JPS63108339A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To prevent propagation of bacteria in a bath, without damaging preservable property of an image after processing by processing a photosensitive material contg. a specific coupler with a washing water and/or stabilizer which are reduced Ca and Mg contents. CONSTITUTION:The titled material comprises a two equivalent yellow coupler shown by formula I and a two equivalent cyan coupler shown by formula II. The titled material is processed with the washing water and/or the stabilizer in which the concentrations of Ca and Mg compds. are reduced to <=5mg/l expressed in terms of Ca and Mg, respectively. In said processing, the replenishing amount of the washing water and/or the stabilizer is controlled to 1-50 times of the amount carried from a fore bath. In the formula, R1 is N-phenyl carbamoyl group, R2 is 4-20C tertiary alkyl or phenyl group, R3 is an aliphatic or an aromatic group, etc., R4 is H or more than 1C an aliphatic group, etc., Z is H or halogen atom etc., X1 and X2 are each a group capable of releasing by reacting with an oxidant of a developing agent except hydrogen atom.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and in particular to a method of processing a silver halide color photographic material, in particular a method that can be operated continuously while significantly reducing the amount of water (for example, the amount of water used for washing). The present invention also relates to a processing method in which cloudiness and mold due to bacteria do not occur in a water washing bath or a stabilizing bath, and the photographic material after processing has excellent storage stability.

[Conventional technology]

In recent years, it has been suggested that the amount of water used in the washing process included in the processing of silver halide photographic materials should be reduced due to environmental conservation, water resource, or cost concerns. For example, the Journal of the Society of Motion Picture and Television Engineers (Journal of the 5
Ociety of Motion Picture
and Television Engineer
+s) Volume 4g, Jg/~, Page 2jJ (/ri!!2019/month issue) 1 Water Flow Rates in I
mmersion-Wahingof Motion
According to S.R. Goldwasaer (S.R. Goldwasaer), a method has been proposed in which the amount of water used for washing is reduced by making the washing tank multi-stage and causing the water to flow counter-currently. Further, US Patent No. 41.JJt, J2' proposes a system that saves water by carrying out a stabilization process after a bleach-fixing process without substantially undergoing a water washing process.

These methods have been adopted in various automatic machines as effective means for saving water.

However, simply saving water increases the residence time of water in the washing tank, and bacteria breeds in the washing tank, causing turbidity and suspended matter. Furthermore, various types of fungi can grow easily.

Such bacteria and mold adhere to color photosensitive materials during the washing process, resulting in a significant loss of quality after processing. Furthermore, color photosensitive materials washed with water under such conditions have a serious problem of mold growth during storage after processing. In addition to the above, the growth of bacteria and mold can be caused by various problems that need to be resolved, such as the circulation pump or filter in the washing tank becoming clogged in a short period of time, or the water becoming rotten and producing a bad odor. A problem arises.

As a solution to the above problems, patent application No. 4/-137632
One example is the method of reducing calcium and magnesium in the washing water and stabilizing solution as presented in the above issue. Although this method is effective in solving the above problems, the photosensitive materials processed using this method have a color <1, storage stability, and stability of yellow and cyan dyes when aged under high temperature and high humidity. Gender was not always a mutually exclusive factor.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to reduce the calcium and magnesium content in washing water and stabilizing solution without impairing the image stability of processed light-sensitive materials, and to prevent bacteria and mold from multiplying and causing problems. The purpose is to provide a processing method that is not available.

[Means for solving problems]

The above purpose is to reduce the concentration of calcium and magnesium compounds in the washing water and/or stabilizing liquid as calcium and magnesium, respectively! m1g/l or less, and the silver halide color light-sensitive material to be processed contains a 2-equivalent yellow coupler represented by the general formula (2) and a 2-equivalent cyan coupler represented by the general formula (If). I can be mistaken.

General formula (R2-COCH-R1... (1) (In the formula, R1 represents a substituted or unsubstituted N-phenylcarbamoyl group. R2 has q to 20 carbon atoms,
represents a class alkyl group or a substituted or unsubstituted phenyl group.

Xl represents a group other than a hydrogen atom that can be separated during a coupling reaction with an oxidized form of a developing agent. Further, R1, R2 or Xl may form a dimer or higher multimer) General formula (II) In the formula, R3 is a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aromatic group. represents an amino group or a heterocyclic amino group, R4 represents a hydrogen atom, or a substituted or unsubstituted aliphatic group having one or more carbon atoms or an acylamino group; 2 represents a hydrogen atom, a hydrogen atom, a substituted or unsubstituted aliphatic group, or an acylamino group; represents an aliphatic, aromatic, or acylamino group,
l represents a group other than a hydrogen atom that can be separated during a coupling reaction with an oxidized form of a developing agent.

Here, R4 and 2 may be connected to each other to form a ring.<R
One group among a, R4, Xl, and 2 may form a dimer or more multimeric coupler.

Generally, tap water or well water is used as washing water, stabilizing liquid, or water for preparing these liquids. These waters usually contain /
It contains about 10-odd milligrams to over 100-odd milligrams of calcium and magnesium per liter, but if such water is used for water-saving washing or stabilization treatment, it may cause problems due to the growth of bacteria and mold as described above. There are many. As a means for suppressing the growth of bacteria in such washing water and stabilizing liquid, Japanese Patent Application No. 4/131432
The method of reducing calcium and magnesium described in the above issue is the most effective, and the environmentally safe method is also preferred. However, the method of reducing calcium and magnesium in washing water and stabilizing solution decreases the color image stability of processed photosensitive materials and causes problems when stored for long periods at high temperature and high humidity.
In particular, it has been found that this method has the disadvantage that the yellow and cyan dyes undergo significant fading. The cause of this increase in discoloration is currently being analyzed and the details are unknown, but as a result of examining various methods, we found that the general formulas (1) and (II)
It was found that in light-sensitive materials using such couplers, such an increase in color fading hardly occurs, and it is possible to achieve both excellent color image stability and stable water-saving processing.

The method of the present invention makes it possible to reduce the amount of washing water and/or stabilizing liquid.

Specifically, the amount of supplementary light in the washing water or stabilizing solution can be reduced to 0 times, preferably 3 to 30 times, the amount brought in from the previous bath.

The couplers of general formulas (1) and (II) will be explained in detail below.

The monoequivalent yellow coupler used in the present invention has the general formula (
1), in formula (1), Rt(N
-phenylcarbamoyl group) are well-known substituents in yellow couplers, such as alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups,
-rogen atom, alkoxycarbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group , arylsulfamoyl group, arylsulfonamide group, arylureido group, carboxy group, sulfo group, nitro group, cyano group, thiocyano group, etc. There may be two or more substituents, and in that case, they may be the same or different from each other.

The tertiary alkyl group having 9 to 20 carbon atoms in R2 is, for example, t-butyl group, t-amyl group, t-octyl &, /, /
-diethylpropyl group, /, /-dimethylhexyl group,
／、／、! -,! -tetramethylhexyl group, etc. are mentioned as typical examples. Representative examples of the substituent for the substituted phenyl group of R2 include the substituents shown for R1.

The coupling-off group of Xl is a coupling-off group forming a monoequivalent yellow coupler, for example, the following general formula (II).
, (F/), (V) or (M).

(III) R5 represents an optionally substituted aryl group or heterocyclic group.

R6 and R7 are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amine group, an alkyl group, an alkylthio group,
It represents an alkoxy group, an alkylsulfonyl group, an alkylfurfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different.

Represents a nonmetallic atom required to form a self-ring or a t-membered ring.

A preferred yellow coupler for use in the present invention is represented by the following general formula (■).

General formula (■) R<1 In the formula, R8 is a tertiary alkyl group having g to /co carbon atoms, a phenyl group substituted with a halogen atom, an alkyl group, or an alkoxy group, or an unsubstituted phenyl group. represent. R9 represents a halogen atom or an alkoxy group. RIO represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent. Even if R11 has a substituent, it is an ioacylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonamide group, an arylsulfonamide group, an alkylureido group, an arylureido group, or a succinimide group. group, alkoxy group, or aryloxy group.

X3 is the following general formula (■), (K), (X) or (XI
) represents a group represented by

In the formula, R12#i represents a substituted or unsubstituted alkylsulfonyl group, arylsulfonyl group, acyl group, hydroxy group, or a substituent represented by R1 above. j is ko, 3
．． 4t or! and when l is 3 or more, R12 may be the same or different.

In the formula, R13 and "14 are each a hydrogen atom, an alkyl group,
Represents an aryl group, an alkoxy group, an aryloxy group or a hydroxy group. R15, R16 and R1? are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group,
Or represents an acyl group. W2 represents an oxygen or sulfur atom.

A particularly preferred yellow coupler used in the present invention is represented by the following general formula (XI).

General Formula (XI) In the formula, R18 represents an alkyl group or a phenyl group which may have a substituent. X4 is represented by the following general formula (XII[
) or the general formula (K) (X) or (XI).

In the formula, R19 represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted acylamino group, an alkyl or arylsulfamoyl group, or an alkyl or arylsulfonyl group.

R20 represents a hydrogen atom, a cyano group, an optionally substituted alkyl or arylsulfonyl group, an alkyl or arylsulfamoyl group, an alkyl or arylsulfonamido group, an acyl group, an alkyl or aryloxycarbonyl group, or a carboxy group, and 819
%'' At least 7 of 2G represent an optionally substituted alkyl or arylsulfonyl group, an alkyl or arylsulfamoyl group, an alkyl or arylsulfonamido group, an alkyl or aryloxycarbonyl group or a carboxy group.

Specific examples of the yellow coupler represented by formula (1) will be shown next, and these may be used alone or as a mixture of one or more.

(Y-/,) Su1 (Y-1) (Y-3) υh (Y-4t) (Y-, r) (Y-, <) (Y-7) (Y-/) (Y-ta ) (Y-70) (Y-//) (Y-/2) (Y-/J) (Y-/4t) (Y-/z) h3 (Y-/G) (Y-/7) H (Y-//) (Y-/ri) 02CH3 (Y-ko0) (Y-,2/) Shif13 (Y-koko) (Y-JJ) (Y-a4t) (Y-ko!) (Y-26) (00H (Y-27) (Y-,2J') 12H25 (y-1ta) (Y-30) L;2Mfit, :2a5 (Y-37) (Y-3a) ( Y-33) (Y-34t) CM2CH20C2H5 (Y-3j) (Y-3a) H (Y-32) (Y-3♂) (Y-39) (Y-4tO) (Y-ai) (Y- 4t=) H3 (Y-da3) (Y-g4t) (Y-4tt) M3 (Y-4t7) (Y-g♂) (Y-4tp) (Y-!θ) aO- (Y-t /) (Y-t, z) α (Y-r3) α (Y-j4t) These yellow couplers are, for example,
? No. 3, J/-JJ4t/θ, J2-21733
No., JP-A No. 4T7--6733, q♂-73141
No. 2, same j/-10 Koro No. 36, same! 0-/JO4t4
tJ issue, same! 0-43a1, same jO-/2J3'12
Same issue! L-co/12th issue, J-0-/7th issue 30,
same! -1/J4tJ4 is the same! Ko//j2/9 issue,
゛British patent/4t2!0coO, West German patent/j417♂
No. 4♂, West German Application Publication Coco/Wata/ri No. 413
It can be synthesized according to the method described in No. 4/, No. J4t74toot, etc.

The phenolic co-equivalent cyan coupler in the general formula (It) will be explained.

R3 is preferably an aliphatic group having a carbon number/~3d, preferably an aromatic group having a carbon number of 4 to 36 (e.g., a phenyl group,
naphthyl group), heterocyclic group (e.g., 3-pyridyl group, 1,2-7lyl group, etc.), or aromatic or heterocyclic amino group (e.g., anilino group, naphthylamino group, -
1penzothiazoli/7mino group, copyridylamino group, etc.), and these groups further represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., a methoxy group, a -1methoxyethoxy group, etc.), an aryloxy Group (
For example, 2.4t-di-tert-amylphenoxy group, -1chlorophenoxy group, guccianophenoxy group, etc.), alkenyloxy group (e.g., coproynyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethyl carbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group) , dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, cyano group. , a carboxy group, a nitro group, a sulfo group, a halogen atom, and the like.

As used herein, the term "aliphatic group" may be linear, branched, or cyclic, and may include an alkyl group, an alkenyl group,
The meaning includes both saturated and unsaturated groups such as alkynyl groups (representative examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, alkynyl group, is.

-propyl group, tert-butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclointyl group, allyl group, vinyl group, cohexadecenyl group, pronogyl group, etc.).

R4 is a hydrogen atom, preferably an acylamino group C having carbon number/~jj (e.g., acetylamino, butyrylamino, tetradecanoylamino, benzoylamino group, etc.), a fatty acid having carbon number/or more, preferably carbon number/~- Represents a family group. These groups may be substituted with a permissible substituent in R3, for example, R4 includes a methyl group and a methyl group having a substituent, and this substituent includes an alkyloxy group (e.g., methoxy group, butoxy group). group, benzyloxy group, etc.), aryloxy group (e.g., phenoxy group, q-chlorophenoxy group, cucyanophenoxy group, 41-tert-7 milk enoxy group, etc.), alkylthio group (e.g., methylthio group, dodecylthio group, etc.) ), arylthio groups (e.g. phenylthio group, q-chlorophenylthio group, tardodecylphenylthio group, etc.), alkyl or arylsulfonyl groups (e.g. ), acylamino groups (e.g., acetylamino groups, benzoylamino groups, etc.), imide groups (e.g., succinimide groups, 7-thalimide groups, hydantoinyl groups, etc.), ureido groups (e.g., phenylureido groups, methylureido groups, etc.), and cyanogen groups. is preferred.

2 is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a ^ atom, etc.), preferably carbon number/-20f
) represents an aliphatic group, an aromatic group having 4 to 20 carbon atoms, or an acylamino group, and these groups may be substituted with a substituent allowed for R3.

Furthermore, ``4 and 2 may be linked to each other to form a saturated or unsaturated !-membered ring (excluding a benzene ring), in which case R4 forms a nitrogen-containing heterocycle together with an acylamino group. It is preferable to do so.

Z represents a coupling-off group, examples of which include halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group) , carboxypropyloxy group, methylsulfonylethoxy group), aryloxy group (e.g., terchlorophenoxy group, termethoxyphenoxy group, tercarboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocallyoxy group) group, pentyloxy group, etc.), sulfonyloxy group (e.g., ttf, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group,
heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group), ), aliphatic, aromatic or heterocyclic thio groups (e.g., ethylthio, phenylthio, tetrazolylthio, etc.), imide groups (e.g., succinimide, hydantoinyl, etc.), aromatic azo groups (e.g., phenylazo). etc.) etc. These leaving groups may include photographically useful groups.

General formula (1[) is preferably a cyan coupler represented by general formula (XW) and general formula (XV).

General Formula (XW) In General Formula (XIV) and General Formula (XV), X2 and 2 are the same as defined in General Formula (1).

R21s R22 and R23 each have carbon number/~3
6 substituted or unsubstituted aliphatic groups or 6 to carbon atoms
3 represents a substituted or unsubstituted aromatic group, R24
represents a hydrogen atom, an aliphatic group having from 7 to -0 carbon atoms, or a substituted aliphatic group having from / to -0 carbon atoms, and 2 and R22, or 2 and R24 are mutually connected to form a saturated or unsaturated 1 Table 2
It may form a membered ring (excluding a benzene ring).

Preferred substituents for these groups include the substituents allowed for R3.

Preferred examples of R21 include a substituted alkyl group and a substituted or unsubstituted aryl group. As a substituent for the alkyl group, an optionally substituted phenoxy group and a halogen atom are particularly preferred. Particularly preferred are phenyl groups substituted with a rogene atom, an alkyl group, a sulfonamide group, or an acylamino group.

Preferred R22 is a substituted alkyl group or a substituted aryl group, and a phenoxy group which may be substituted is particularly preferred as a substituent of the alkyl group.

In the general formula (Xll/), preferable 2 is a hydrogen atom,
These are an alkyl group, an alkenyl group, an aralkyl group, and an acylamino group.

It is also preferable that 2 and R22 form a j~2-membered ring, and in that case! It is particularly preferable to form a membered ring.

In general formula (XIV), X2 is preferably a halogen atom, with a chlorine atom being particularly preferred.

Preferred R23 is an optionally substituted alkyl group or a substituted aryl group, with a substituted or unsubstituted alkyl group being particularly preferred.

Preferred R24 is an alkyl group or a substituted methyl group having a carbon number of /j to /j, and an ethyl group is particularly preferred.

In general formula (XV), 2 is preferably a halogen atom.

In general formula (XV), preferred X2 is a halogen atom.

When R24 is a hydrogen atom, 2 is preferably an acylamino group.

The cyan coupler represented by the general formula (If) can be used alone or in plurality, and can also be used in combination with other known couplers (not limited to cyan). Also, the general formula (
XI'/) and couplers of general formula (XV) can also be used in combination (single or in combination).

(C-/) Cε (C-J) (C-4t) (C-7) (C-/) (C-?) (C-72) ((-/J) a (C-7j) (C -/7) (C-/♂) (C-/ri) (L)shi5”11 (C-ko0) (C-2/) (C-22) (C-ko3) (C-, z4t) (C-27) (C-ko♂) (C-kota) (C-io) (C-i/) (C-32) (C-33) Csi (C-39) (C-3r ) (C-3a) (C-J7) (C-,?/) Lshi (C-39) (C-4to) (C-a/) (C-octopus) (C-4t3) (C-4t4t ) (C-abu) (C-4t7) (C-1/) (C-<t?) (C-!tO) (shi(C-z/) (C-!ko) r゛(C- t3) Cε (C-!g) α Next, although any magenta coupler can be used, the following general formula [X
Couplers represented by M ) or (Xi) are preferred.

General formula (XM) General formula [X■] Return aJb R2S and R27 represent a substituted or unsubstituted phenyl group, R26 represents a hydrogen atom, an aromatic acyl group, an aliphatic or aromatic sulfonyl group, and R28
represents a hydrogen atom or a substituent, and Xl5SX6 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent; examples thereof include the above general formula (II).
Examples include those exemplified in X2.

In the formula, Za and Zb represent =CH-1=(knee spanning=N-, R28 and R29 represent a hydrogen atom or a substituent, and X6 represents a hydrogen atom or an oxidized aromatic primary amine developer. Represents a group that can be separated by a coupling reaction with.When Za=Zb is a carbon-carbon double bond, it includes the case where it is a part of an aromatic ring.Furthermore, R28, R29
It also includes the case where X6 forms a multimer of zt form or more. However, if Za or zb is =C-, R28
Or, when at least 7 of R29 is =N- for both Za and Zb, R28 represents a group in which at least 7 of the hydrogen atoms of the methylene group directly connected to the skeleton are substituted, and R28 or R29 contains at least one -NH8O2- substituent.

Specific examples of the general formula (XM) and [Jun] are shown below.

(M-2) (M-3) (M-4t) (M-, t) (M-6) (M-7) (M-, r) (M-ta) (M-10) (M- //) (M-72) (M--J) (M-26) (M-a2) (M-ko/) (M-kota) (M-30) Rishi 4-i1Q (M-J/ ) rl (M-Jko) (M-33) (M-3ge) (M-3t) (M-37) rl (M-3ri) (M-4to) /'/ (M-<t3) C-(M-<t, g) Cyan couplers represented by general formulas (IN) and (III) can be synthesized by known methods. For example, general formula (II
The cyan coupler represented by ) is synthesized by the method described in U.S. Pat. On the other hand, the cyan coupler represented by the general formula (III) is disclosed in U.S. Patent No. 2! , /26
Same number, same number! ! ! , Tade No. 9, same No. 3, 3 cores,
It is synthesized by the method described in No. 773, etc.

The magenta coupler represented by the general formula [X■] is disclosed in Japanese Patent Application Publication No. 74T02, Datar 74tOλ♂, Japanese Patent Application Publication Shota♂--Kuta No. 30, J3-331G No. 6, and U.S. Pat. ! It is synthesized by the method described in /2, 4t, 2, etc.

The magenta couplers represented by the general formula [80] are each Tokkai Sho! /4JJlr, U.S. Patent No. 3.2
, No. 067, JP-A No. 3 Ta1/2/9 JD and JP-A No. 60-, ? It is synthesized by the method described in No. jjjJ.

In addition to the couplers mentioned above, functional materials such as colored couplers, DIR couplers, diffusible dye-forming couplers, and DIR hydroquinone can be used in the light-sensitive material of the present invention.

The coupler of the present invention can be added to the light-sensitive material in any amount, but it is used in an amount ranging from 0.01 mol to 10 mol, preferably from 0.01 mol to 0.001 mol/mol per mol of silver halide. 0.2 mol to 0. Most preferably, a range of J-mol is used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-ice dispersion method is U.S. Patent No. 2.322.02.
It is written in No. 2, etc.

Further, the process and effects of the latex dispersion method, as well as specific examples of latex for impregnation, are described in US Patent No. D/9.

No. 333, West German Patent Application (OLS) No. 2. Tai.

No. J74 and No. 2. ! 4t/, No. 230, etc.

In the present invention, washing with water is a process for ensuring the performance after processing by washing out the processing liquid components that have adhered to or occluded in the color photosensitive material as well as the constituent components of the photosensitive material that are no longer needed during the processing process. .

The stabilizing liquid refers to a liquid that imparts an image stabilizing effect that cannot be obtained only by washing with water, as described above.
For example, examples include formalin as an image stabilizer.

In the present invention, the concentrations of calcium and magnesium compounds in the replenishment solution to be replenished in the water washing step and/or stabilization step are defined as magnesium and calcium, respectively! m
It can be further increased by reducing it to below g/l. Therefore, the replenisher for the water washing step and/or stabilization step in the present invention preferably has a calcium and magnesium concentration of less than Jmg/l, preferably less than Jmg/l, more preferably less than 7mlz/l. It is.

Calcium and magnesium in the replenisher in the water washing step and/or stabilization step can be reduced as described above by various known methods. For example, the content of calcium and magnesium compounds can be reduced by means of ion exchange resins, zeolites or reverse osmosis devices.

Further, these concentration lowering or deionizing means can be used not only for replenishing liquids, but also for circulating liquids in processing tanks (washing baths, stabilizing baths).

Although various cation exchange resins can be used as the ion exchange resin, it is preferable to use a Na type cation exchange resin in which Ca and Mg are replaced with Na. Further, a HW cation exchange resin can also be used, but in this case, the pH of the treated water becomes acidic, so in order to avoid this, it is preferable to use it together with an OH type anion exchange resin.

Furthermore, aminocarboxylic acid type chelate resins can also be used as seven types of cation exchange resins.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such ion exchange resins include Mitsubishi Kasei's split product name Diaion SK-/B or Diaion PK-1/
4 etc. can be mentioned. The substrate for these ion exchange resins is preferably one in which the amount of divinylbenzene charged is 1/6 of the total amount of monomers charged during production. As an anion exchange resin that can be used in combination with an H-type cation exchange resin, a strongly basic anion exchange resin that has a styrene-divinylbenzene copolymer as a base and has a tertiary amine or primary ammonium group as an exchange group is preferable. . Examples of such a strong anion exchange resin include Diaion SA-#7A and Diaion PA-4t//'4 manufactured by Mitsubishi Kasei Corporation.

All known methods can be used to remove calcium and magnesium from the replenisher using these ion exchange resins, but it is preferable to pass water through a column filled with the ion exchange resin. The water flow rate is preferably 7 to 100 times the resin volume per 7 hours! ~! It is Q times.

Zeolite is an insoluble aluminum silicate containing Na(
It is expressed by the general formula: AIOz)x-(Si02)y-Z(HzO). Both A-type zeolite and X-type zeolite, in which X and y are the same in the general formula, and X-type zeolite, in which X and y are different, can be used in the present invention. preferable. An example of such a zeolite is Molecular '/-7'' LI manufactured by Union Carbide.
I can give you NDE ZB-JOo. Zeolite comes in various particle sizes, but particles larger than 30 mesh are suitable when packed in a column and brought into contact with water.

As the reverse osmosis treatment equipment used in the present invention, any known equipment can be used without limitation, but the area of the reverse osmosis membrane is 7 m
It is desirable to use an ultra-compact device with a working pressure of JOkg/m2 or less, particularly preferably -m2 or less, and θkg/rn2 or less. When such a small device is used, the workability is good and a sufficient water saving effect can be obtained.

Furthermore, it is also possible to pass activated carbon or a magnetic field.

The reverse osmosis membranes included in the reverse osmosis treatment equipment include cellulose acetate membranes, ethylcellulose polyacrylic acid membranes,
A polyacrylonitrile film, a polyvinylene carbonate film, a polyethersulfone film, etc. can be used.

In addition, the liquid feeding pressure is usually j-6Okg/cm2, but in order to achieve the purpose of the present invention, it is sufficient to set it at 3Okg/cm2 or less. It can be fully used.

As for the structure of the reverse osmosis membrane, any of the following types can be used: a spiral type, a Tupler type, a hollow fiber type, a pleated type, and a rod type.

Replenishment to be added to the water washing process and/or the stabilization process in the present invention! (hereinafter referred to as water washing replenisher and stable replenisher) is preferably sterilized before use.Specific sterilization methods include heavy application of disinfectant, pore size o, t.
Temporary use with micron or smaller filters, heating, ultraviolet irradiation, etc. are unsuccessful, but from the point of view of certainty of effectiveness, it is preferable to use a sterilizing agent. Acids, active 7% such as dichloric acid, dichloroisocyanuric acid, and salts thereof
Ofun-releasing compounds,! -Exa-Kometeru-san-
Inteazolin-J-one, comethyl-derinthiazolin-J-one, 120-isothiazoline-a-based compounds, /, benzisoteazolocy-based compounds represented by J-benzisothiazolin-J-one, triazoles such as benzotriazole compounds, silver ion releasing compounds such as silver nitrate, S oxide, sul-7 anilamide, 10. /DI-
``Chemistry of antibacterial and antifungal agents'' by Hiroshi Horiguchi, including oxybisthraenoxyarsine Sanitary technology gold wire ``Sterilization and sterilization of microorganisms,
The fungicides described in "Mildewproofing Technology" can be used.

These fungicides can be used in the range of /-1000 t/l, but preferably in the range of 1 to 1 ooay/l.
-30119/lj.

Among these, from the viewpoints of the above effects, little influence on photosensitive materials, ease of use, and the like, active agamine-releasing compounds are preferred for washing replenishers, and isothiazocune-based compounds are preferred for stable replenishers.

The washing bath and/or the 4-stable bath of the present invention can also contain calcium and magnesium and an intermediate rate agent having a stability constant of 4 or more.

Here, the stability constant (KM^) is expressed by the following equation.

CM) (A) Here, (MA) is the molar concentration of the residual chelate, CM) is the molar concentration of the metal ion, and [A] is the molar mK of the medium-rate chelate.

Chelating agents having such stability constants are listed in "Metal Chelation) [g" by Keihei Ueno (published by Nankodo), "Dotite Reagent General Catalog 1J Edition" published by Isotope Kagaku Kenkyusho, and Silene (L, G, 8i11enet ml,) “Stability constant of metal complexes (8tabilIsyConsta
It can be easily selected from the medium-rate compounds described in ``Int of Metal Complex'' published by Ill. 4 Dachemistry Society.

Among these killing agents, the following are specifically exemplified.

Stability constant Ca Mg Hydroxyethyl ethylenedi7(NE Vinegar 11(EDTA r,/$7.
.

-0H) Ethylenecyatron-N, Nl-diacetic acid-di(cobropio) 10.74A, μ
lnfl) The above compound FiJX10 ~3 x 70 mol/l,
Preferably, 1×10 to 1×10 mol/l is used.

Such intermediate rate agents are expected to have the effect of further enhancing the effects of the present invention.

In the present invention, the pH in each washing bath constituting the washing device S
is from 3 to ri, preferably from 1 to r. Also, what is the pH of the washing replenisher solution supplied to these baths? range, preferably! ~r.

The water washing step of the present invention has a treatment time of 20 seconds to 3 minutes, preferably 30 seconds to 2 minutes, and a treatment temperature of 10 to 30 minutes.
, preferably 30 to -〇〇〇.

On the other hand, in the present invention, a compound having an image stabilizing effect is added to the stabilizing bath, and specifically, formaldehyde, acetaldehyde, propionaldehyde, geltalaldehyde, Aldehyde compounds such as formaldehyde sodium bisulfite adduct, geltaraldehyde bisulfite 61 [sodium adduct, acetic acid, boric acid, phosphoric acid, citric acid, tartaric acid and its salts, and amino acids for the purpose of adjusting the membrane pH after treatment. Chelating agents such as polycarmenic acid, aminopolyphosphonic acid, alkylidene diphosphonic acid, homephonocarbon e11 and their salts, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, etc., in amounts that exhibit their respective effects and added in the form of

The pH of each stabilizing bath used in the stabilization step is from da to rederop1, preferably da, tj, j. In addition, the pH of the stable replenisher supplied to these baths is between 9 and 9, preferably between 9 and 9.
It is 7.

In addition, the treatment time in the stabilization step is 20 seconds to 3 minutes, preferably 30 seconds to 2 minutes, and the treatment temperature is 10 to 30 minutes.
JFF t C<FiJ O~4' 0 ”C tel.

Furthermore, if the washing step and/or the stabilization step follows the fixing or bleach-fixing step, the overflow liquid discharged from the washing step and/or the stabilization step along with the supplementation may be partially or completely used in the fixing or bleach-fixing step. It can be supplied to the process.

In addition to the above, when the washing step or stabilization step of the present invention is the final step of the treatment, a surfactant is added to obtain uniformity of drying. Further, a fluorescent whitening agent and a hardening agent can also be added.

The present invention is widely applicable to the processing of color I-genated 1j14 photosensitive materials, particularly color bases, color negative films, reversal color papers, etc. f,
It is preferable for processing silver halide photosensitive materials such as & color films and +N bonded positive papers, and is particularly preferably used for color beneau.

Hereinafter, as an example to which the present invention is applied, processing of an I''aCX silver gunkide photographic light-sensitive material will be mainly described.

In the treatment method of the present invention, washing with water or stabilizing burial is a fixed method.
R1! ! The above-mentioned problem can be further solved when the method is used in processing No. 6 of the present invention. Applications to various processes for color photographic materials include, for example, the following.

Person 1 color development - bleaching, fixing - washing, drying B, // - washing, bleaching, fixing, washing, drying C0
Color development - bleaching, washing, drying D, //
- Bleach - Bleach-fixing - Constant observation - Washing with water - Drying - E0 Color development Development Bleach - Bleach-fixing - Washing with water - Drying p,
tt constant skin, white fixing, washing, drying (j,
n - labeling, washing with water, constant setting, stabilization, drying) 1. /
I - Bleach constant - Stable - Drying, // - Prefecture white - Bleach fixing - Stable - Drying J, tt - Bleaching fixer - Stable - Drying Kh 〃 Constant fixing - Bleach fixing - Stable - Drying, above G In ~H, a water washing process may be provided before the stabilization process.

The above treatment bath will be explained below.

Color Development The color developer used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developer as a main component. Although amine phenol compounds are also useful as the main color developing system, p-
Phenyl diamine compounds are preferably used, typical examples of which are 3-methyl-7-amino-N, N-diethylaniline, 3-methyl-≠-amino-N-ethyl-N
-β-hydroxylethylaniline, 3-methyluda-
Amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-methoxyethylaniline and their sulfate salts, salt ester salts, phosphate salts or rip -Toluenesulfone M
, term, tetraphenylborate, p-(t-octyl)
Examples include benzenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Examples of aminophenol derivatives include O-7 minophenol, p-abanophenol, Hiro-aminocometerphenol, Loamino-3-methylphenol, J-oxy-3-amino-/, 4t-dimethylbenzene, etc. is included.

In addition, "Photographic Processing Chemistry" by F. A. Menn, Focal Press (
/ P4 bu years) (L, p, person.

' Mason, Photographic
Processing Chemlstry”, F
ocal Press), pp. 226-Kokota, U.S. Patent λ, l,! ,0/! No., same co, j octopus, 3bu≠ No.,! Kumquats described in #Kaisho #Ir-44 #33 etc. may also be used. If necessary, a combination of color developing agents greater than or equal to 100% may be used.

Is the color developer an alkali metal charcoal? pH buffering agents such as iR salts, borates or phosphates; bromides, iodides,
Development inhibitors such as benzene dazoles, benzothiazoles or mercapto compounds are also anti-capri agents; hydroacylamine, diethylhydrochloramine,
Triethanolamine, West German license application (oLs) No. 2≦
42 pages! Compounds described in No. 0, sulfites or 7t are preservatives such as bisulfites; organic + such as diethylene glycol! 1j: benzyl alcohol, polyethylene glycol, 4411 ammonium salt, amines, thiocyanate, 3,6-thiaoctane-/! - phenomenon accelerators such as diols: dye-forming couplers; nucleating agents such as sodium carbonate 2-1; auxiliary developers such as l-phenyl-3-pyrazolidone; viscosity-imparting agents; Agent: Ethylenediamine 4-chain, nitrilotriacetic acid, Siku-a
Hexanediami.

N-tetraacetic acid, iminodiacetic acid, N-human e! Medium dimethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, t. Liethylenetetraminehexaacetic acid and JP-A-Sho! r-/
Aminopolycarboxylic acids represented by the compounds described in No. 111 Ko No. 3, l-hydroxyethylidene-/, /'-
Diphosphonic acid, Research Disclosure/r/7
0C, I March 1972) Own M-phosphonic acid, aminotris (methylene phosphonic acid), ethylenediamine-
N, N.

pJ/, *N/-aminophosphonic acids such as natrametele/phosphonic acid, JP-A-12-10-7-J,
and Research Disclosure/No. 1170 (/
It can contain a chelating agent such as phosphonocarinic acid described in 2007).

The color developing agent is a color developing solution/lδ9 of about 0.
7t to about 309, more preferably a color developer i
It is used at a concentration of about 1 it to about ijt. However, the pH of the color developing solution is usually 7 or more, and R7 is also generally used at a pH of about 2 to about 13. Also color development tjLfJ1
The replenishment tr can also be reduced by using a replenisher with a concentration t-adjusted of a hagnide, a color developing agent, etc., for the second liquid.

In the present invention, it is preferable that the above-mentioned benzyl alcohol is not substantially contained as a development accelerator.

Here, "not containing *X" means color developer/l
Teeth 2td or less, preferably 0. More preferably, it does not contain at all. When the benzyl alcohol is not contained, the present invention exhibits a better cooling effect.

The processing temperature of the color developer of the present invention is preferably 10-1011C, more preferably 30 to ao''c.The processing time is 20 seconds to 10 minutes, more preferably 30 seconds to ! minutes.

As the bleaching agent used in the bleach solution or bleach constant fII solution used in the present invention, a ferrous ion complex is combined with a t4 iron ion and a chelating agent such as aminopolycarphonic acid, aminopolyphosphophone 26, or a salt thereof. It is a complex of Aminopolycarboxylate salts or aminopolyphosphonates are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Examples of alkali metals include sodium, potassium, lithium, etc.69, and water-soluble amines include alkyl amines such as methylamine, diethylamine, trietheramine, butylamine, ring amines such as cyclohexylamine, aniline, and aryls such as m-toluidi/. amines, and heterocyclic amines such as pyridine, morpholine, and piperidine.

Typical examples of intermediate rate agents such as these aminopolycarboxylic acids and aminopolyphosphophones or their salts include ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid 7,3-cyaminopropanetetraacetic acidcyclohexanediaminetetraacetic acid iminodiacetic acid glycol ether diamine Examples include tetraacetic acid and salts thereof such as N a SN ) la , but of course the compounds are not limited to these exemplified compounds.

The ferrous ion complex salts may be used in the form of complex salts, or may be used in combination with ferrous salts such as ferrous sulfate, ferrous chloride, ferric nitrate, ferric ammonium sulfate, ferrous phosphate, etc. A @λ iron ion complex salt may be formed in solution using a chelate such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. When used in the form of a complex salt, i
Complex salts of type d may be used, or complex salts of type d or more may be used.On the other hand, when a complex salt is formed in a solution using a ferrous salt and a chelating agent, Fi ferrous salt "f" :/Chestnuts or two or more types may be used.Furthermore, a chelating agent/type or 24 or more types may be used.It may be used in excess to form the tζ salt.Among the iron complexes, aminopolymer Iron calmitic acid complexes are preferred, and the amount added is 0.0 to 0.0 mol/l, preferably 0.2 to 0.00 mol/l, for bleaching solutions for color photographic materials such as color negative films.
0.03 to 0 in the bleach-fix solution.
．． 3 moles/7? , preferably 0.1 to 0. ! Mall/E
It is. However, in the bleaching solution or bleach-fixing solution for color photographic materials for printing such as color paper, it is 0.0.
3 to 0.3 mol/II, preferably 0. Oj~Q, 2 mol/g.

In the bleaching solution, bleach-fixing solution and/or bleaching solution, compounds of F1 can be used as a bleaching promoter n+. For example, U.S. Pat. No. 4J, r. 3. r11 Akira d
l, Germany ql" f$1,290,1112 specification,
Mercapto f5 maku described in JP-A No. 33-21430 and Research Disclosure No. 17/Kota (Idefr No. 78) is a compound having a disulfide donor alloy, JP-A-Sho! 0-7μ0 Inthiourea derivatives described in Japanese Patent No. 3,704,111, JP-A-1986-1996 R-IT Co.
Iodide described in Publication J, German Patent No. 2.7441
, 4c70 No. 8A specification, polyamine compounds described in Japanese Patent Publication No. Sho at-grit, etc. can be used. In particular, compounds having a mercapto group or a disulfide bond described in the above-mentioned publications are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (
For example, potassium bromide, sodium bromide, beautified ammonium), chlorides (eg, potassium chloride, sodium chloride, ammonium chloride), and iodides (eg, ammonium iodide). If necessary, use boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, II acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
Corrosion inhibitors such as ammonium nitrate and guanidine can be added to inorganic acids and organic acids of lfl class or higher having a buffering capacity, and their alkali metal salts and ammonium salts.

The fixing agent used in the bleach constant M solution or fixing solution of the present invention is:
classification fixing agents, i.e. thiosulfate-rich sodium theoquanate, such as sodium thiosulfate, ammonium thiosulfate;
Thiocyanates such as ammonium thiocyanate; ethylene bisthioglycolic acid, 3,4-dithia-1,r-
These are water-soluble silver halide dissolving agents such as thioether compounds such as octanediol and thioureas, and these can be used alone or in combination of two or more. Also, Tokukai Akira! /-13!3! A special bleach-fixing solution, etc., which is described in No. U and consists of a combination of a specific fixing agent and a large amount of potassium iodide, etc. can also be used. Preference is given to using ammonium osulfate salts.

The amount of fixing agent per liter is preferably 0.3 to 1 mole, particularly 0.3 to 1 mole, particularly in the processing of color photographic materials for photography. l~
/, 1 mol, in the processing of color photographic materials for printing, 003 to 1 mol of I#11! It is surrounded.

The pH range of the bleach-fix solution or fix solution in the present invention is J-
10 is preferable and even better! -2 is particularly preferred.

To adjust the pH to a#1m, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

In addition, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinyl vicritone and methanol.

The bleach-fix solution and fixer of the present invention contain sulfites (e.g., sodium saliva sulfate, potassium sulfite, ammonium sulfite, etc.) and bifL sulfates (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. Mu,
etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), and sulfite ion-releasing compounds such as metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 to 0 in terms of sulfite ions,
It is preferable to contain 0 mol/l, and further KtFP or o, o a-o, go%le/lteh'
;b.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carmenyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

In addition, it has buffering agents, fluorescent brighteners, chelating agents, and mold prevention! @ etc. may be added as necessary.

Examples of photosensitive materials used in such processing include color paper and color negative film.

First, as a color paper, silver chlorobromide having an iron bromide content of 10 molar or more is used. In addition, in order to obtain an emulsion with sufficient sensitivity without increasing fog, the silver bromide content should be 2.
It is preferable that the amount is 0 molar or more, but if a rapid connection is required, a value of 10 molar or less or j molar or less may be used.

In particular, an emulsion close to pure silver chloride of 1 mol or less is most preferred as it allows rapid development.

Further, the photographic emulsion layer of the color negative film used in the present invention may contain any of the halogenated steels such as copper bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. i,
Preferred silver halide IIJO iodide at-
Contains silver iodobromide or silver iodochloride. Preferred for 1% is silver iodobromide containing 2 moles to Jj moles of iodide.

In photographic emulsions, it is possible to use regular crystal grains such as cubes, octahedrons, dodecahedrons, and rhombic l-cohedrons; t/%, even those with irregular crystal shapes, crystal defects such as twin planes, or composite forms thereof.

Tabular grains may also be used, and their use can improve sensitivity including improved color sensitization efficiency, improve the relationship between sensitivity and graininess, improve sharpness, improve IA image progression, and improve covering power. , crossover improvements, etc. can be achieved.

Here, the flat plate-like agunized faako is one whose diameter/thickness ratio is 3 or more, such as I-Jo! More than r
There are the following:

A monofilamentary emulsion can also be used as a silver halide emulsion, in which silver halide grains have an average grain diameter larger than about a,/i, and at least about Pj weight - is within ± of the average grain diameter.
An emulsion within 4Io@ is typical. The average particle diameter is about 0,000 yen, and at least 700 yen is about 2
! Emulsions containing at least about 1,000 halogenated grains by weight or number within a range of ±20 mm of average grain diameter can be used in the present invention.

The dyes used in the present invention may be spectrally sensitized by methine dyes and others. polar
Included are cyanine dyes, hezocyanine dyes, styryl dyes and hexioquinol dyes. 4? Useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

As the sensitizing dye used in the present invention, LeE8EA&C
HDE8CLO8U&E ttt volume, item/7buoJ1 section p, KoJ (-/ri7 in 2019!-Month issue) K! e
I can list things that are comparable to @.

In this case, the sensitizing dye can be used in any step of the photographic emulsion preparation process, or can be present in any stage after manufacture up to just before coating. Examples of the former include an iron halide particle formation process, a physical ripening process, and a chemical ripening process.

In particular, U.S. Pat.

J. Co., Ltd., No. 444, by adding a spectral RI-sensitizing dye to the emulsion after the formation of stable nuclei for the formation of silver halide grains, the photographic sensitivity can be increased by 77G and the spectral sensitizing dye can be increased by silver halide grains. It is disclosed that there are advantages such as enhanced adsorption.

The silver halide photographic emulsion used in the present invention contains the following ingredients for the purpose of preventing fog during the manufacturing process of light-sensitive materials, storage or photographic processing, or stabilizing photographic performance.
Various compounds can be included. i.e. azoles, such as benzothiazolium salts, nidroimidazoles, nitropenziedazoles; Deadiazoles, aminotriazoles, benzotriazoles, nido abenzotriazoles, mercaptotetrazole fi ('19/-722ru!-mercaptotetrazole), etc.; mercaptobili gins; mercaptotriazines ; thioketo compounds such as oxadorintheone; azaindenes, such as triazaindenes, tetraazaindefs, especially those with ruhydro-a-oxy substitution (/.

J, Ja, 7) tetraazaindene), pentaazaindene fA, etc.; anti-capri agents such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.; compounds can be added.

It is preferable to use a colored coupler in combination with a color negative photosensitive material for deep shadows in order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers. U.S. Patent No. G, Ibu 3゜470 and Special Publication
Yellow colored magenta kagura described in 7-3 Tada IJ No. 1 or U.S. Painting Patent No. 00, RI 2, No. DA, /31゜co! r and British Patent No. 1. / Hirot, Jt
Typical examples include magenta-colored cyan couplers described in No. R and the like.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blur couplers are described in U.S. Patent No. 744,237 and British Patent No. 2. /Ko! , No. 170 contains a specific example of a magenta coupler.
European Patent No. PJ.

No. 370 and West German Application Publication igJ, Co., 333.
The issue includes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat.
, No. 120 and No. a, oro.

It is described in No. 271. Specific examples of polymerized magenta couplers include Eiho Patent No. 2,10, No. 173, U.S. Patent No. G, No. 367.122, and Japanese Patent Application No. 1971-710≠7.
．． and the same 0-//J! It is stated in the above.

Each f-coupler has the characteristics f required for the light-sensitive material.
Two or more types of TI4* may be used in combination in the same photosensitive layer, or compounds between them may be introduced into two or more different layers.

The amount of 1111 color coupler used depends on the photosensitivity.
The range is from o, ooi to 1 mol per mol of silver halide, preferably #-jo, o in yellow couplers.
i to 0.2 moles, 0.003 for magenta couplers
to 0.3 moles, and 0.002 moles for cyan couplers.
0.1 to 0.1 mole.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

Examples of DI couplers include those that release heterocyclic mercapto type development inhibitors as described in US Pat. The benzotriazole rust conductor described in r-2-4c, etc., which is released as a ftgA image suppressor; Tokko Sho! So-called black coloring described in /-/41≠No. 1 etc. 1) IR, coupler; JP-A-Sho J coater 0
No. 132, which releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after separation; US Pat. 7-! 4137, which releases a development inhibitor with an intramolecular nucleophilic reaction after separation; JP-A-Sho! 1-//Buddhari 4L issue, same! 7
-t'tax J issue, same! No. 7-/11031, Jt-
Tara r7 ko r issue, same! ! - Ko0ri 7J issue, same it-, 2
Ori No. 737, same! r-20?7Jlr issue, same! r-2
No. 09732 and the same! r-2027da No. 0, etc., which releases a development inhibitor by electron transfer via a conjugated system after separation; JP-A-Shojt7-/! /91AIA issue and I Tsukasa! R-217932, etc., which releases a diffusible development inhibitor whose development inhibitory ability is deactivated in a developer; patent application! Tar 3r No. 247, same! Examples include those that release reactive compounds described in Turf 5F No. 33, etc., and generate development inhibitors through reactions in the film during development, or deactivate development inhibitors and then release them. can. Bear'2n mentioned above
Among the DIR couplers, those that are more preferable in combination with the present invention are JP-A-17-17-/! Developer deactivated type represented by /W4t1; U.S. Patent No. Hiroshi.

A timing board represented by Koda F, No. 112 and JP-A-17-1μ23≠; a reaction type represented by JP-A No. 3-RIB 33; particularly preferred among them is the timing board from JP-A No. Showa 37-/! /YILt≠ issue, same jt-2i
Yuri 3J issue, special request! Turf 3 Da 7≠, Turf 1 Tur 11
4/# issue, same! f-r2 Corda and J Tata Oμ
developer-deactivated TiD IR couplers described in No. 3r, etc.; and reaction fiDI-deactivated couplers described in Chichiton Shojter No. 32613, etc.

The photosensitive material that can be used in the present invention includes a nucleating agent or a development accelerator that can be used to form an image during development. ! Compounds that release their precursors (hereinafter referred to as "development accelerators, etc.") can be used.

Typical examples of such compounds are described in British Patent No. 2. 7.
/No. 40 and No. 2. /J/, No. 111, a coupler which releases a development inhibitor etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer;
That is, it is a DA coupler.

It is preferable that the development accelerator released from the DA coupler has an adsorption group for silver halide, and a specific example of such an AR coupler is disclosed in JP-A-12-117
No. 431 and Iter No. 17 or No. 0. Particularly preferred are DA & couplers that produce N-acyl korean hydrazines having a monocyclic or condensed hetea ring as an adsorption group, which detaches from the coupling active site of the photographic coupler with a sulfur atom or an ffl-chord atom. A specific example of such a coupler is given in Japanese Patent Application Sho it-co 3710/
listed in the number.

Compounds described in JP-A-6O-371Jt which have a development accelerator moiety in the coupler residue, and compounds described in JP-A-6O-371 that have a development accelerator moiety in the coupler residue; The compounds described in No. 2i4Aror can also be used in the photosensitive material of the present invention.

The D coupler is preferably introduced into the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention, and
Tar 17-t4to or! + Hope! l-237II
Photo composition as described in issue II! - at least one layer of 'i1. It is preferable to use qualitatively non-photosensitive silver halide grains.

The texture material made using the present invention can be used as a color anticaprilant or color mixing inhibitor. It may contain non-derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, and the like.

Known anti-fading agents can be used in the light-sensitive material that can be used in the present invention. Examples of known anti-fading agents include Hyde-A-Kino-Y, t-Hitomixychromans, etc. −
Focusing on hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols, there are nine hindered phenols, gallic 1m2 derivatives, methylene dioxybenzenes, aminephenols, hindered amines, and the phenolic hydroxyl group of each of these compounds. Typical examples include ether or ester conductors that undergo conversion or alkylation. Further, total 84,11 complexes represented by (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

In the photosensitive material that can be used in the present invention, an ultraviolet absorber "fC" can be added to the hydrophilic colloid layer. For example, benzotriazoles, butadienes, cinnamon eR esters, benzophenones, ultraviolet absorbing residual compounds, etc. A polymer compound can be used. Mayu ultraviolet absorbing fluorescent whitening 41f: May be used. Typical examples of ultraviolet absorbers are 几D2 弘ゆ 3ri (/PJr4' year to month) etc. 6 self is listed.

The light-sensitive materials that can be used in the present invention are used for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification fraction, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). It may also contain one or more surfactants.

The light-sensitive material that can be used in the present invention may contain water-soluble chusen 4+ as a filter dye in the hydrophilic colloid layer for the purpose of preventing radiation, preventing halation, and other various purposes. As such dyes, oxonol dyes, hemiosonol dyes, steryl dyes, mea7 anine dyes, a/trachyno heptadate, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, Futa c17 Amon Chestnutaceae is also useful. An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The binder used in photosensitive materials is used as a protective colloid.
It is advantageous to use the entire amount of gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used. Specifically, research
Disclosure (几E8EAALOHDISCl, 0
808E) Volume 17, JkL/74gJ(/ri71
It is stated in section ■ of 2011.

The photosensitive material that can be used in the present invention may contain an inorganic or organic hardening film #Jt in any hydrophilic colloid layer constituting the photographic photosensitive layer or the pack layer. For example, chromium salts, aldehydes ( Specific examples include formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.).

Active halogen compounds (such as co, 4-hydroxy-/, !, !t-) riazine) and active vinyl compounds such as N-carbamoylpyridinium salts and heloacetic acid are preferred because they quickly harden woody co9oids such as gelatin and provide stable photographic properties. Dinitam salts also have a fast saponification rate.

Regarding the above-mentioned additives, etc., please refer to Research Dis '10-
Gee? -(Ag4:8EA&CHDI8CLO8υ几E
) magazine, compilation/74 good% A/7 Buda J (December 1171)
Those described in p, Jco-p, and JfK can be used.

Plastic films (cellulose nitrate, cellulose nitrate,
cellulose acetate, polyethylene terrescopide, etc.),
It is applied to a visible support such as paper or to a rigid support such as glass. X special holiday and application method':)%/'
For details #i 8g8EABCHDISCLO80
RB it4 lane 1t@m/744AJXV term (p,
-27) Described in Section X4 (p, Jr) (/Deaf 1st year l month issue).

(Example) Examples of the present invention will be shown below.

Example-1 The first paper was placed on a paper support lined on both sides with polyethylene.
A multilayer color printing paper having the layer structure shown in the table was prepared. The coating solution was coated in a thickness of 114 m as follows.

First layer coating liquid backside yellow coupler (a) /2.11 and color image stabilizer Φ) u, If, ethyl acetate 27. coCC and solvent (c
) 7.7 cc was added and dissolved, and this solution was emulsified and dispersed in 10% gelatin aqueous solution/rjcc.

-1 Silver chlorobromide emulsion (Silver A 0.0 molar, Ag70
f / 14 containing) and the blue-sensitive sensitizing dye shown below with silver 1
1.0 x 10 moles added per mole t-fA
After manufacturing, the emulsified dispersion and this emulsion are mixed and dissolved,
Prepare the first layer coating solution to have the same composition as the second layer. Coating solutions for the second to seventh layer phases were also prepared in the same manner as the first layer coating solution. As a gelatin hardening agent for each layer, /-O medium 3. ! -Diacs-s-triazine sodium salt was used.

Use the following as the spectral sensitizing dye for each layer.

Evening-sensitive emulsion layer tcn,)4so3'''' (CH,)480. H@N
(C. For the red-sensitive emulsion layer, the following 7 tons/1.io mole of the compound was added per mole of silver halide.

Also, for the back-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, /-(j-methylureidophenyl)-! -mercaptotetrazole t-to each 〇ge silver heptide/'&ni'A
Ratio t)r, jX/ o-”moh, 7°7×10
mol, Co#X10-4 mol was added.

For the Mayuyo-sensitive emulsion layer and the green-sensitive emulsion layer, 91.2 x lOa//1% of silver halide was added with 6-hydroxy-6-methyl-/, J, JR,7-titrazaindene, respectively. , /X10-'' moles added.

Add the following dyes to the emulsion layer before applying irradiation.

and (b) Color image stabilizer (C) Solvent (d) Color mixing prevention agent H (0 color image stabilizer (-color image stabilizer (h)! medium Conil mixture (volume ratio) (i) Ultraviolet absorber C4 [(,(su) C4H, (t) Koni 2:r mixture (1 ratio) U) Color mixing prevention agent H (k)! medium 0=P+0-09)1. , (tgo)).

(e) Color 1st stabilizer CH2CH2CU(JC, 1(□7 C4H, (S z:r:y mixture @('iIL amount ratio) (n) Polymer 4 months ago 3! ,000 (0)! medium EX-/ (”1 EX-- EX-J t EX-μ EX-z EX-bu EX-7 EX-r Out of the nine samples prepared as described above, seven samples were prepared.

The film was cut into 1 m wide pieces, exposed to light using an automatic printer, and subjected to subsequent processing using an automatic developing machine according to the processing steps shown in Table 1. Incidentally, the amount of the pre-bath carried into the washing step in each treatment was r, j m/m width, 7 m, jd.

The treatment was carried out using ioam for 10 consecutive days on the 7th day of treatment Fi.

The formulations of each treatment solution used are as follows.

Color development liquid> Mother liquid Uramitsu liquid water 100d ro
ordl-hydroxyethylidene/, /-diphospho, /, jd/
, 1 ml @ (40 q,) Sodium sulfite 06-t O,3? Potassium bromide 0. Deno-diethyl hydroxyl urea 11.2t,! ,Ofmin/,! -SheaξNo- Ko, Of Ko, JP Gropanol Potassium Carbonate Ko J, Of Ko! ,Of
Potassium hydroxide J, It bu, Jt Fluorescent whitening (Stilbene t, ot i, !f series) Sodium hydrogen carbonate! ,Of -N-ethyl-N-(β-!,!t 7.If methanesulfonamidoethyl)-3-methyl-ruaminoaniline sulfate solution is added 1000dj 10008
1pH10, J7 10.110 Bleach-fix solution> Mother solution Replenisher water 700al
700dl ammonium thiosulfate /! Ord
Ko00zu (70 fights) sacrificial @ sodium acid /If Ko! tEthylenediamine iron acetate tjp tzf(I
n) Ansonium ethylene cyano [jt IO? Aqueous ammonia or acetic acid to pH 4.7j t, 10 Add water to 10,100 O, 1,000 nl, water α water> Added 0.2 f of sodium incyanurate dichloride and Ql a to the mother liquor and replenisher solution.

Washing water B: Washing water tt-H type strongly acidic cationic silicate resin (manufactured by Mitsubishi Kasei ■, Diaion i9 1/B) and OH base strong basic anion exchange resin (manufactured by Mitsubishi Kasei@#, Diaion 8A- / OA) was passed through a hotbed column filled with water to obtain the following water quality, and then 0.2 f/lt of sodium inocyanurate dichloride was added.

After performing the above-mentioned run-on processing, the yellow and cyan concentrations of samples/~J2 were 1. Process the single color a element so that it becomes J.

In addition, we also processed unexposed samples for evaluation of yellow stain. Each sample t-to@c after treatment.

Store it for 10 days at a relative humidity of 70'lh, and examine the changes after storage.

The results are shown in Table 3. When the coupler of the present invention is used, the stability of the dye is high even when processing is performed using washing water with reduced calcium and magnesium content.

Therefore, it is possible to achieve both good image storage stability and prevention of microbial growth in washing water. Same, 9mK used in this example
Sodium isocyanurate is added for the purpose of pre-preparing the washing water, and it has been confirmed that it does not affect image storage stability.

Example-2 No. μ was placed on a paper support laminated on both sides with polyethylene.
A multi-I bud Cassie photographic paper having the layer structure shown in the table was prepared. Paint 4
The solution was prepared as follows.

First layer food cloth liquid preparation yellow coupler (a) /P, /l and color image stabilization (
b)≠, 4t2 contains acetic acid ether core, coCC and solvent (
c) Dissolve 7.7 cc with a knife and emulsify and disperse this solution in Hirzcc, an aqueous gelatin solution containing 10% sodium dodecylbenzenesulfonate.

On the other hand, salt-based milk cutting (silver bromide/, 0 molt, Aλ゛70?
/Contains the following sensitizing dyes per 7 moles of sickle! , 0") e, 10 mol. Mix and dissolve the emulsified dispersion and this emulsion to prepare a coating solution having the composition of the second layer. The coating solutions for the second to seventh layers are prepared in the same manner as the first layer.The gelatin hardening agent for each layer is /-Okiku 3.!-Dichlorog-)Ryazine sodium salt Remember to use it.

The following was used as the spectral sensitizing dye for each NO.

Back-sensitive emulsion layer (CH2) 3803H (z, oxio mole per mole of silver halide) Green-sensitive emulsion layer (t lida, 0XIO mole per mole of silver halide) and 803)IN(C2H,)3 (halogenated 1 mol of silver @ 7?: 9 7.0X10 mol) Red-sensitive emulsion layer knee (hagnization @ O, fXlo mol per i mol) For the red-sensitive emulsion layer, add the following compound to 1 mol of silver halide. per J, 4X/7-3 mole addition ratio.

For the secondary blue-sensitive emulsion ta, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, /-(j-methylureido 7EL)-! - mercaptotetrazole to silver halide, respectively.
fl knee #) 1, AX/0-”mol, 7°7
X/ o senyl, 7, jX/ 0 -1
- I added 7Jn.

Next to preventing irradiation, apply the following dye to the emulsion layer:
Add a sword to the mouth.

3s 3 people 3s, ni (b)
Color image stabilizer (C) Solvent (d) Anti-fading agent H (f) Color brightness stabilizer H3CH3 (2) Color image stabilizer (h) 1:1 mixture of solvent * (volume filtration ratio) (JH OH - :R:L mixture (coulometric ratio) U) Color mixing inhibitor OH (k) Solvent 0==+P+0-C,)11. (i80)).

- Color image stabilizer CH2C center C00C8H1□ C4)1. (t) (n) Polymer C:C)NHC4H0(t) Average molecule it! ! , 000 (0) Solvent When the color photographic paper mentioned above was subjected to two tests similar to those in Example 1, similar results were obtained.

In the above process, the amount of bleach-fixing solution brought into the washing process was determined by r, zm/m width photographic paper, tm, and jd.

The formulations of each treatment solution used are as follows.

Color developing solution mother solution Brightening solution Triethanol and 7i7 1. Of 10. Ifl
N,N-dietherhidoku 〆,xt t,Oychyzyluaneζn fluorescent brightener (da,g'-i,at a,otsiaζnosterbene series) Ethylenecyamine tetranodic acid /,Of /Jf? Potassium carbonate JOoOf! 0. O? Sodium chloride /, 4c9 0. /l daloo ξ no 3-methyl! ,Of 7,0f-N-
Add ethyl-N-1β-(methanesulfonamide) ether)-p-phenylenesia water 1000tll 1000
dp)l/a, 10
10. ! 0EDTAFe([)NH,−,2)12(J
OfE D'r A -J Na --
2H204' tAnthonium thiosulfate (70%)
/20d Sodium sulfite
add itt water 1000 gop
Hi,z Rinsing water A': Used in Example-7 and added to nine tap water (ratio 9
I! Example 2) Washing water B' with silver nitrate 0.3/E added instead of sodium incyanurate: Same as washing water B in Example 1 (invention). Nitric acid @0 instead of sodium incyanurate di-salt in water. Addition of Jη/l In addition, the addition of nitrate silver to the pilot water was used for the same purpose as the dichloride incyanuric sodium in Example-l, and #4111t- was not added to the image preservability. It has been confirmed.

Example-3 In Example-/IC, using stabilizing solutions A and B shown below instead of washing water A and B, Kuike carried out the test in the same manner as in Example-1. Even in the case where a t6 stabilizer is used to obtain the same result as in the case of -/, the present invention can be used to obtain a nine-color image with excellent image stability, as in the case of washing water.

Contains stable solution (mother solution and replenisher are the same (comparative example)) Tap water -〇d Bismuth trichloride pentahydrate 0.07f Nitri e+-N,
N,N-trime/,Oftyrenephosphonic acid (0
2. Ifl-
Diphosphone #1 (but 0%) Fluorescent brightener (蓼、蓼'-DIAMI/、Ofnosterbene type) Ammonia water (2≦CH) Add Ovd tap water 1000M7y%=7water (JAts)K The pH was 7.0, and the quality of the tap water used was the same as in Example-1.

Stable W1. B (Main #4) Tap water't - Same as Example 7, ion exchanged, round wood used, except for the stabilized liquid.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Showa era 1 month 1 day three

Claims (2)

[Claims] (1) In the method of processing a silver halide color photographic light-sensitive material, the concentration of calcium and magnesium compounds in the washing water and/or stabilizing solution is reduced to 5 mg/l or less as calcium and magnesium, respectively,
Processing of a silver halide color photographic light-sensitive material, characterized in that the light-sensitive material to be processed contains a 2-equivalent yellow coupler represented by general formula (I) and a 2-equivalent cyan coupler represented by general formula (II). Method. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 represents an N-phenylcarbamoyl group. R_2 is a tertiary alkyl group having 4 to 20 carbon atoms or , represents a phenyl group.
General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ In the formula, R_3 is an aliphatic group, an aromatic group, a heterocyclic group, represents an aromatic amino group or a heterocyclic amino group; R_4 represents a hydrogen atom, or an aliphatic group having 1 or more carbon atoms or an acylamino group; Z represents a hydrogen atom, a halogen atom, an aliphatic, aromatic, or acylamino group; , X_2 represents a group other than a hydrogen atom that can be separated during a coupling reaction with an oxidized form of a developing agent. Here, R_4 and Z may be connected to each other to form a ring, and by one group among R_3, R_4, X_2, and Z,
A dimer or more multimeric coupler may also be formed. (2) The method for processing a silver halide color light-sensitive material according to claim 1, wherein the amount of washing water and the replenishing amount of 1 or the stabilizing solution is 1 to 50 times the amount brought in from the previous bath.