JPH04204733A - Color development processing agent and method for preparing color development replenishing solution using same - Google Patents

Abstract

PURPOSE:To prevent occurrence of hardly soluble precipitates and insoluble oil-droplets ready to occur at the time of preparing a color developing solution by incorporating a specified surfactant in the color development processing agent comprising >=2 parts and substantially not containing benzyl alcohol. CONSTITUTION:This processing agent for color development replenishing solution comprises >=2 parts and at least one part contains an anionic surfactant and a nonionic surfactant having a carboxy, sulfo, phosphono, hydroxy groups, sulfate ester, or an alkyleneoxide structure in the hydrophilic moiety, and when it has a polymer structure, it has not a benzene ring or an N-containing substituent in monomer units, and each part does not contain substantially benzyl alcohol, thus permitting occurrence of hardly soluble precipitates and insoluble oil droplets to be prevented at the time of preparing the color developing solution and preparation to be facilitated.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a processing agent for color development of silver halide color photographic materials.

(Prior Art) Color development processing of silver halide color photographic materials (hereinafter sometimes simply referred to as color sensitive materials) has been progressing in recent years.
From the viewpoint of environmental conservation and processing cost reduction, research and development of low-replenishment processing, including the chemicals that make up each processing solution, is at the 9th speed. Among these processing solutions, the color developing solution in particular plays an important role in controlling the environmental conservation and reduction of processing costs, including the photographic performance of color sensitive materials.

Regarding this low replenishment amount processing, it is necessary to concentrate the components (chemicals) necessary for forming the color developing solution in order to maintain photographic performance etc. with respect to the low replenishment amount.

On the other hand, in the color developing solution used for processing color sensitive materials,
Including aromatic primary amine color developers, various preservatives for the purpose of preventing oxidation of color developers, various buffers to maintain the preferred pi for color development, other chelating agents, and preventing fogging. Used are halogen ions, organic fog suppressants, development accelerators, optical brighteners, etc. There are many types of chemicals that exist in color developing solutions.
As can be roughly guessed from the specific compound examples described below, there are some compounds that have poor solubility. Therefore, if the solution used to prepare the color developing solution is one part, and if you try to make it more concentrated, there is a limit to its concentration, and there are major problems with storage and handling, making it difficult to prepare the solution. do.

Therefore, color developing solutions are usually made up of kits consisting of multiple parts.
The liquid is prepared by mixing.

The same applies to the color developer replenisher.

Furthermore, the concentration of the chemicals used in these color developing solutions is higher in the replenisher than in the color developing solution, for example, with respect to the consumed color developing agent and preservative, by -fQ,L. Patent: In low replenishment processing, the difference in the concentration of the child is large, so the amount required for creating multiple parts is high. However, in color developing solutions, when the concentration of the drug in each part increases due to low replenishment processing. When preparing solutions using these, if stirring is insufficient or the order of addition is incorrect, or insoluble crystals may precipitate during mixing, or insoluble matter in the form of oil droplets may occur. In addition, if the temperature at the time of liquid preparation is increased to promote dissolution, problems may occur, such as accelerating the decomposition of the drug and increasing the burden on costs and equipment.

It has been found that this problem is especially serious when the replenisher has a high color developer concentration and a high pH. Furthermore, it has been found that when these solutions are aged, a problem arises in that the color developing agent precipitates, especially if the storage temperature is low.

Furthermore, Japanese Patent Publication No. 58-1 [1179] describes a method of dividing and adjusting the composition of a color developer into three parts, in which the precipitation of the developing agent in the color developer can be prevented by using a specific polymer. recorded. Furthermore, International Publication No. WO-8710,+S34 describes the use of a polystyrene polymer into which sulfonic acid groups have been introduced in a color developing solution that does not contain Hensyl alcohol; It is described respectively that the ionic concentration is defined and that a polystyrene polymer into which sulfonic acid groups are introduced is used.

(The problem with ff that the invention seeks to solve, however, is that as mentioned above, color developing agents become more concentrated due to low replenishment, and especially when the color developing agent is in a high concentration and has a high P content.
When preparing H color developing solution using a processing agent divided into two or more parts, using only the technique described in Section 5, insoluble compounds may be generated during preparation, or it may take a long time to dissolve, resulting in poor workability. It was found that it lowers the

On the other hand, regarding the prevention of crystal precipitation when the color developing solution becomes cloudy, for example, JP-A No. 53, 69 (135) describes the use of higher fatty acids and their salts, and JP-A No. 62-42154 discloses the use of higher fatty acids and their salts, and JP-A No. 62-42154 discloses the use of higher fatty acids and JP-A No. 62-56961 describes the use of nonionic or anionic surfactants having polyoxyalkylene groups to determine the bromide ion concentration and surface tension of the liquid. The use of a carboxylic acid or a salt thereof in combination with a polyoxene ethylene nonionic surfactant is disclosed in British Patent No. 669,505, the use of an alkylhenzenesulfonate is further described in U.S. Patent No. 4. No. 565,776 describes the use of diphenyl ether-based anionic surfactants substituted with alkyl and sulfonic acid groups, but these contain hensyl alcohol in the color developer, and the color development The concentration of the developer is also low, and the above-mentioned problems, particularly those that occur when a low replenishment type developer is prepared, cannot be solved.

Therefore, one problem to be solved by the present invention is that when preparing a color developing solution using a processing agent divided into two or more parts, M-soluble crystallized products and oil droplet-like insoluble The object of the present invention is to provide a processing agent for color development that prevents the generation of substances and facilitates liquid preparation.Furthermore, it is a replenisher for color development that has a high concentration of color concentrating agent and a high PH value, which is the most prominent problem in U4. An object of the present invention is to provide a processing agent for color development that is suitable for preparing liquids.

(Means for Solving !1 Problem) In order to achieve the above-mentioned problem, the inventors of the present invention have conducted various studies and found that a processing agent for a color development replenisher for silver halide color photographic light-sensitive materials has been developed. It is composed of the above parts, and at least one part has a hydrophilic group such as a carboxyl group, a sulfo group, a phosphono group, or even a hydroxyl group! , < refers to anionic surfactants and non-ionic surfactants that have a sulfate ester or algylene oxide structure, and if they have a polymer structure, do not have a Hensen ring or a nitrogen-containing substituent in the monomer unit. A color development replenishment prepared using a processing agent for color development, which contains at least one kind selected from ionic surfactants and in which each part does not substantially contain Hensyl alcohol. The concentration of the color developing agent in the solution is in the range of 9.0 g/1 to 16 g/l, and the pi
It has been found that the present invention can be achieved by using a processing agent for color development of silver halide color photographic materials, characterized in that t is 10.7 or more.

That is, the present invention provides a high-concentration and high-pH color development replenishment agent characterized by using the above-mentioned specific surfactant in a color development processing agent consisting of two or more parts and substantially free of Hensyl alcohol. Regarding processing agents for color developing agents for e-preparation, as mentioned above, there is a particular W problem when preparing low-replenishment type developing solutions in recent years, that is, preparing replenishing solutions with high color developing agent concentration and high pH. The above-mentioned problem that occurs when liquid is liquidized was first clarified in the present invention, and the effects of the present invention related to the presence or absence of Hensyl alcohol and a specific surfactant cannot be inferred from the above-mentioned known technology. do not have.

The present invention will be explained in detail below.

Each processing solution used in the color development process for color sensitive materials is
In recent years, with the exception of some large laboratory companies, most of them are supplied as one or more liquid preparations for the purpose of simplifying the liquid preparation work of laboratory companies.

The present invention relates to a color developing processing agent for preparing a color developing solution, and this processing agent is composed of two or more parts.

When a color developing solution is actually used in color development processing, the entire amount or specified amount of the processing agent consisting of two or more parts is weighed, mixed, and used as a color developing solution. As described above, by dividing the liquid into two or more parts, it is possible to stably increase the concentration of the liquid agent, which is advantageous.

When the composition of the solution for preparing the color developing solution is two parts or more, the combination of chemicals in each part can be, for example, the following combinations.

(For 2 parts) Part 1 Buffer, chelating agent, antifoggant, preservative, fluorescent whitening Part 2 Color developing agent, preservative (For 3 parts) Part 1 Preservative, Anti-fogging agent, fluorescent whitening remover 2 bar 1 Color developing agent, preservative 3 part II Shock agent, chelating agent, preservative (for 4 bars) part 1 Development accelerator part 2 chelating agent, The combinations of antifoggant, preservative, optical brightener 3, color developing agent 4, buffering agent, and alkaline agent are just one example each, but in the present invention, combinations can be further adapted to suit the purpose. Several combinations of 1 and 2 are possible. Furthermore, it is possible to use more than 5 parts, but as the number of parts increases, the complexity of liquid preparation work and the probability of making a mistake in the UiA liquid increases, so it is preferable that the processing side for color development consists of 2 to 4 parts. It is preferable that

When the processing side for preparing the color developing solution of the present invention is composed of two or more parts, one of the parts is an aromatic primary
When a replenisher for color development is prepared from a class amine color developer, it is 9.0g/l! ~16g#! Contains so that Preferred are P-phenylenediamine derivatives, typical examples of which are shown below, but the present invention is not limited thereto.

D-IN, N-diethyl-p-phenylenereamine D-22-amino-5-diethylamino)herene D-32-amino-5-(N-ethyl-N-laurylamino)toluene 1)-44-[ N-ethyl-N-(β-hy4'oxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline D-64-amino-3-methyl -N-ethyl-N-Cβ
-(methanesulfonamido)ethyl]-a,-phosphorus D-7N-(2-amino-5-diethylaminophenylethyl D-8N,N-dimethyl-p-phenylenediamine D-9 4-amino-3-methyl- N-ethyl-N-
Methoxystylaniline D-10 4-amino-3-methyl-N-ethyl-
NN--β-ethoxyethylaniline-11 4-amino-3-methyl-N-ethyl-N
-β-Butoxyethylaniline Among the above P-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-
(methanesulfonamido)ethyl]-aniline (exemplified compound D-6) and 2-methyl-4-[N-ethyl-N
-(β-hydroxyethyl)aminocoaniline (exemplified compound D-5).

Moreover, these P-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and P-toluenesulfonate.

Next, in the color development semi-preparation processing agent of the present invention comprising two or more parts, at least one of the parts is selected from a specific anionic surfactant and a nonionic surfactant. Contains at least one kind.

The specific anionic and nonionic surfactants of the present invention are those in which the hydrophilic part is a carboxyl group, a sulfo group, a phosphono group,
It is characterized by having a hydroxyl group or a sulfuric acid ester, or having an alkylene oxide structure, and when having a polymer structure, does not have a benzene ring or a nitrogen-containing substituent in the monomer unit.

Specific examples of the above-mentioned specific surfactants include the following compounds.

WI C+zLsCOONa W 2 Cl5H3tCOONaH3 Hff cH, CH2COOH CH co Na03SCHCOOC@ll+.

W -9C++LsCH-CHCLSO3NaW 1
0 C++HxsCHCHzCH1SO3NacH W-11selfJzsO(CHz)asOJaW 12
C+JssCONCHzCHzSOJaCH3 W 17 CJ1q 03Na W 25 CH*C00CJ+3N
a0sSCFICOOCJ+s W 26 C+J250SOJaW-27C
,,H,,O20,Na W-29Na0iSO(CiHt,0)tsO:+Na
W-30 funnel oil n'+n''+n'= 4 Wi4 80(Cl(2CH,O)r HW 3
5 HO(CthCHzO)-iUIIW-36
lo(CH3CH2O), (CICI+20)b
(CIIZC) 120) cHW 37
C+zHzsO<CH3CH2rJ) 1o
HW-38C+aLzO(CLCLO)zoHCHz
Ct(3 W-39CH3CH2-C-C=CC-CH□CLj These surfactants may be used independently, and 2
It is also possible to use a mixture of more than one species.

In the present invention, these surfactants can be used in a range of 0.001 to 10 g/l. Preferably it is in the range of 0.005 to i, Og/l. Added amount is 0
．． 001 g/I! If it is less than 10 g#, the effect on the stability of the liquid, which is the object of the present invention, will be small and unsatisfactory. If it is above, the solubility of the surfactant,
Foaming of the prepared color developing solution, sometimes resulting in decreased stability, can lead to other problems.

In addition, a surface active agent may be contained in 2 parts or more, but for example, 1 part) is an anionic surfactant, 2 part is an anionic surfactant,
A different surfactant such as Jl' ionic surfactant may be used in Bart, or it can be mixed and added to each part in arbitrary proportions.

In addition, in the present invention, the anionic group of the anionic surfactant may be the above-mentioned group or a salt thereof,
Salts of sulfonic acids are preferred. More preferred is an aliphatic or aromatic sulfonic acid or a salt thereof.

Further, the pi of the replenisher for color developing clear images obtained by mixing the above-mentioned parts needs to be 10.7 or more in order to obtain a sufficiently low replenishment treatment for the above-mentioned keyaki.

If the pt+ of the replenisher is lower than 10.7, the pH (for example, 9.5) required to maintain sufficient activity of the color developer (tank solution)
~1. In order to maintain o and o), for example, in color paper processing, a replenishment amount of approximately 100 to 150 d or more is required per processing, making it impossible to perform sufficiently low replenishment processing.

In order to achieve low replenishment of 100 d or less per treatment, it is necessary to use a replenisher having a pH of 10.7 or more as described in the present invention. Preferably 10.8 or more,
More preferably, it is 1140 or more.

Next, various additives involved in the preparation of the color developing replenisher of the present invention will be explained.

Various organic preservatives can be used for the purpose of preventing oxidation of the color developing agent. The organic preservative herein refers to any organic compound that slows down the deterioration rate of aromatic primary amine color developing agents.

In other words, it is an organic compound that has the function of preventing acidity caused by Q such as air in color development, but among them,
Hydroxylamine derivatives (hereinafter referred to as hydroxylamine), hydroxamic acids described in JP-A-63-43138, hydranones and hydrazide described in JP-A-63-146041 [, JP-A-63-44657 and JP-A-63]
Phenols described in No.-58443, No. 63-4465
It is preferable to add α-hydroxyketones and α-aminogetones described in No. 6 and/or various saccharides described in No. 63-36244. In addition, in combination with the above compounds,
JP-A-63-4235, JP-A No. 63-24254, JP-A No. 6
No. 3-21647, No. 63-146040, No. 63-
Monoamines described in No. 27841 and No. 63-21647, etc., diamines described in No. 6330845, No. 63-14640, No. 63-43139, etc., No. 63
-21647 and polyamines described in No. 63-26655, polyamines described in No. 63-44655, nitroquino radicals described in No. 63-53551,
It is preferable to use the alcohols described in No. 343140 and No. 463.53549, the oximes described in No. 63-56654, and the tertiary amines described in No. 63-239447.

Further, the amount of the following compound added to at least one part of the color developer processing agent consisting of two or more parts is 0.005 mol/l to 065 mol/l! , preferably 0.03 mol/1 to 0.1 mol/I! It is desirable to add it to a concentration of .

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

The hydroxylamine derivative is preferably one represented by the following -G formula (1).

General formula (1) In the formula, (2) represents a linear or branched alkylene group having 1 to 10 carbon atoms and may be substituted, and preferably 2 and 15 carbon atoms. Specifically, methylene, ethylene, propylene,
Butylene is mentioned as a preferred example. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, and an ammonio group which may be substituted with an alkyl group, and preferred examples include a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group. .

A is a carboxyl group, a sulfo group, a phosphono W, a bosphinic acid residue, a hydroxyl group, an amino group that may be substituted with argyl, an ammonio group that may be substituted with alkyl, a carbamoyl group that may be substituted with alkyl, or a carbamoyl group that may be substituted with alkyl. represents a sulfamoyl group which may be a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group, or an alkyl substituted 1
Preferred examples include carbamoyl groups which may be .

Examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group,
Preferred examples include a phosphonoethyl group and a hydrogynoethyl group, and particularly preferred examples include a carboxinmethyl group, a carboquinoethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. R is a hydrogen atom, carbon number 1-10
represents a straight-chain or branched optionally substituted alkyl group, preferably having 1 to 5 carbon atoms, and examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group which may be substituted with alkyl;
Represents an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, there may be two or more substitutions, R is a hydrogen atom, a carboxymethyl group, Carboxyethyl group, carboxypropyl group, sulfoethyl group,
Preferred examples include a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group, and a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group are particularly preferred. This can be cited as a preferable example. L and R may be connected to form a ring. These may also be alkali metal salts (eg, sodium, potassium, lithium).

Next, the long compounds of the present invention will be described, but are not limited thereto.

[−---−Mata−−−−−7−−−−−Rin−'−””””
−”””””−”””−””” ””−””'l' ”
””””' −””””−−|−””””−p ””
"""""'-'-ification, Yomono No., I-A
1r""'-(1""']""Q-4) -"""'
i""""'I-c""'fπl"'=-"'-'-
"""' -Trigram: H4♀(C"fHz)'-1・L (,,'-413'),,,,,,JC・-,,
N,(,C,H・)・ ,: -C2117,,,c:
? −〃−(]−53) )to−N )i
-C)1. C)1. cO211\-----''(1-5,111111-N':N-CH2Cl
1. SO,, Il\□□□□ (l-55>110-N', N-CII
zPOIfizV□□□ In addition, as hydrazine derivatives, for example,
The compounds described in PO254280A 2 ) are preferably used.

In order to improve the effect of the present invention, the color developing processing agent that is composed of two or more parts according to the present invention contains a compound shown in the following - Noshiro (A) as one of the two or more parts. It is more preferable to use it for at least part 1.

- Noshiro (A) In the formula, R11 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R1 and RI3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group, or a formula Alternatively, it represents a hydroxyalkyl group having 2 to 6 carbon atoms.

Preferred specific examples of the compound represented by -Noshiro FA) above are as follows.

(A-1) Ethanolamine, (A-2) Jetanolamine, (A-3) Triethanolamine, (A-4) Di-
Isopropanolamine, (15) 2-methylaminoethanol, (A-6) 2-ethylaminoethanol, (
A-7) 2-dimethylaminoethanol, (A-8)2
-dimethylaminoethanol, (A, -9) 1-diethylamino-2-propatol, (A, -10) 3--diethylamino-1-propatol, (A-11) 3-dimethylamino-1-propatol , (A-12) Isopropylaminoethanol, (Al
1) 3-amino-1-propatol, (A-14)
2-Amino-2-methyl-1,3-propanediol (A-15) Ethylene diamine isopropanol (A-16) Hensylethanolamine (A-17)
2-amino 2-(hydroxomethyl)-1+3-propanediol (A-18) L 3-diaminopropanol, (A
-19) 1.3-bis(2-hydroxyethylmethylamino)-propanol These compounds represented by the above-mentioned form (A) can be used in an amount of 3 to 100 g per If per liter that exhibits the desired effect of the present invention.
It is preferably used in a range of 2 parts or more (both are preferably used in 1 part, and more preferably in a range of 6 g to 50 g).

The color developing processing agent composed of two or more bars 1 according to the present invention can be used in the following formats [B-1] and [B-■] from the viewpoint that the effects of the present invention can be more effectively applied. It is more preferred to use at least one of two or more compounds.

One format: B-1)・H R+4 General formula [G]] In the formula, R14, R15, R1, and R17 are each a hydrogen atom, a halogen atom, a sulfonic acid group, and a carbon atom number of 1
~7 alkyl group, -'OR1m, represents a group. Also,
RI I, R1, , R7° and Rtl each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, if RIS does not represent -OH:i or a hydrogen atom, R3
4 is norogen, sulfonic acid group, number of carbon atoms 1 to 7
represents a furkyl group, -, , OR, ll.

The alkyl groups represented by R, d, R, , R1 and R1'l include those having substituents, such as methyl group, ethyl l, 1so-propyl group, n-propyl group, t-butyl group, n -butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, Hensyl group, etc., and also R1°, R19, Ro. The alkyl group represented by Rffil is as defined above, and further includes an octyl group.

Furthermore, the aryl groups represented by R34, RIS, R1 and RI7 include phenyl group, 2-hydroxyphenyl group, 4
-aminophenyl group and the like.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(B-1-1) 4-isopropyl-1,2-dihydroxybenzene (B-1-2) 1,2-dihydroxybenzene-3,5-25; soufflefonic acid (B-1-3)! , 2.3-) Lihydroxy-5-carboxylic acid (B-1-4) 1.2.3-) Lihydroxy-5-carboxymethyl ester (B-1-5) 1.2.34 Hydroxybenzene-5-carboxy-
n-Butyl ester (B-16) 5-t-butyl-1,2,3) dihydroxybenzene (B-1-7) 1,2-dihydroxybenzene-3,4,6-) lysulfonic acid (B-1 -8) 1.2-Dihydroxybenzene-4,6-disnomonophonate sodium (B-n-1) 2,3 dihydroxynaphthalene-6-sulfonic acid (B-It-2) 2.3.8-) Lihydrokizinaphthalene-6-sulfonic acid (B-II-31 2,3-dihydroxynaphthalene-6-carboxylic acid (B-11-4) 2,3-dihydroxo-8 isopropyl-naphthalene (B-n-5) 2.3-dihydroquine-8chloro-naphthalene-6-sulfonic acid Among the above compounds, compounds preferably used in the present invention include (B-1-2), (B-1-8) and (B-IT- 1) can be mentioned, and 2 can also be used with alkali metal salts such as sodium salts and potassium salts.

In the present invention, the above-mentioned format 1B-1) and CB-1
The compound represented by [1] can be used in the range of 5 mg to 15 g per li in at least 1 part consisting of 2 bar[· or more, preferably 1511 g to 1
It is desirable to use it in a range of 0 g, more preferably 25 mg to 7 g.

The replenisher for color development prepared using the processing agent for color development consisting of 2 parts and 1 or more of the present invention has a pll of 10
．． 7 or more, preferably pH 10.7 to 13.0,
It is more preferably from 11.0 to 12.0, and at least one part consisting of at least 2 parts may contain other compounds of known developer components.

In order to maintain the above pl+, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sulfurium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate,
Dipotassium phosphate, lithium borate, potassium borate, 1 lithium tetraborate (borax), potassium tetraborate, sodium 0-hydroquinobenzoate (1 salicylate)
potassium 0-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
etc. can be mentioned.

The amount of the buffer added to at least 1 part is 0.1
Mol/! The above is preferable in order to maintain buffering capacity at high pH, and particularly preferably 0.1 mol/β-0.4 mol/l.

In addition, at least one part of two or more parts is used as a precipitant for calcium or mag7sium, or to improve the stability of color developers.
[In addition to the following chelating agents, the following chelating agents can be used.

Specific examples are shown below, but are not limited to, nitrilotriacetic acid, diethylene I/liamine b acetic acid, ethylenediaminetetraacetic acid, triethylenetelamine hexaacetic acid, 21-lilo N, N, N-1 lis (methylenephosphonic acid), ethylenediamine-N, N, N', N'--
Tetrakis (methylenephosphonic acid), 1,3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid,
Glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroquinphenylacetic acid, 2-phosphonobutane-1゜2.4-1licarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis (2-hydroxyhensyl)
Ethylenediamine-N,N'-diacetic acid, catechol-3
, 4,6-) disulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid.

Among these chelating agents, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, and ethylenediamine-N are preferred.

N, N', N'-tetrakis (methylenebosphonic acid)
, hydroxyethyliminodiacetic acid is good.

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 at least one part of the color developing solution processing agent composed of two or more components. For example, it is about 0.1 g to 10 g per 11.

If necessary, any development accelerator can be added to at least one part of the color developer processing agent composed of two or more components.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, 38. ．． No. 7826, 44-12
No. 380, No. 459019 and U.S. Pat. No. 3,813,
thioether compounds shown in JP-A No. 247, p-phenylenediamine compounds not shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-1
No. 37726, Japanese Patent Publication No. 1977-30074, Japanese Patent Publication No. 1983
-156826 and 52-43429, etc., quaternary monoium salts, U.S. Patent No. 2.610
．． 1.22 and p- described in No. 4,119.462
Aminophe, nols, U.S. Patent No. 2,494,903
No. 3.128.182, No. 4,230.796, No. 3,253. ! lH9, Special Publication No. 41-11431
No. 2,482,546, U.S. Patent No. 2,596,
Amine compounds described in Japanese Patent Publication No. 37-16088 and Japanese Patent Publication No. 42-25
No. 201, U.S. Patent No. 3,128.318, Special Publication No. 4
Polyalkylene oxides shown in No. 141431, No. 42-23883, and U.S. Patent No. 3,532.501, etc., 1-phenyl-3-birapritones, hydrazines, meso-ionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

In the present invention, any part of the processing agent for preparing the color developing solution of the present invention does not substantially contain hensyl anocohol. "Substantially not containing" means that color developer I
The content is 2.0 or less per E, more preferably not at all. Substantially no content is advantageous in terms of ease of solution preparation and stability of the solution.Furthermore, when the prepared color developing solution is used, fluctuations in photographic properties during continuous processing, especially an increase in staining, can be avoided. Smaller, more favorable results are obtained.

For the purpose of preventing fogging, etc., it is preferable to use chloride ion and bromide ion in a color developer prepared using a color developer processing agent comprising two or more parts according to the present invention. In the present invention, the concentration in the color developing solution after preparation is preferably 1.0 x 10-'' as chlorine ions.
~1.5XIO-'mol/l, more preferably 5X10
-''~lXl0-' mol/l.If the chlorine ion concentration is more than 1.5X10' mol/l, it has the disadvantage of delaying development.
If it is less than
Continuous photographic fluctuations (especially minimum density) are large;
Undesirable.

In the present invention, preferably 3.0X10-'mol/l-1,0X10-'XI of bromine ions are added to the color developing solution.
O-'mol/l, more preferably 1.0X10-
'~3XIO-'mol/l. Bromine ion concentration is I
X 10-'mol/I! If the amount is higher, development will be delayed and maximum density and sensitivity will be reduced.7.3. O x 10-'
Mol/I! ．． If it is less than 2, it is not possible to prevent staining and furthermore, fluctuations in photographic properties due to continuous processing become noticeable, which is not preferable.

Here, the chloride ions and bromine ions may be directly added to at least one part, or may be prepared and extracted from the light-sensitive material during development when a color developer is used.

When added directly to at least one of the two or more parts, sodium chloride,
Examples include potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred are sodium chloride and potassium chloride.

It may also be supplied in the form of a range of optical brighteners added to at least one of the two or more parts. With the bromide ion supply substance and L7, helium bromide, potassium bromide, ammonyl bromide A, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, dibromide, Kel, cadmium bromide , cerium bromide, and thallium bromide, among which preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during development, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

In the present invention, in addition to chloride ions and bromide ions, any antifoggant can be added to at least one of the two or more parts, if necessary.

As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used.

Examples of organic antifoggants include hensitriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenztriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole. Representative examples include nitrogen-containing heterocyclic compounds such as , 2-thiazolylmethyl-henzimidazole, indazole, hydroxyazaindolizine, and adenine.

At least one bar of the color developer processing agent of the present invention comprising two or more parts preferably contains an optical brightener, and the optical brightener is 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 10 g/l, preferably 0.
It is 1-6 g/l.

In addition, polyvinyl alcohol, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide,
Various known water-soluble polymers such as polyvinylpyrrolidone or a copolymer thereof, arylphosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, etc. may be added.

As the silver halide used in the present invention, silver chloride, silver bromide, silver (iod)chlorobromide, silver iodobromide, etc. can be used, but especially for the purpose of rapid processing, silver iodide can be used substantially. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content of 90 mol % or more, more preferably 95 mol % or more, especially 98 mol % or more.

In the photosensitive material according to the present invention, a hydrophilic colloid layer is incorporated into a hydrophilic colloid layer for the purpose of improving image sharpness, etc.
．． 337.49OA2, pages 27 to 76, dyes that can be decolorized by treatment (especially oxonol dyes) are used to produce optical materials whose optical reflection density at 680 nm is 0.
170 or more, or 12% by weight of titanium oxide that has been surface-treated with di- to tetrahydric alcohols (e.g. trimethylolethane) in the water-resistant resin layer of the support.
It is preferable to contain at least 14% by weight (more preferably at least 14% by weight).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277.589A2 together with a coupler.

Use in combination with the patented pyrazoloazole coupler is preferred.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

In addition, the photosensitive material according to the present invention contains an anti-mildew agent as described in Kikai No. 63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration. It is preferable to add.

In addition, the support used in the light-sensitive material according to the present invention is a white polyester support for display or a support in which a layer containing a white pigment is provided on the support on the side having a silver halide emulsion layer. may also be used. In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support.

In particular, it is preferable to set the transmission density of the support in the range of 0.35 to 0.8° so that the display can be viewed in both reflected light and transmitted light.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-intensity exposure or high-intensity short-time exposure, and especially in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 seconds is preferred.

Also, upon exposure, U.S. Patent No. 4,880,726
It is preferable to use the Hunt-Stomb filter described in No. This eliminates optical color mixture and significantly improves color reproducibility.

Exposed light-sensitive materials can be subjected to conventional black-and-white or color development processing, but in the case of color light-sensitive materials, for the purpose of rapid processing, it is preferable to carry out bleach-fixing processing after color development.
In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 6.5 or less, more preferably about 6 or less, for purposes such as desilvering.

The photosensitive material according to the present invention is applied to the silver halogen emulsion and other materials (additives, etc.) and photographic constituent layers (
(N arrangement, etc.), as well as the processing method and processing additives applied to process this sensitive material, the following patent publications,
In particular, European Patent EP0.355.66OA2 (Patent Application No. 1
-107011) are preferably used.

Furthermore, as a cyan coupler, in addition to the diphenylimidazur cyan coupler described in JP-A No. 233144, the 3-cyan coupler described in European Patent EP 0.333.185A2 is also used.
Hydroxypyridine cyan couplers (among them, the 4-equivalent coupler of coupler (42) listed as a specific example has a 7-equivalent coupler with a chlorine leaving group), and couplers (6) and (9) are particularly useful. preferred) and JP-A-64-322
Cyclic viscous methylene/uncoupler described in No.
．． 34 is particularly preferred).

(Examples) The present invention will be described below with reference to Examples, but the present invention is not limited to these embodiments.

Example 1 Liquid preparations for each part consisting of the compositions shown below were prepared.

Part (1) Wednesday 8
00m benzyl alcohol (B2011) (1st
Table Reference M) Diethylene glycol (DEG) (
〃) At the water 1! part
(II) Water 7
00m Surfactant (See Table 1) Triethanolamine 200g Optical brightener 70g Preservative (1-7)
Add 200g water
Part 11 (I [l) Sodium hydrosulfite 4.0 g 4-Amino-3-methyl-N-ethyl-N (β-(methanesulfonamido)ethyl]-aniline sulfate (color developing agent) (see Table 1) Add water 11 Bart (TV) Water 7
00d Potassium hydroxide pH when mixing each part is 1
Ethylenediaminetetraacetic acid 60g Surfactant (see Table 1) Potassium carbonate
Add 540g water
,.

Store each of these pars in a plastic bottle, seal it tightly, and hold it at 25°
It was stored for one month under C conditions. After a period of time, to prepare a replenisher for color development, 00i of each bar was added to 1.6p of water in the order of Part (I), Bar) (n), Part (■), and Part (■). The solution was adjusted to 21 with water, and the state of dissolution was visually evaluated. However, if Hensyl alcohol and diethylene glycol are not used, do not use part (I) and use the remaining parts (■), part (■), and part (T).
Only V) was used.

. ;2K,V,;T:1zasa! -*.

藏 These results are shown in Table 1.

As is clear from Table 1, if the concentration of one color developing agent is 9.0 g/(!) or less, the melting state is good, and it can be seen that it deteriorates slightly due to the presence of Hensyl alcohol ( 1.2), and the effect of surfactants is not very clear (Na5, (old).

The color developing agent has a replenisher concentration of 9.0g/l! In this case, the dissolution state deteriorates significantly (N+13.4
).

However, in the presence of surfactant, 9.0 g/I
Similarly, it can be seen that a good dissolution state can be obtained (N
a8 to 14), it can also be seen that the presence of L or pencil alcohol almost eliminates the effect (comparison of numbers 7 and 8).

In addition, when amphoteric surfactants other than those of the present invention are used, insoluble compounds are formed especially during liquid preparation, which proves to be ineffective (No, 14.15). The structure of is shown below.

SO, O.

B, Cs41+ffO+CHtCHtO±1”'5
BD, C++HtsCHCH1COONaH Rate 0 (CH2CH1O)1CH,CH,CH2Cl'!
zso, NaF, HO+CLCLO-h-bH G, gu*-CHICH, CH, SO
,Na＞1Uno(i)CiL H1,C+aHx,05OJa Comparative compound> (a) Su3 CH3 (b) 11・G)I C+++Hz7CONI(C)IzCHzC]l□-N
-C11□coo QC11゜Example 2 Regarding sample M4 and failure 8 in Example 1, (II)
, (■), and (IV), and then add each bar 1- for 50 d each from (II) to (IV) at 40°C to prevent the formation of insoluble materials. Mix while maintaining the liquid temperature, make up to 1f with water, and then add p
H was adjusted as shown in Table 2, and a replenisher for color development was prepared. At this time, pH adjustment was performed using an aqueous solution of potassium hydroxide and sulfuric acid.

After adjusting the pH and completing the spinning, it was confirmed that there were no abnormalities in the condition of each color developing solution. Thereafter, it was stored in a sealed polyethylene L-N container and stored at 10°C for 15 days, and the stability of the colored visual solution over time was examined.

The evaluation was based on the following.

There is little coloration of the O solution, and no precipitate is formed.Δ There is coloration or turbidity of the solution. It is clear from the results in Table 2 that the prepared color developing solution has excellent stability when stored over time. In addition, if the prepared color developing solution has a pi value of less than 10.7, there will not be much problem with the stability of the solution. 1
When it is 0.7 or more, precipitation occurs in the solutions of Comparative Examples No. 4 and 4, but there is no problem in the case of the structure of the present invention (Na3). Furthermore, it can be seen that when the pH becomes high (pH 11.6 or higher), liquid coloration increases in Comparative Example Nα4, whereas the present invention exhibits excellent stability.

Example 3 The surfactant used in the experiment Ni1ll of Example 1 was used only in bar) (+>, and was changed to one with the following structural formula17.The amount added was 0.1 g/j'! When the dissolution state at this time was evaluated in the same manner as in Example 1, good results were also obtained.

The structural formula of the surfactant used is shown below.

H L, CzHz3CHyuCHCH! 5O3Kp+q
=20 Q.

C3H? Example 4 Color developer (D) of bar 1-(III) in Example 1
The same experiment as in Example 1 was conducted by changing the weight ratio of -6) to (D-6)/(D-5) = 6/4.

The results were exactly the same as those in Table 1.

Subsequently, using part (III) of the child chain, Example 2
I conducted a similar experiment, but the results obtained were similar to the second one.
We were able to obtain results similar to those shown in the table.

(Effects of the Invention) By using the processing agent for color development consisting of two or more parts according to the present invention, when preparing a color development solution, it is possible to prevent It prevents the generation of insoluble matter, can be easily prepared, and has excellent stability over time.

Furthermore, the processing agent of the present invention is particularly effective in preparing a low-replenishment color developing replenisher having a high color developing agent concentration and a high pH value of 4, where problems such as the generation of insoluble matter are noticeable. be.

Therefore, according to the present invention, it is possible to obtain a processing agent for color development that can be thickened, has excellent stability over time, and can be easily prepared in 1'-solution.

Representative Patent Attorney (6642) Toshio Fukasawa・Kane “(
,1'', N (and 3 others) -5- Procedural amendment dated February 1, 1991

Claims (2)

[Claims] (1) A processing agent for a color development replenisher for silver halide color photographic light-sensitive materials is composed of two or more parts, and at least one part has a hydrophilic group such as a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, or a sulfuric acid ester. anionic surfactants and nonionic surfactants that have an alkylene oxide structure and, if they have a polymer structure, do not have a benzene ring or a nitrogen-containing substituent in the monomer unit. A processing agent for color development of a silver halide color photographic light-sensitive material, characterized in that each part contains at least one selected from among these, and each part is substantially free of benzyl alcohol. (2) A replenisher having a color developing agent concentration in the range of 9.0/l to 16 g/l and a pH of 10.7 or more using the color developing processing agent according to claim (1). 1. A method for preparing a replenisher for color development of a silver halide color photographic light-sensitive material.