]

[ka]

【formula】

[ka]

【formula】

[ka]

[C] (-12) (n)C ₁₃ H ₂₇ -O(-CH ₂ CH ₂ O) ₅ --SO ₃ Na (-13) (n)C ₁₂ H ₂₅ -O(-CH ₂ CH ₂ O ) ₃ --SO ₃ Na (−14) (n)C ₁₀ H ₂₁ −O(−CH ₂ CH ₂ O) ₄ --SO ₃ K (−15) (n)C ₁₆ H ₃₃ −O(−CH ₂ CH ₂ O) ₄ --SO ₃ Na

【formula】

【C】 (−18) (n)C ₁₃ H ₂₇ −O(—CH ₂ CH ₂ O) ₄ --H

[Chemical formula] Among the compounds represented by the general formula [], (-1),
(-12) and (-13) are particularly preferably used. These compounds are described in British Patent No. 1022878,
It is synthesized by a general synthesis method as described in US Pat. No. 3,723,341, US Pat. No. 3,437,598, etc. Alternatively, commercially available products (e.g. Olin
Mathieson Chemical Corp.). Further, the compound represented by the above general formula [] is 0.001 to 10% per color developer replenisher of the present invention.
When the amount is used in the range of 0.001 to 3 g, the object of the present invention is particularly well achieved, and when the amount is used in the range of 0.001 to 3 g, the effects of the present invention are particularly well achieved. Next, preferred representative examples of the compound according to the present invention represented by the above general formula [] will be listed. [Exemplary compounds]

【formula】

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

【formula】

[Chemical formula] These compounds are synthesized by general synthetic methods such as those described in US Pat. No. 3,632,637 and Journal of the American Chemical Society, Vol. 89 (1967), page 837. Next, typical examples of the compound preferably used in the present invention represented by the general formula [] will be listed. (-1) 1-hydroxyethylidene-1,1
-diphosphonic acid (-2) 1-hydroxypropylidene-1,
1-diphosphonic acid (-3) 1,2-dihydroxyethane-1,
1-diphosphonic acid (-4) 1-hydroxybutane-1,1-diphosphonic acid (-5) 1-hydroxy-2-carboxy-
Ethane-1,1-disulfonic acid (-6) 1-amino-ethylidene-1,1-
Diphosphonic acid Specific example compounds represented by the general formulas [] and [] include 1,2-dihydroxybenzene, 4-isopropyl-1,2-dihydroxybenzene, 1,2-dihydroxybenzene 3,5-
Disulfonic acid, 1,2,3-trihydroxybenzene, 1,2,3-trihydroxybenzene-5
-carboxylic acid, 1,2,3-trihydroxybenzene-5-carboxymethyl ester, 1,2,
3-trihydroxybenzene-5-carboxy-
n-butyl ester, 5-t-butyl-1,2,
3-trihydroxybenzene, 2,3-dihydroxynaphthalene-6-sulfonic acid, 2,3,8-
Examples include trihydroxynaphthalene-6-sulfonic acid, but are not limited thereto. Among the above compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,5-disulfonic acid and its sodium and potassium salts, exemplified compounds (-1), (-2), ( -10), and particularly preferably 1,2-dihydroxybenzene-3,5-disulfonic acid and its salts (sodium salt, potassium salt). The compounds of the general formulas [] to [] are preferably used in an amount of 0.01 g to 10 g, more preferably 0.03 g per color replenisher of the present invention.
It is used in the range of ~3g. Next, typical examples of the compounds preferably used in the present invention represented by the above general formulas [] and [] will be listed. [Exemplary compounds] (-1) HO-CH ₂ CH ₂ -OH (-2) HO(-CH ₂ CH ₂ O) ₂ --H (-3) HO(-CH ₂ CH ₂ O) ₂ --H

[Chemical value] (-5)HO(-CH ₂ CH ₂ O) ₁₀ --H (-6)HO(-CH ₂ CH ₂ O) ₃₅ --H (-7)HO(-CH ₂ CH ₂ O) ₈ --H (-8) HO (-CH ₂ CH ₂ CH ₂ O) ₂ --H (-9) HO (-CH ₂ CH ₂ CH ₂ O) --H (-10) HO-CH ₂ CH ₂ CH ₂ CH ₂ −OH (−11) HO (—CH ₂ ) ₅ —OH (−12) HO (—CH ₂ CH ₂ O) ₄₉₂ —H

[Formula] (-1)N(-CH ₂ CHOH) ₃ (-2)N[(--CH ₂ CH ₂ O) ₂ --H] ₃

【formula】

[Formula] (-5)N(-CH ₂ CH ₂ CH ₂ OH) ₃ (-6)N(-CH ₂ CH ₂ CH ₂ CH ₂ OH) _3In the compounds represented by the above general formulas [] and [] , as compounds particularly preferably used in the present invention, (-1), (-2) and (-1)
can be mentioned. The compounds represented by the above general formulas [] and [] are contained in an amount of 0.3 per 1 color developer replenisher of the present invention.
It is preferable to use in the range of ~50g, especially 1g
The effects of the present invention are particularly well achieved when used in the range of 20 g to 20 g. The aminocarboxylic acid compound and aminophosphonic acid compound of the present invention represent an amino compound having at least two or more carboxylic acid groups and an amino compound having at least two or more phosphonic acid groups, respectively, and are preferably represented by the following general formula: It is a compound represented by [] and []. General formula []

[ka] General formula []

[Formula] In the formula, E is a substituted or unsubstituted alkylene group,
Cycloalkylene group, phenylene group, -
R ₁₃ OR ₁₃ OR ₁₃ −, −R ₁₃ represents ZR ₁₃ , Z is >N−
R ₁₃ −A ₆ , >N−A ₆ ; R ₉ to R ₁₃ represent a substituted or unsubstituted alkylene group; A ₂ to _{A 6} represent a water atom, −OH, −COOM, −PO ₃ M; and M represents a hydrogen atom or an alkali metal atom. Next, preferred specific examples of the compounds represented by the general formulas [] and [] are listed below. [Exemplary Compounds] [-1] Ethylenediaminetetraacetic acid [-2] Diethylenetriaminepentaacetic acid [-3] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid [-4] Propylenediaminetetra Acetic acid [-5] Triethylenetetraminehexaacetic acid [-6] Cyclohexanediaminetetraacetic acid [-7] 1,2-diaminopropanetetraacetic acid [-8] 1,3-diaminopropan-2-ol-tetraacetic acid [-9] ] Ethyl etherdiaminetetraacetic acid [-10] Glycol etherdiaminetetraacetic acid [-11] Ethylenediaminetetrapropionic acid [-12] Phanylenediaminetetraacetic acid [-13] Ethylenediaminetetraacetic acid disodium salt [-14] Ethylenediaminetetraacetic acid Tetra(trimethylammonium) salt [-15] Ethylenediaminetetraacetic acid tetrasodium salt [-16] Diethylenetriaminepentaacetic acid pentasodium salt [-17] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-tri Sodium acetate salt [-18] Propylenediaminetetraacetic acid sodium salt [-19] Ethylenediaminetetramethylenephosphonic acid [-20] Cyclohexanediaminetetraacetic acid sodium salt [-21] Diethylenetriaminepentamethylenephosphonic acid [-22] Cyclohexanediaminetetramethylene Phosphonic acid [-1] Nitrilotriacetic acid [-2] Iminodiacetic acid [-3] Hydroxyethyl iminodiacetic acid [-4] Nitrilotripropionic acid [-5] Nitrotrimethylenephosphonic acid [-6] Iminodimethylenephosphonic acid [- 7] Hydroxyethylimino dimethylenephononic acid [-8] nitrilotriacetic acid trisodium salt Among these aminocarboxylic acid compounds and aminophosphonic acid compounds, compounds that are particularly preferably used from the viewpoint of the desired effects of the present invention include (
-1), (-2), (-5), (-8), (-
19), (-1), (-3), and (-5). The amount of the alinocarboxylic acid compound and aminophosphonic acid compound according to the present invention is preferably used in the range of 0.1 to 20 g per color developer replenisher, particularly 0.3 g from the viewpoint of the purpose of the present invention.
A range of 5 g to 5 g is particularly preferably used. In the present invention, "not substantially containing bromide" means that the color replenishing solution of the present invention contains bromide within a range of 2 x 10 ^-3 mol/or less. A p-phenylenediamine color developing agent is used in the color developing replenisher of the present invention, and because it is more stable than a free state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. Also, the p
- The phelenediamine color developing agent is generally used at a concentration of about 0.5 g to about 30 g per color change developer. In the present invention, a particularly useful p-phenylenediamine type color developing agent is an aromatic primary amine color developing agent having at least one water-soluble amino group, particularly preferably represented by the following general formula []. The compound shown is General formula []

embedded image In the formula, R ₁₄ represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and may have a substituent. R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group, or an aryl group, but these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. and _R15
and at least one of R ₁₆ is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, or ((--CH ₂
) _t --O) _r --R ₁₇ . This alkyl group may further have a substituent. In addition, R ₁₇ represents a hydrogen atom or an alkyl group,
This alkyl group is linear or branched and has 1 carbon number.
-5 alkyl group, t and r represent integers of 1-5. Next, typical examples of the compound represented by the above general formula [] will be listed, but the invention is not limited thereto. [Exemplary compounds]

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

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【formula】

[Chemical formula] These p-phenylenediamine derivatives represented by the general formula [] can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, phosphate, p-toluenesulfonate, Acid salts, oxalates, benzenedisulfonates, etc. can be used. In the present invention, these general formulas []
Among the p-phenylenediamine derivatives represented by R ₁₅ and/or R ₁₆ are ((--CH ₂ ) _t --O) _r ---R ₁₇ (
t,
r and R ₁₇ have the same meanings as above. ), the effects of the present invention are particularly well achieved. When a triazylstilbene type optical brightener is used in the color replenishment solution of the present invention, the effects of the present invention are better exhibited, and the additional effect of improving the tar characteristics during retention of the replenishment solution is also obtained. It is more preferably used in the present invention because it also has the additional effect of improving the present invention. The triadylstilbene type optical brightener used in the present invention is preferably one represented by the following general formula [XI]. General formula [XI]

[Chemical formula] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group,
Halogen atoms such as chlorine or bromine, morpholino groups,
Alkoxy groups (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy, p-sulfophenoxy, etc.), alkyl groups (e.g., methyl, ethyl, etc.), aryl groups (e.g., phenyl, methoxyphenyl, etc.), amino group, alkylamino group (e.g. methylamino, ethylamino, propylamino, dimethylamino,
Cyclohexylamino, β-hydroxyethylamino, di(β-hydroxyethyl)amino, β-
Sulfoethylamino, N-(β-sulfoethyl)-
N'-methylamino, N-(β-hydroxyethyl-N'-methylamino, etc.), arylamino groups (e.g. amylino, o-, m-, p-sulfoanilino, o-, m-, p-chloroanilino, o -, m
-, p-toluidino, o-, m-, p-carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M has the same meaning as the general formula []. Specifically, the following compounds may be mentioned, but the invention is not limited thereto. [Exemplary compounds]

[ka]

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[ka]

[ka]

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[ka]

[ka]

[Chemical] The triazylstilbene-based brightener of the present invention can be synthesized, for example, by the usual method described in "Fluorescent Brighteners" (published in August 1976), edited by Japan Chemical Industry Association, page 8. can. These triadylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per color developer replenisher of the present invention. In addition to the metal ion sequestering agent described above, it is optional to add and use other metal ion sequestering agents (polyphosphoric acid, oxycarboxylic acid, phosphonocarboxylic acid, etc.). The color developing replenisher according to the present invention contains an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. is possible,
Furthermore, various additives such as benzyl alcohol,
It may contain an alkali metal halide such as potassium bromide or potassium chloride, a development regulator such as citradinic acid, and a preservative such as hydroxylamine or sulfite. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethyl formamide, and dimethyl sulfoxide, etc. can be appropriately contained. Further, the pH of the color developer replenisher according to the present invention is usually 7 or more, preferably about 9 to 13. In addition, the color developer replenisher used in the present invention may optionally contain antioxidants such as hydroxylamine, ascorbic acid, tetronic acid, tetonimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, and hydroxysam. Acid, pentose or hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained. The color development replenisher of the present invention can be applied as a color development replenisher for any general silver halide color photographic light-sensitive materials such as color negative film, color paper, color positive film, color reversal film, and color reversal paper. [Effects of the Invention] According to the present invention, amine crystals do not precipitate in replenishment tanks and piping in cold regions or in winter, and when stored for long periods in high temperature or highly dry regions such as tropical regions or desert regions. It can also improve crystal precipitation caused by amines due to evaporation at the replenishment tank liquid interface, and can be dissolved quickly and also made possible to maintain a high pH. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto. Experiments were conducted using the following color paper developer replenisher as a basic formulation. (Color developer replenisher composition) Potassium carbonate 30g Benzyl alcohol 17ml Ethylene glycol 15ml Potassium sulfite 2g Hydroxylamine sulfate 3g 3-Methyl-4-amino-N-ethyl-N-(β
-methanesulfonamidoethyl)-aniline sulfate 8g Potassium hydroxide 2g Add water to make 1, potassium hydroxide or 20%
The pH was adjusted to 10.6 using sulfuric acid. The above color developer replenisher was used as a control sample, and the chelating agent and surfactant shown in Table 1 ((-1)
(0.1 g/addition) was added as appropriate, and the mixture was divided into two equal parts. In addition, when the pH of the color development replenisher changed due to the addition of these chelating agents and surfactants, the pH was adjusted to 10.6 using potassium hydroxide or 20% sulfuric acid. One of the samples was placed in a soft vinyl chloride hose and stored at a low temperature of 3°C for 10 days, and the state of crystal precipitation (low temperature precipitation) was observed. Furthermore, the remaining one was placed in a 500 ml hard vinyl chloride container with an opening area of 100 cm ² and stored at 40°C and 10% RH for 10 days, and the state of crystal precipitation at the evaporation interface (evaporation precipitation) was observed. Furthermore, the PH difference before and after storage was measured. The above results are summarized in Table 1.

[Table] In the table, ○ means that there is no crystal precipitation, and × means that there is some crystal precipitation.
XX means that a large amount of crystal was precipitated. As is clear from Table 1 above, only when the chelating agent of the present invention is used and the surface tension is within the range of the present invention, there is no precipitation at low temperatures, no crystal precipitation during evaporation, and a decrease in pH. It turns out that there are few. However, when the chelating agent and the surface tension of the present invention are used alone, the low-temperature precipitation properties are poor, the pH decreases greatly,
Alternatively, it can be seen that the evaporation and precipitation properties are poor and the evaporation precipitation property is poor. Example 2 Regarding Experiment No. 1 of Example 1, surfactant (
The same experiment as in Example 1 was conducted by changing the amount of addition of -1) as appropriate and setting the surface tension of the color developer replenisher as shown in Table 2.

【table】

[Table] In the table, ○ means that there is no crystal precipitation, △ means that there is no actual damage but slight precipitation occurs, and × means that crystal precipitation has occurred to the extent that it becomes a problem. XX means strongly precipitated. From Table 2 above, it can be seen that low-temperature precipitation properties and evaporation precipitation properties are good when the surface tension is in the range of 20 to 60 dyne/cm. Furthermore, the surface tension is 25~42dyne/
It can be seen that the results are particularly good for cm. Example 3 The surfactant (-1) used in Example 1 was replaced with surfactants (-12) and (-13), which were added to give the same surface tension. Thereafter, an experiment similar to that in Example 1 was conducted, and the same results as in Example 1 were obtained. Example 4 Surfactants (-3), (-1), (-2),
(-10) was added at 0.1 g/each, Example 1
When an experiment similar to that was conducted, Example 1 Experiment No. 3
got the same result. Further, the surfactant (-
3), (-1), (-2), and (-10) were added, and the replenisher had a lower degree of coloration and was better than that without addition. Example 5 When the same experiment as in Example 1 was conducted by removing ethylene glycol from the color developer replenisher of Example 1, the low-temperature precipitation properties and evaporation precipitation properties deteriorated. Furthermore, it took a long time to dissolve the color developer replenisher. In addition, when the same experiment was performed in which this ethylene glycol was replaced with the same amount of diethylene glycol and triethanolamine, the solubility and PH stability of the replenisher were further improved. Example 6 Add 1 part of potassium bromide to the color developer replenisher of Example 1.
×10 ^-3 mol/, 2 × 10 ^-3 mol/, 3 × 10 ^-3 mol/, etc., and an experiment similar to Example 1 was carried out by adding 2 × 10 -3 mol/, 3 × 10 ^-3 mol/, etc. When the amount was ³ mol/less or less, the evaporation precipitation properties were particularly good. Example 7 3-Methyl-4 in the color developer replenisher of Example 1
-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate was replaced with 3-methyl-4-amino-N,N-diethylaniline hydrochloride and a similar experiment was carried out. Also, the crystal precipitation property and replenisher solubility due to evaporation were slightly deteriorated.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material containing at least one of an aminocarboxylic acid compound or an aminophosphonic acid compound and having a surface tension of 20 to 60 dyne/cm. Color developer replenisher. 2. A color development replenisher for silver halide color photographic materials according to claim 1, which contains a compound represented by the following general formula []. General formula [] R-O(-A) _o --(-B) _n --D [wherein R is an alkyl group having 4 to 25 carbon atoms which may have a linear or branched substituent or [Chemical Formula] (However, R ₁ and R ₂ 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.) A and B each represent [formula], and may be the same or different (however, n ₁ ,
m ₁ and l ₁ each represent 0, 1, 2 or 3).
D represents a hydrogen atom or _-SO3M (M represents a hydrogen atom, sodium, potassium, ammonium or lithium). n and m each represent 0 or an integer of 1 to 25. 3. Color development replenishment for silver halide color photographic light-sensitive materials according to claim 1 or 2, characterized in that it contains at least one of the compounds represented by the following general formulas [] to []. liquid. General formula [ ] [Chemical formula] In the formula, A ₁ represents a carboxylic acid group, a phosphoric acid group, or a salt thereof, and X represents a hydroxyl group or a salt thereof. B ₁ is a halogen atom, a hydroxyl group,
Represents an alkyl group, a carboxylic acid group, a phosphonic acid group, or a salt of a hydroxyl group, a carboxylic acid group, or a phosphonic acid group. r and l ₂ are 0 and 1 respectively
or 2, n ₂ represents an integer from 1 to 4, m ₂
represents an integer from 0 to 3. General formula [] [Formula] In the formula, R ₃ represents an alkyl acid or an amino group which may have a substituent having 1 to 5 carbon atoms. General formula [] [Formula] General formula [] [Formula] In the formula, R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, a halogen atom, a sulfonic acid group, or the number of substituted or unsubstituted carbon atoms. 1-7 alkyl group, -OR ₉ , -
COOR ₁₀ , [Formula] or represents a substituted or unsubstituted phenyl group. Further, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. 4. A color development replenisher for silver halide color photographic materials according to claim 1, 2, or 3, which contains a compound represented by the following general formula [] or []. . General formula [] HO(-A) _o3 --(-B) _n3 --H General formula [] N[(--A) _o --(-B) _n --H] In the ₃ formulas, n, m , A and B have the same meanings as the corresponding symbols in the general formula [], and n ₃ and m ₃ each represent 0 or an integer from 1 to 600. 5. The color development replenisher for silver halide color photographic materials according to any one of claims 1 to 4, which is substantially free of bromide.