JPH0467038A - Color development replenishing solution for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain stable photographic performance in continuous processing by processing the silver halide color photographic sensitive material containing a specified compound with a color developing solution containing a water-soluble polymer comprising repeating units each having an anionic group. CONSTITUTION:The color development replenishing solution contains a buffering agent having a pKa of >= 10.5 and a surfactant and a color developing agent in a concentration of >= 2.0X10<-2> mol/l, and it has a pH of >= 11.0. In order to enhance an effect, the anionic surfactant is contained in the solution, preferably, in an amount of 0.02 - 2.0 g/l, thus permitting a sufficient amount of color developing agent to be dissolved in order to reduce the replenishing solution to an extremely small amount and deposition and precipitation not to occur even at low temperature and coloring deterioration to be not caused, even when a processing amount is small and the replenishment rate of the processing solution is lowered for a long period.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color development replenisher for silver halide color photographic light-sensitive materials, and more particularly to a replenisher for continuous processing. This technology relates to technology for preventing precipitation and coloring of the processing liquid during low-temperature storage.

[Background of the invention]

Processing of silver halide color photographic materials basically consists of two steps: color development and desilvering, and desilvering (=bleaching and fixing step or bleach-fixing step).

In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

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 dye to form a dye. In the second step, the silver halide produced by the reduction of silver halide dissolves and accumulates in the developer. 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, the silver produced by development is bleached with an oxidizing agent, and then all the silver salts are removed from the photographic material as soluble silver salts with a detergent.

A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously.

In the color developing solution, as mentioned above, development inhibiting substances accumulate during the development and processing of the photographic light-sensitive material, or the color developing agent and benzyl alcohol are consumed, or they accumulate in the photographic light-sensitive material and are carried out. The component concentration decreases. Furthermore, the pH also decreases due to hydrogen ions released by the development reaction.

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., the components of the color developer are kept within a constant concentration range in order to avoid changes in the development finish characteristics due to changes in component concentration. A means is needed to maintain it. As such, a method is usually used to replenish the missing components and to dilute unnecessary increased components with a replenisher. This method poses a major economic and pollution problem because a large amount of overcoat 70- is necessarily generated by replenishing the replenisher and is discarded.

Therefore, in recent years, in order to reduce the overflow liquid, methods for regenerating the developer using an ion exchange resin method or electrodialysis method, a concentrated low replenishment method, and another method include adding a regenerating agent to the overflow liquid and using it again as a replenisher. etc. have been proposed and put into practical use.

The developer is regenerated by removing eluates from the photosensitive material, which are unnecessary accumulated components, and replenishing the missing components.This method (ion-exchange resin method and electrodialysis method) It has the disadvantage that unless it is quantified and kept constant, the processing method of the photosensitive material will be damaged, and as it requires complicated management, it is rarely introduced in small-scale photo labs or mini-labs that do not have special skills. And it is impossible. Another disadvantage is that 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 is also complicated for photo labs. It is extremely difficult to introduce this into other areas. 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, in order to obtain stable photographic properties during continuous processing with an extremely small amount of replenishment, it is necessary to form the color developer replenisher into a highly concentrated solution. However, with conventional techniques, there is a limit to the solubility of color developing agents, and it has not been possible to achieve very high concentrations. Furthermore, even if dissolved, the color developing agent will precipitate when stored at a low temperature in the winter, which will reduce the concentration of the color developing agent in the replenisher, which will not only affect the finished development characteristics but also cause problems with the replenishment pump. The strainer, etc. of the
There is a problem that normal replenishment is not possible.

Furthermore, with the expansion of minilabs in recent years, the number of small-scale photofinishing labs (minilabs) with a small throughput is also increasing. In such a minilab with a low throughput, by performing a low replenishment process, the renewal rate of the replenisher decreases accordingly. In other words, it will be stored for a long period of time as a replenisher. Therefore, the replenisher becomes colored and deteriorates due to decomposition products of the replenisher components due to air oxidation or the like. If continuous processing is performed using such a replenisher, the color developing tank solution will become tarry, which will eventually cause stains in the processing tank and on the rollers, and this stain will damage the photosensitive material being processed. Failures occur that contaminate the materials. It also causes an increase in stain during continuous processing.

To solve these problems, JP-A No. 62-250444 discloses a method using alkanolamines, JP-A No. 63-32547 discloses a method using dialkylhydrokine lamino compounds, 63.48548 discloses a method using a preservative such as a hydranone derivative. However, none of these are dramatically effective, and adding too much of these preservatives inactivates the photographic performance, making them difficult to use and having the disadvantage of being costly. =.

[Problem to be solved by the invention]

Therefore, the first object of the present invention is to provide a silver halide color photographic sensitizer which is capable of dissolving a sufficient amount of color developing agent in order to extremely reduce the amount of replenishment and which does not cause precipitation or precipitation at low temperatures. An object of the present invention is to provide a color development replenisher for materials.

A second object is to provide a color development replenisher for silver halide color photographic light-sensitive materials that requires a small amount of processing and does not cause color deterioration over a long period of time even if the solution renewal rate decreases.

[Failure to solve the problem]

The present inventors have made extensive studies to achieve the above object, and as a result, have arrived at the present invention. That is, the color developer replenisher for silver halide color photographic light-sensitive materials according to the present invention contains a buffer agent and a surfactant with a pKa of 1015 or more, and has a color developing agent concentration of 2.0×10−.
It is characterized by being 2 mol/Q or more and a pH of 11.0 or more.

The pKa referred to here is a numerical value expressed as pKa −-12og+oK& with acid dissociation of HA#14++8-. H+ here represents an acidic type, and A- represents a conjugate base.

In order to better achieve the effects of the present invention, it is necessary that the surfactant contained in the color developer replenisher be an anionic surfactant, and that the color developer replenisher contain 0.01 to sg of the surfactant.
/l, and the content of the surfactant is preferably 0.02 to 2. (The range is h/Q.

In addition, the pKa of the buffer agent contained in the color development replenisher
It is essential that the pKa is 1015 or more, and the pKa is preferably 11. It is in the range of θ to 130. Furthermore, the pH is II
.

0 or more is essential, preferably in the range of 11.5 to 13.0. The amount of color developing agent is 2. OX 10-2 mol/
Must be Q or higher, preferably 2.3X 10
-'' to 46X 10-'' moles/Q.

It is well known that the solubility of a color developing agent can be increased by increasing the pI (pI), and that a buffer agent with a high pKa can be used to maintain the high pH. This allows color developer replenishers containing a high concentration of color developer to be stored for long periods of time without precipitation or sedimentation at low temperatures, and without coloring and deterioration of the solution. The improved stability was unexpected to the inventors.

The present invention will be explained in more detail below.

The surfactant used in the present invention is a so-called ampholytic substance that has two groups in its molecule, a parent group and a hydrophobic group, which have contradictory solubility in a solvent, and is water-soluble.

Surfactants are divided into ionic surfactants and nonionic surfactants depending on whether they exhibit ionicity in aqueous solution, and ionic surfactants are further divided into ionic species that exhibit surface activity in aqueous solution. They are divided into anionic surfactants, cationic surfactants, and amphoteric surfactants. Any of these surfactants can be used to achieve the purpose of the present invention, and two or more types can also be used in combination.

As surfactants preferably used in the present invention, compounds represented by the following female mosquitoes [I] to [XI] - female mosquito CI) is a monovalent organic group, such as an alkyl group having 6 to 50 carbon atoms, preferably 6 to 35 carbon atoms (for example, 6 groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, or F-decyl) or 3 to 3 carbon atoms; It is an aryl group substituted with a 35 alkyl group or a noalkenyl group having 2 to 35 carbon atoms.

Preferred groups to be substituted on the aryl group have 1 carbon number.
~18 alkyl groups (e.g. methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,
unsubstituted alkyl groups such as de/ru, undecyl or dode/ru), substituted alkyl groups such as benol, phenethyl, or alkenyl groups having 2 to 20 carbon atoms (e.g. unsubstituted alkenyl groups such as myoleyl cetyl, allyl group, etc.); group, substituted alkenyl group such as styryl group).

Examples of the aryl group include six groups such as phenyl, biphenyl, and s7tyl, with phenyl being preferred. Aryl group! The position for this substitution may be either the ortho or meta-para position, and a plurality of groups can be substituted.

B and C are each an ethyleneoxy group, a globyleneoxy group, a trimethyleneoxy group, or 01 is 0, 1.2 or 3, and p is 0 or 1. ) m and n represent integers from 0 to 100.

X is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and examples thereof include the groups explained in A.

Female Mosquito [■] RIX (Elya E 2) - (E - R2 - Female Mosquito [■] R2
is a propylene oquin group, R3 represents an ethyleneoxy group, X represents a carbonyloxy group, -〇- or -N- group, R1 is an aliphatic group, a hydrogen atom, or an aliphatic group, a hydrogen atom, or an aliphatic group,
E' represents number i, and R' represents a hydrogen atom or an aliphatic group.

Q1+ 02+ 111+ m! +n and n each represent an integer from 0 to 100.

General formula CI[[] R'-(X -L)-COOM In the general formula (I[I), R1 is an aliphatic group (e.g., saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group) , X represents -CON- or SO2N-, R2 and R3 each represent a hydrogen atom or a group defined in R1), Q is O or 1, and M is a hydrogen atom or an alkali metal atom ( For example, Na1%')
, ammonium ion or organic ammonia shell Formula (IV) , straight chain or minute is 1000-
R2 and R3 each represent a hydrogen atom or a group defined in R1), g and m are each 0 or 1, and L
represents an alkylene group, Y represents an oxygen atom, and M represents an alkali metal atom (for example, Na.

K, Li, etc.).

General formula [■] A' (CH2CH!Ot S Os M-female mosquito (
V), M is an alkali metal atom (e.g. Nas
Ks Ll, etc.), where n is an integer from 1 to 100,
A is a monovalent organic group, for example an alkyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms (e.g., a polygroup such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), or Substituted with an alkyl group having 3 to 20 carbon atoms! It is a nearyl group, and the substituent is preferably an alkyl group having 3 to 12 carbon atoms (for example, a polygroup such as methyl, butyl, pentyl, hequinyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). The aryl groups include phenyl, tolyl, quinyl,
Examples include multiple groups such as biphenyl or naphthyl, preferably phenyl or tolyl.

The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta, and para positions.

Female mosquito [■] R3 In the female mosquito (VT), R, , R, and R1 are each substituted or unsubstituted alkyl group, and R1 and R2, or R2
and R3 may each form a ring. A is −((J
l)n (R* represents a hydrogen atom or an alkyl group, n
l! 1.2 or 3).

- Numerical formula [■] In the general formula [■], Ro has the same meaning as A in the general E[:l. R2 represents a hydrogen atom or an alkyl group (e.g., methyl group, ethyl group), m and n are each 0.1 or 2
and A is an alkyl group or a substituted or unsubstituted aryl group.

X is -COOM or -5o, )I, and M represents a hydrogen atom or an alkali metal atom.

General formula [■] R, -N-R, -Xe R3 In general formula [■], R+, R2, R3 and R4
each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group.

) (e represents an anion such as a halogen group, a hydroxyl group, a sulfuric acid group, a carbonic acid group, a nitric acid group, an acetic acid group, or a p-toluenesulfonic acid group.

General formula (II) R, -CH-C0AR1 R2CHC00R4 In the general formula [C], one of R1 and R2 is a hydrogen atom or an alkyl group, and the other is a formula -5o3M (M represents a hydrogen atom or a -valent cation ).

A represents an oxygen atom or a group represented by the formula -N(Rs)- (RS represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

R1 and R4 each represent an alkyl group having 4 to 30 carbon atoms. However, the alkyl group represented by R, R4 or R5 may be substituted with a fluorine atom or a hydroquine group, and an oxo group may be present between the carbon atom chains of the alkyl group.

- Formula (X) - Formula 〇m) Compound represented by formula (1)) In the general formulas [X] and [■], R,,R,.

R3, R and R6 each represent a hydrogen atom or an alkyl group, and M has the same meaning as M in general formula CIII). n and p each represent an integer of 0 to 4, 1≦n+p≦8
This is a value that satisfies the following.

Examples of the compounds represented by the general formulas [■] to (I[) are listed below, but the invention is not limited thereto.

CstH2s Oi C2H, O juice “HCJ, 7-O
-(C3Ha T "H CsH+ s o-cc, t+, osu, HC+oHz
+ 0 (CJ+0 juice ``H ■ C12H2Sba21(, O car H ■ C,H,th leaf fCz f(,O+Vr-H■ Ca Hl 7 o-+c2 Ht 0TrH■ CI OH21ba, H,0te toH ■ CI2HIS Kanabao 2H10 sho "H C,, H,, o-+C, H, Ou,, 0 ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ 4] ■ H Su1" JH Jl -1 ■ iI ■-46 (n)C+xHzt O(CI(zCH2, HC,
2H□-0-(CH2Cl(, O juice, HCl)137
0iC1+2CH20)-,-1-H(b)C,oH
2,-0-(CH,CH20i1((n)C,6H3s
-0(CH2CH20 catty H(n)C+ 2H2s-0
-(CH2C)ICH, O piece H(n:)C+ 2H2s
0-rco, c■c11□oh CH=CI120
:)r HH (n)C,3H2+ O(CI(2CH20VI(■ ■ ■ ■ ■ ■ Lll.

■ ■ ■ ■ (-Compound represented by Formula 1F-1 (I[)) CI 2) I! 5cOo(CJ*0hy)1C*Hr
*C00ICzH*O+r-'ACI! Hx 1NH
(: C2H40 Juice rH1[-4 C+2HziNH+CJaO Masu rH CH.

■-22 1 (0 I? HC) 1.0 CH2C) 1.0 sun H ■ HObeC,) 1.0 employment? HCT(,OpresentingC,H,O7H
CH.

CIJ! 6 NHCHzCHzOH ■ HOiCHC) 1,0←→CH2CH2O dry H116,
4 CH3 I [-10 HO ball C) IcH, Kano-Yun C) l, CLC)) π■HC
H.

l-11 HO(CHCH20廿CH,CH2吋[HCH.

■-12 80 pe CHCH, O 廿CH, CH, 0 sun HCH.

■ 1(0-(blank 1, snout T(C1(:CH, 噌 CH3 CH.

(-compound represented by formula (III)) I[[I C
+2H2s So2NHCH2CHzCOONam-2
C,,)12. CC00N a 3 CIsHztCOOK ml -4CI 7)+35cONHc)IzCHzC
○ONa! [15C+7H3sCON CtbC○ON
aH3 116C17) 133CON CI(2COO)lCH
.

(Compound represented by - formula (TV)) V-1 C+7H3sCONa V-2 CI+Hz3CONHCH2CJO5O3NaIV-3 IV-4 IV-5 IV-6 ClzHz 1cONH (C8zcHxo%C) I z
cHxO5Os NaCtJxsO5OINa C+ 1F123c00cH2cH(○H)C)I20
SO3NaCIrgo3CON C'A2CH2SO
3NaCH.

■-7 C+2Hzh -CON-C)1. CH,5OJaCH
2CI120H IV-9 IV ■ C+Jss CON co2c)12so, l(C
,H.

CzHzZ CON CHzSO,NaCH3 C+2Hzh CON CH2Cl(2SOzNa
CH1 (compound represented by general formula [■]) CJ+s○(C2H,0)lsO3NaC,OH210
(C:HIO) l sso, NaC, H.

C no HI CH3 T-5 C1,)1. ! -48-C)I, CooeCH.

(C2H, O optical unit C+2Hzh,% C)12cOQe(C21(,0
-)n-H (Compound represented by general formula [■]) ■-I C+2Hzh N(C4CHzCOON
a).

■-2(+7HssNHCH2CH2SO3Na■C+ 2H!5O(CJIO-47-5O3Na (compound represented by general formula [)) CH.

(General formula compound represented by) 12t,,n2un ■ ■ C■.

C+aHx7N Czlls CI(.

Br” II3 ■ (Compound represented by - formula [Go]) I-1 ■ Go ■ f-5 ■ ■ ■ Compound represented by formula [X]) Compound represented by formula) ■ ■ +1 1 !-13 ■ ■ ■ Go10 ■ ■ SO, Na 5S, Na The content of surfactant in the color developer replenisher of the present invention is 0.
O1 to 5.0g/12 is preferable, more preferably 0.0g/12.
02~2°Og/Q. The content of surfactant is 2
If it exceeds 0 g/12, there is a problem of precipitation and cloudy liquid, which is not practical.

Nonionic and anionic surfactants are preferably used as the surfactant for use in the present invention, and anionic surfactants are particularly preferred since they exhibit the effects of the present invention.

When a cationic surfactant is added to a color developer replenisher, it may form a precipitate during continuous processing.

Further, in order to further enhance the effect of the surfactant according to the present invention, a substance generally called a builder can be used in combination. Builders include carbonates such as soda carbonate and sodium bicarbonate, silicates such as sodium metasilicate, sodium orthosilicate, and sodium sesquisilicate, and inorganic phosphates such as sodium pyrophosphate, sodium tripolyphosphate, and sodium tetraphosphate. There are builders and organic builders represented by carboxymethyl cellulose, mecarpoxymethyl starch, etc., and any builders can be used, but organic builders are preferred as they provide the effects of the present invention. Solutions containing surfactants are generally known to foam, but in the case of photographic processing solutions, foaming is often a disadvantage, so antifoaming agents may be used as necessary. can.

The buffer agent as used in the present invention refers to a substance that is resistant to changes in the concentration of free hydrogen ions in a solution. The buffering capacity of a buffering agent is generally in the range of approximately the acid dissociation constant pKa±l of the substance, with the maximum capacity at pH=p
It's at Ka.

Among these buffer agents, those having a pKa of 1000 or more can be added to the color developer replenisher to satisfactorily achieve the object of the present invention, and two or more types can also be used in combination.

Buffer agents preferably used in the present invention include the following buffer agents having a pKa value of 10.5 or more. The buffer agent may be used in the form of a salt such as Na salt or K salt.

The buffer agent to be contained in the phenomenon replenisher of the present invention has a pea of 1015 or more as described above, preferably has a pKa of 11.0 to 13.0, and most preferably phosphoric acid. be.

In the color development replenisher of the present invention, JP-A-63-1
No. 46043, No. 63-146042, No. 63-14
No. 6041, No. 63-146040, No. 63-135
No. 938, hydroxylamine derivatives described in No. 63-118748, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, a-ami7 ketones, described in JP-A No. 64-62639,
Saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines, and the like are preferably used as organic preservatives.

In particular, when a compound represented by the following formula [A] or (B) is contained, it is preferable for rapid processing and reduction of bluing, and is also good for crystal precipitation on the liquid surface of color development replenisher types. This is cited as one of the more preferred embodiments of the present invention.

General formula (A) In formula (A), R1 and R2 are each an alkyl group, an aryl group, or R'-CO- which is not a hydrogen atom at the same time.
1 or a hydrogen atom, but the alkyl groups represented by R1 and R2 may be the same or different, and each has 1 carbon number.
~3 alkyl groups are preferred.

R' represents an alcohol, an alkyl group or an aryl group.

The alkyl groups and aryl groups represented by R, Rffi and R' include those with substituents, and R1 and R8 may be bonded to each other to form a ring, such as piperidine,
It may also constitute a heterocyclic ring such as pyridine, triazine or morpholine.

Specific examples of the hydroxylamine compound represented by formula [A] are disclosed in U.S. Pat. No. 3,287.125, U.S. Pat.
No. 293,034 and No. 3,287.124, etc., and particularly preferred specific exemplary compounds are shown below.

CH, Co-NHOH Formula (B) In the general formula CB), R, R2 and R1 are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocycle (represents a group) Ri is a hydroquine group, a hydroquine amino group,
Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloquine group, substituted or unsubstituted carbamoyl group, or amine Represents 7 groups. The heterocyclic group is a 5- to 6-membered ring, composed of C, H, O, N, S, and halogen atoms, and may be saturated or unsaturated. R5 represents a divalent group selected from -co-, -5o2 or -C(-NH)-, and n is O or l. In particular, when n-00, R1 represents a group selected from an alkyl group, an aryl group, and a petero ring;
and R2 may jointly form a heterocyclic group.

- In formula CB), R+, R2 and R1 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and most preferably R1 and R2 are hydrogen atoms.

In the general formula CB), R1 is preferably an alkyl group, an aryl group, a carbamoyl group, or an amino group, and particularly preferably an alkyl group or a substituted alkyl group. Preferred substituents for the alkyl group include carboxyl group, sulfo group, nitro group, amino group, and phosphono group.

Specific examples of the compound represented by formula CB) are shown below.

NH,NH-(CH2÷"S○,H NH2NH-(CH2chirOH NH,NHCOCH3 NH2NHCOOC:R5 N82 NHCONH2 NH2NH5O,H N.H.

N82NHCN)+2 NH2NHCOCONHNI(.

N82Nl(CH2CH,CH,S○3HHOOCC8
2N)INHC)I2COO)INH,NHCI(2C
H,Coo)I C61(+3(n) H2NNHCHCOOH CJI+(n) H,NN(CHC○0H)2 HzNN(CHzCHzSOxH)z C2H.

H2NN(CHC○0H)2 →CH.

N-CI (2C) 12 children ■ N1 (2 Average molecular weight approximately 4000 These compounds represented by formula (A) or formula CB) are usually free amines, hydrochlorides, sulfates, p-toluenesulfonates. It is used in the form of , oxalate, phosphate, acetate, etc.

The above formula (A) or formula (B) in the color developer replenisher
The concentration of the compound represented by is usually 0.2 to 50 g/(1
, preferably 0.5 to 30 g #, more preferably 1 to 1
5g/(l).

Further, the compound represented by formula [A] or formula CB) can be used in combination with conventionally used hydroxylamine and the above-mentioned organic preservative, but preferably hydroxylamine is not used. This is preferable from the viewpoint of developability.

The color developer replenisher of the present invention has the following formula [CD or C
When the compound represented by D) is contained, it is preferably used because it exhibits an effect of improving the air oxidation of the color developer replenisher and has almost no adverse effect even if mixed into the bleach-fix solution.

- Formula (C) In the general formula (C), R1 is a hydroxyalkyl group having 2 to 6 carbon atoms, R3 and R1 are each a hydrogen atom, and 1 carbon number
-6 alkyl group, hydroxyalkyl group having 2 to 6 carbon atoms, benzyl group or an integer of, X and Y are each a hydrogen atom,
It represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.

Preferred specific examples of the compound represented by the above-mentioned formula [CD] are as follows.

C-1 Ethanolamine C-2 Jetanolamine C-3 Toethanolamine C-4 Di-isopropanolamine C-52-Methylamine Ethanol C-62-Ethylaminoethanol C-72-Dimethylaminoethanol C-82 -diethylaminoethanol C-91-diethylamino-2-propatool C-10
3-diethylaminopropanol c-1t 3-
Dimethylamino-1-propatol C-12 Isopro and Ruaminoethanol C-133-Amino-1-propatol C-142-Amino-2-methyl-1,3-propazinol C-15 Ethylenediamine Tetrain Propanol C -16benzyljetanolamine C-172-amino-2-(hydroxymethyl)-1,
3-Propanediol General formula CD) H-O-A+-(0-B'+-OH nm In the general formula (D), A and B each represent a linear or branched alkylene group, and n and m are Each represents an integer from 0 to 100. However, both n and m cannot be 0.

Preferred specific examples of the compound represented by formula CD) are as follows.

HO-C)1. CH, -0)1 Hs 80-C)1. CIhCH, -OH CH.

HO-CH2C)IC)I2-OH D! ll CH.

)10-C)ICH2C1(-OHD CH.

140　Cf(zcH2cl(xcH20HCH.

HO-C)ICH, C)12C)I2-0)ICH.

110-C) 12cHcH2CH, -0HCH, CI(
.

HO-CHCH2CH2CH-OH HO-CHCH, -0H CI(.

CH3 HO-CHC)1. cl(, -0H CH3 )10-CHCHCH2-OH CH.

CH.

HO-C-CH2C1+2-0H CH.

D-15 HOCHCHzCHCl(zOFIHOCHgCH
OCHCHz 0H CH.

CH.

8O-CH-CHCH, CH2-0H CH.

CH3 HO-CHICHCHCHy-0H C.F.I.

HOCHzCHz　OCH:CH20HH3 HO-CHCH! -0-CHICL -0HCH.

FIO-CM2CH-0-CH, CH2-0)ICH.

HO-CHCH2-0-CHCt12-0)ICH.

HOCHzCHtCHz OCHzCHx 0HH
OCHxCHzCHz OCdayxcHtcH*
OHH gorge CHtCHzO-H n=3 H gorge CH, CH, O square? -1(HO(-CH,CH,O□H n 7)10(CHgCH2)rH HO(CHzCHzO-H n=12 HO(CH2CH,O sho rH HO(CH2CHzO sho rH CH.

HO+CH2CHzOh-H HO-CHCH2-0-CH, CH-OHCH.

From the viewpoint of preventing air oxidation, the compound represented by formula [C] or CD) should be added in an amount of 1 to 100 ml per 1Q of color developer replenisher.
It is preferably used in the range of 2 to 50 g, more preferably 2 to 50 g.
It is used in the range of g.

The color developing agent used in the color developer replenisher of the present invention is:
A p-7 nylene diamine compound having a water-soluble group is preferable, and the water-soluble group is at least one on the amino group or benzene nucleus of the p-7x nylene diamine compound, and the specific water-soluble group is As a group, (C4)n CHzOH.

(CHx)m　NH30z　(CHz)n　CHx.

(CHz)m　O(CL)n　CHs.

(CH2CH3O)ncmHlm, + (m and n each represent an integer of 0 or more), -COOH group, -5O
Preferred examples include 3H group.

Specific examples of color developing agents preferably used in the present invention are shown below.

(Exemplary color developing agent) (A-1) C・H・＼ノ・H・NHSO・CH・ (A CxH&X),)1. OH C・1・＼ノ・1・0H to (A-4) C・H・℃ME・H・OCH・ issue C・H6℃Me・H・SO・H M CH・＼ノ・H・OH )10H-C2Xノ,H,O)I to (A-8) C・H・＼ノ・H・so・H Enter C, H, (CH2C)120), C, H.

C,) IS entered/(CHjCH20), C,H.

(A-15) C2Hs,,,乃H,N)IsO,CH.

niC・H・\ノ・H・OH (A C,H,ノ,H65O3H H2 (A-10) H\noH・C0OH Among the above-mentioned color developing agents, preferred for use in the present invention are the exemplified No, (A-1), (A-2), (
A-3), (A-4), (A-6), (A-7) and (p, -15), with No. and (A-1) being particularly preferred.

The above-mentioned color developing agent is usually used in the form of a salt such as hydrochloride, sulfate, p-toluenesulfone salt, or the like.

In the present invention, the p-phinidine diamine compound having a water-soluble group that is preferably used is the color developer replenisher 1.
2 per 0. It is necessary that OX 10-" moles or more, preferably 2.3X 10-" to 4.6X 10-"
It is in the molar range.

The color developer replenisher used in the present invention may contain the following developer components in addition to the above components.

Inorganic and organic antifoggants can be added if desired. Further, a development accelerator can also be used if necessary.

As the development accelerator, U.S. Pat. No. 2,648.604,
3,671,247 and Japanese Patent Publication No. 44-9503, other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate, and U.S. patents. 2゜533
．． No. 990, No. 2,531,832, No. 2,950.
No. 970, No. 2゜577127 and Special Publication No. 1977-1995
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 04, phenethyl alcohol and others described in U.S. Patent No. 2,304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, Examples include pyridine, ammonia, hydrazine, and amines.

Benzyl alcohol is not preferred for use in the present invention;
In order to efficiently achieve the object of the present invention, it is preferable to eliminate the use of poorly soluble organic solvents such as phenethyl alcohol.

Due to the long-term use of the color developer replenisher, tar is likely to be generated, especially during running processing using a low replenishment method, and such tar adheres to the paper photosensitive material to be processed, significantly impairing its commercial value. This can even lead to serious malfunctions.

In addition, poorly soluble organic solvents have poor solubility in water, which not only requires a stirring device to prepare the color developer replenisher itself, but also the use of such a stirring device does not easily dissolve the solution. Due to the poor rate, there is a limit to the development promotion effect.

Furthermore, poorly soluble organic solvents have low biochemical oxygen demand (B
Benzyl alcohol In addition, it is preferable to reduce or eliminate the amount of other poorly soluble organic solvents used as much as possible.

The color development replenisher of the present invention preferably contains a triazinylstilbene fluorescent brightener.

As the triazinylstilbene fluorescent brightener, those represented by the following formula [E] are preferred.

Numerical formula [E] In general formula [E], X 1. X x, Y +
and Y2 are each a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group (e.g. methyl, ethyl, etc.), an aryl group (e.g. phenyl, methoxyphenyl, etc.), where R1
1 and R12 each represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, R13 and Ro each represent an alkylene group that may have a substituent, R21 represents water 11i, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and M represents a cation (eg, sodium, potassium, lithium, ammonium, etc.). R21, R2□ and Ro
The argyl group represented by preferably has 1 to 6 carbon atoms, and the alkylene group represented by R0 and R14 above preferably has 1 to 2 carbon atoms.

Above R! l+R! ! Substituents for the alkyl group and aryl group represented by and Ro, and the alkylene group represented by Rts and R1, include a hydroxy group, a sulfo group,
Sulfamino and carboxyamino groups are preferred.

Amino groups (e.g. methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β
-hydroxyethylamino, di(β-hydroquinethyl)amino, β-sulfoethylamino, N-(β-sulfoethyl)-N-methylamino, N-(β-hydroxyethyl-N-methylamino, etc.), or Arylamino group (
For example, anilino, o-, +n-.

p-sulfoanilino, 0-9rrl-3p-chloroanilino, o-.

m-, p-toluidino, o-+ ”-r p-carboxyanilino, olm, p-hydroquinanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o
-+ m-+ p"anilino, etc.), and specific examples of -0R1 include alkoxy groups (
Examples include methoxy, ethoxy, methoxyethoxy, etc.) and aryloxy groups (eg, phenoxy, p-sulfophenoxy, etc.).

A preferred compound of the optical brightener represented by the above formula is one in which X, , X, , y, and Y are all the same, and the most preferred compound is one in which X and Yl are -OR When one of and Y is 10R1°, the other is.

Specifically, the following compounds may be mentioned, but the invention is not limited thereto.

The triazinylstilbene-based brightener preferably used in the present invention can be synthesized, for example, by the usual method described in "Fluorescent Brighteners" edited by the Japan Chemical Industry Association (published in August 1976), page 8. can.

Among the exemplified compounds, E-4 is particularly preferably used.
E-24, E-34, E-35, E-36, E-37,
E~41.

The choleratriazinylstilbene brightener is preferably used in an amount of 0.2 to 10 g, more preferably 0.4 to 5 g, per color developer replenisher II2.

Furthermore, the color developing replenisher used in the present invention may include methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and others described in Japanese Patent Publications No. 47-33378 and No. 44-9509, if necessary. can be used as an organic solvent to increase the solubility of the developing agent.

Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, tlfN-methyl-p-aminophenol hexulfate (methol), phenidone, N,N-diethyl-p-aminophenol hydrochloride, N,N,N',N'- tetramethyl-p
-Phenylenediamine hydrochloride etc. are known, and the amount added is usually 01 to 1. Og/Q is preferred.

Furthermore, various other additives such as anti-staining agents, anti-sludge agents, interlayer effect promoters, etc. can be used.

Further, from the viewpoint of effectively achieving the object of the present invention, it is preferable that a chelating agent represented by the following formula (K) be added to the color developer replenisher of the present invention.

General formula [K] In formula (K), E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R, OR,
-, -R, OR6○R1 or -R, ZR5-, Z
represents >N-R5-As or >N-A, R1-R
5 each represents a substituted or unsubstituted alkylene group, A, ~
As each hydrogen thickness, -OH, -COOM and bar POs
(M) represents t, and M represents a hydrogen atom or an alkali metal atom.

(Example chelating agent) To -7 To -2 To -9 To -4 K To -10 To -5 To -11 To -12 To (IJl, Shin○HCH, GOOH OOH OOH To -16 To HA2uJtJH To 112uUtJ11 Each component of the above color developer replenisher can be prepared by sequentially adding and stirring to a certain amount of water.In this case, components with low solubility in water may be mixed with the above-mentioned organic solvent such as triethanolamine. Can be added.

More generally, the color developer replenisher of the present invention is prepared by adding a concentrated aqueous solution or a solid state of a plurality of components that can coexist stably in a small container to water and stirring. It can be used as

It is essential that the pH of the color development replenisher of the present invention is 11 or more, and more preferably in the range of 11.5 to 13.0.

In the present invention, since the effect of the present invention is remarkable when the replenishment is low, the replenishment amount of the color developer replenisher is 12
0mff/m" or less is preferable, more preferably 20-
100m1'm', particularly preferably 25-70m
(1/m".

Photosensitive materials using the color development replenisher of the present invention include color paper, color negative film, color positive film, and color reversal film for slides, if the photosensitive material contains a coupler and is processed by the so-called internal development method. It can be applied to any photosensitive material such as color reversal film for movies, color reversal film for TV, and reversal color paper, but it is most preferably applied to color paper mainly containing silver chloride.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A color developer replenisher having the following composition was prepared.

Color developer replenisher triethanolamine logN,
N-diethylhydroxylamine 8.0g Surfactant (listed in Table 2) 0.5g Color developing agent (3-methyl-4-amino-N-ethyl-N-(
β・methanesulfonamidoethyl)-aniline sulfate)
Buffer agent listed in Table 2 (listed in Table 2) Add 0.2 mol water to bring the total amount to 1Q, and adjust the pH to 12.0 with potassium hydroxide or sulfuric acid.

The following experiment was conducted using the above color developer replenisher.

Experiment 1 Each layer of the composition shown below was coated on a support laminated with polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side to produce a multilayer silver halide color photograph. A photosensitive material was created.

The coating solution was prepared as follows.

1st layer coating liquid Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) 10.0g, (ST-2) 6.
67 g of additive (IQ-1) and 0.67 g of high boiling point organic solvent (DNP) were added and dissolved in ethyl acetate 60IIIQ, and this solution was mixed with 20% surfactant (SU-1).
10% gelatin aqueous solution containing 7fiQ 220m+
2 was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

shr+3 OP dinonyl 7 tala to NP dinonyl 7 tala to IDP diisodecyl phthalate V.P. Polyvinylpyrrolidone B5-1 Q-1 Q-2 T-1 T-3 U- I- T-4 shstl (t) In addition, the following H-1 was used as a hardening agent.

[Preparation method of blue-sensitive silver halide emulsion] The following (solution A) and (solution B) were added to 1000 mff of a 2% aqueous gelatin solution kept at 40°C while controlling the pAg to -6.5 and pH -3.0. The following (solution C) and (solution D) were added at the same time over 30 minutes, and pAg-7,3,p! (They were simultaneously added over 180 minutes while controlling the temperature to -5.5.

At this time, l) Ag was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) Sodium chloride 3.42g Potassium bromide 0.03g Add water 200ml (Liquid B) Add silver nitrate 10g water 200+n12 (Liquid C) Sodium chloride 102.7g Potassium bromide Add 1.0g water 600 m12 (solution D) Add 300 g of silver nitrate water After adding 600 m12, desalinate using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mix with an aqueous gelatin solution to obtain an average A monodisperse cubic emulsion EMP-1 with a grain size of 0.85 μm, a coefficient of variation (σ/r > 0.07, and a silver chloride content of 99.5 mol %) was obtained.

The following compound was used for the above emulsion EMP-i, and 50°
Chemical ripening was carried out at C for 90 minutes to obtain a blue-sensitive silver halide emulsion (E m A ).

Sodium thiosulfate 0.8 mg 1 mol 1 mol A
Auric acid 0.5 mg 1 mol 1 mol A fixer 5B-55, QXJQ-'% 41 mol AgX sensitizing dye D-14, 3xlQ-' mol 1 mol AgX sensitizing dye
D -40.7 The average particle size was 0.43 μm, except for EMP-1.
Coefficient of variation (σ/r) -0.08, silver chloride content 99.5
A monodisperse cubic emulsion EMP-2 with mol % was obtained.

For EMP-2, the following compound was used at 120°C at 55°C.
Green-sensitive silver halide emulsion (EmB) after separation chemical ripening
I got it.

Sodium thiosulfate l. 5 mg 1 mol 1 mol A Auric acid 1.0 mg 1 mol 1 mol A fixative S B -56X 10-' mol 1 mol AgX
Sensitizing dye D-24XIQ-'Mo/l,/MoJl, A
gX [Preparation method of red-sensitive silver halide emulsion] Same as EMP-1 except for changing the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D). Average particle size 0
．． Emulsion EMP-3 with a coefficient of variation (σ/r) of 50 μm was obtained.

90°C at 60°C using the following compound for EMP-3.
Red-sensitive silver halide emulsion (EmC) after separation chemical ripening
I got it.

Sodium thiosulfate 1.8 mg 1 mol 1 mol A Auric acid 2.0 mg 1 mol 1 mol A fixative S B -56X to-' mol 1 mol Agχ
Sensitizing dye D-31X10-' mol 1 mol AgX-0
, 88, monodispersed cubes with a silver chloride content of 99.5 mol % This sample was exposed to light according to a conventional method and then processed using the following processing conditions and processing solution.

Processing conditions Processing temperature Time Replenishment amount Tank capacity (1) Color development 39.0±0.3°C 45 seconds 4
0mQ 5(1(2) Bleach-fixing 35.0±0
．． 5℃ 45 seconds 51m12 5c (4) Dry
Drying 60-80°0 30 seconds Replenishment amount is photosensitive material 1
The amount is per m2. For stabilization treatment, use a 3-stability tank.
Refill with countercurrent method to 1.

The composition of each treatment liquid is as follows.

Color developing tank liquid Triethanolamine N,N-diethylhydroxylamine Water-soluble surfactant (V-3) Potassium bromide Potassium chloride Diethylene triamine Pentaacetic acid Potassium sulfite 2.5X 10 Color developing agent (3-methyl-4-amino- N-ethyl-N-(β-
(Methanesulfonamidoethyl)-alinine sulfate) Potassium carbonate potassium phosphate aqueous solution was added to bring the total volume to 112, and the pH was adjusted to 10.10 with sulfuric acid.

Color developer replenisher Use the color developer replenisher mentioned above.

Fixer Tank Fluid and Replenisher Ethylenediaminetetraacetic acid 8.0g 0g g Potassium hydroxide or 10.0g 5.0g 0.3g 0ntg g 5.0g 3 mole ferric ammonium salt 530g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate salt ( 70% solution) 123.0g ammonium sulfite (40% solution) 51.0g ammonium bromide 40,0g Adjust the pH to 6.5 with aqueous ammonia or glacial acetic acid, and add water to bring the total amount to 1a.

Stable tank fluid and replenisher ortho-phenylphenol 0.1g Uvitex (manufactured by Ciba Geigy) 1. ogZ nS
O4”7H200-1g Ammonium sulfite (40% solution) 5.Qa
+Ql-Hydroxyethylidene-1,1-diphosphonic acid (60% solution) 3.0g Ethylenediaminetetraacetic acid 1.5g Adjust to pH 7.8 with aqueous ammonia or sulfuric acid and to 112 with water.

Running processing was performed using the prepared color paper and processing solution.

In the running process, the automatic processor is filled with the above color developing tank liquid, as well as the bleach-fixing tank liquid and the stabilizing tank liquid, and the above color developing replenisher is added every 3 minutes while processing the color vapor sample. The bleach-fix replenisher and stable replenisher were replenished through a metering pump.

The running process was carried out continuously at 0.05R per day until the amount of color developer replenished into the color developer tank became three times the volume of the color developer tank solution.

Note that 1R means that the color developer replenisher is replenished to the capacity of the color developer tank.

After continuous processing, the concentration of herbal medicine in the color developing tank solution, color development properties, and changes in fog were evaluated.

Regarding color development, yellow maximum color development density (Y-Dma
x) was measured. Regarding fog, the yellow reflection density (Y-Dmin) of the unexposed area was measured.

The results are shown in Table 2.

Experiment 2 Pour 30m<i> into a 50mQ glass bottle, add a piece of vinyl chloride pipe that is normally used for piping, seal it, and store it in a constant temperature bath at 5°C for 2 weeks. The presence or absence of precipitates was observed.

The results are shown in Table 2, and the evaluation was performed according to the following criteria.

◎No precipitation at all.

○A small amount of precipitate of solder is observed.

△A small amount of crystalline deposits can be seen on the vinyl chloride pipe piece.

×A large amount of crystalline precipitate was observed on the vinyl chloride pipe piece.

XX A large amount of crystalline precipitate is observed at the bottom of the container.

The amount was 0.1 mol each.

Buffer used Table 1 Experiment 3 Pour 100mff into each 100+N12 glass bottle,
Adjust so that the opening area is 0.015c -1, 25
It was stored at ℃ for 4 weeks. The residual rate of color developing agent after storage and the change in absorbance of the solution before and after storage were measured at 440 nm.

The results are shown in Table 2.

The buffing agents used in the examples are shown in Table 1. In addition, when a buffer agent is used in combination, Table 2 shows that only by the combination of the present invention can a sufficient concentration of color developing agent be maintained without deterioration of color development even after low replenishment treatment, and It can be seen that it is possible to provide a color developer replenisher that does not cause precipitation due to low-temperature storage or deterioration due to long-term storage.

Anionic surfactants were the most effective, and cationic and nonionic surfactants had a low inhibitory effect on precipitation.

Example 2 Under the conditions of replenisher No. I-4 of Example 1, several types of surfactants were used and the amount added was changed, and Example 2
The same evaluation as in Experiments 2 and 3 was performed.

The results are shown in Table 3.

Table 3 Table 3 From Table 3, it is clear that there is a dependence on the amount of surfactant added. It can be seen that by containing 1 or less, there is no liquid coloring property and low-temperature precipitation is effectively prevented.

Example 3 In the sample of Replenisher No. 1-4 of Example 1, the chelating agent diethylenetriaminepentaacetic acid was changed to one having the structure shown below, and added in equimolar amounts.

The storage period in Experiment 2 of Example 1 was 4 weeks, and the storage period in Experiment 3 was 6 weeks.
Evaluation was performed in the same manner as in Experiments 2 and 3. The results are shown in Table 4.

As is clear from Table 4, the present invention can be made even more effective by including the chelating agent represented by formula (K) above.

Example 4 Evaluation was carried out in the same manner as in Example 3, except that 2.0 g IQ of the brightener listed in Table 5 below was added to the sample of replenisher No. 1-4 of Example 1. The results are shown in Table 5.

As is clear from Table 5, the effect of the present invention can be further enhanced by adding a triazinylstilbene brightener.

Example 5 The same procedure was carried out except that in replenisher No. 1-4 of Example 1, the preservative N,N-noethylhydroquinylamine was replaced with another preservative and added in equimolar amounts. The same evaluation as in Example 3 was made. The results are shown in Table 6.

Table 6 As is clear from Table 6, the present invention becomes even more effective by adding the organic preservative represented by formula [A] or [B].

Example 6 Replenisher No. 1-4 of Example 1 was evaluated in the same manner as Example 3 except that triethanolamine was replaced with the following additive and added in an equimolar amount. The results are shown in Table 7.

Table 7 As is clear from Table 7, the effect of the present invention can be further improved by using the alkanolamine compound represented by the formula (C) or the glycol compound represented by the general formula CD). It can be done.

〔Effect of the invention〕

According to the present invention, in color development processing of silver halide color photographic light-sensitive materials, it is possible to dissolve a sufficient amount of color developing agent to extremely reduce the amount of replenishment, and to prevent precipitation and precipitation at low temperatures. To provide a color development replenisher for silver halide color photographic light-sensitive materials that does not cause color generation, has a small processing amount, and does not cause color deterioration over a long period of time even if the solution renewal rate decreases.

Claims (3)

[Claims] (1) Contains a buffer agent and surfactant with a pKa of 10.5 or more, and a color developing agent concentration of 2.0 x 10^
-^2 mol/l or more and a pH of 11.0 or more, a color development replenisher for silver halide color photographic materials. (2) The color development replenisher for silver halide color photographic materials according to claim (1), wherein the surfactant is an anionic surfactant. (3) The color development replenisher for silver halide color photographic materials according to claim (1) or (2), characterized in that the surfactant is contained in a range of 0.01 to 5.0 g/l.