JPH01214846A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the thermal fading of a cyan dye in the dark and the increase of a stain in the sensitive material after processing by developing the sensitive material contg. a prescribed cyan coupler with a color developer contg. a prescribed compd., and by specifying the replenishing amount of a development replenisher. CONSTITUTION:The sensitive material having a layer contg. the cyan coupler shown by formula I is developed with the color developer which contains a compd. shown by formula III and does not substantially contain benzylalcohol. And the replenishing amount of the development replenisher is specified to 20-200ml per 1m<2> of the sensitive material. In formula I, R<1> is alkyl or aryl group, etc., R<2> is acylamino or >=2C alkyl group, R<3> is hydrogen or halogen atom, etc., Z<1> is hydrogen atom or a group capable of being released, etc. The component shown by formula I is composed of a compd. shown by formula II, etc. And in formula III, R<5> is a substd. alkylene group, R<6>-R<9> are each hydrogen atom or alkyl group, etc. The component shown by formula III is composed of a compd. shown by formula IV, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application J) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, particularly in low-replenishment processing for color development, which has less staining and excellent color development. The present invention also relates to a processing method that provides photographic performance and provides a color image with excellent image stability after processing.

(Prior art) Color photographic images are stored as records for a long period of time, but during the storage period, the image area may undergo undesirable fading or discoloration due to the influence of atmospheric humidity, temperature, light, etc. A cyan coupler that is robust to humidity and temperature, which often causes problems, is U.S. Special Order No. 7.772.0.
A phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus described in No. 02, and JP-A-Sho! Tar 166, Ri No. 56, Tokko Akira ≠ Tar l/! 72
The cyaflamino cyan couplers described in No. 1, etc. are known. However, these cyan couplers
When continuous color development processing, especially continuous processing in which the amount of color development replenisher is reduced, the halogen concentration in the color development solution increases and the color development performance deteriorates due to the accumulation of components eluted from the photosensitive material. It turned out that the temperature was low. On the other hand, it has been known to use benzyl alcohol as a color development promotion technique. However, when benzyl alcohol is used for the low light compensation processing of color f+iA images as described above, the stain after processing is reduced. It also causes unfavorable results in terms of pollution, liquid preparation properties, etc.

(Problems to be Solved by the Invention) Accordingly, the object of the present invention is to provide a cyan dye that has excellent implicit fading resistance, and that does not increase staining after processing even when low replenishment processing is performed for color development. It is an object of the present invention to provide a processing method capable of obtaining a cyan image without impairing color development.

(Means for Solving the Problems) It has been found that the objects of the present invention can be achieved by the following method. In other words, a silver 10-genide color photographic light-sensitive material of the following general formula (having a layer containing at least /ai+ of a cyan coupler represented by C-13) is prepared by adding a small amount of a compound represented by the following general formula (U). (In a method of processing with a color developing solution containing 7 m2 and substantially no benzyl alcohol, the replenisher of the color developer replenisher is 20 m1 to 200 m2 per 1 m2 of the color photosensitive material.
It has been found that this can be achieved by a method for processing a silver halide color photographic material, which is characterized by the following.

General formula (C-1) (In the formula, R'i alkyl group, cycloalkyl group.

Indicates an aryl group, an amino group or a heterocyclic group.

R2rc represents an acylamino group or an alkyl group having 2 or more carbon atoms. R3 represents a hydrogen atom, ).rogen atom, an alkyl group or an alkoxy group. Further, R3 may be combined with R to form a ring.

Zl represents a hydrogen atom, a hydrogen atom, or a group capable of leaving in reaction with an oxidized product of an aromatic primary amine color developing agent. ) General formula (n) In the formula, R5 is a substituted alkylene group, R6, R7゜R8,
and R9 are the same or different and each represents a hydrogen atom, an alkyl group, or an aryl group. ) For boat fishing, couplers are thought to be subject to fluctuations in color development due to changes in the concentration of competing compounds such as preservatives in the color developer, but due to the stabilization of the preservatives mentioned above, From the viewpoint of improving fluctuations in photographic properties, the compound (n) of the present invention
This is known from Japanese Patent Application No. A/-114!60.

However, as in the present invention, poor color development of the cyan coupler under low replenishment conditions is particularly noticeable in the cyan coupler represented by (C-I) according to the present invention, and due to the presence of the compound (II) of the present invention, It can be said that the remarkable improvement in color development is an effect that cannot be expected only by suppressing the concentration change of the competing compounds.

Next, general formula IC-1) will be explained in detail.

In the general formula (C-17, examples of the alkyl group with carbon number/-jλ of R1 include methyl group, butyl group, tridecyl group, cyclohexyl group, allyl group, etc.; examples of the aryl group include phenyl group, naphthyl group) Examples of the heterocyclic group include λ-pyridyl group,
Examples include a caufuryl group.

When R1 is an amino group, a phenyl substituted amino group which may have a substituent is particularly preferred.

R''U, and further alkyl, aryl, alkyl or aryloxy groups (e.g. methoxy, dodecyloxy, methoxyethoxy, funinyloxy).
Z, ≠-data tar t-amirfunini/-? C:L
j -ter L-'7" hydroxyphenyloxy group, naphthyloxy group), Cal 1+: life group, alkylmuff t has an aryl carbonyl group (e.g., acetyl group, tetradecanoyl group, benzoyl group, etc.) ), alkyl is an aryloxycarbonyl group (e.g., metodicarbonyl group, phenoxycarbonyl group,
], acyloxy groups (e.g., acetyl group, benzoyloxy group, etc.), sulfamoyl groups (e.g., N-
ethylsulfamoyl E, N-ophtacylsulfamoyl group, etc.), carbamoyl group (e.g., N-ethelcarbamoyl group, N-methyl-dodecylcarbamoyl group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), acylamino group (e.g., acetylamino group, penmeamide group, ethoxycarbonylamino group, phenylaminocarbonylamino group), imide group (e.g., succinimide group,
hydantoinyl group, etc.), sulfonyl group (for example, methanesulfonyl group, etc.), cyano group, etc. # with primary ff11 group selected from nitro group and halogen atom
It may be changed to L.

-Symbol ((,'-1) - (Zl is a hydrogen atom, and Zl represents a coupling-off group; examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), Alkoxy groups (e.g., dodecyloxy, methoxycarbamoylmethoxy, carboxydipropyloxy, methylsulfonylethoxy, etc.), aryloxy groups (e.g., chlorophenoxy, ≠-methoxyphenoxy, etc.), acyloxy groups (e.g., acetoxy, tetrazocallyoxy, benzoyloxy), sulfonyl groups (e.g., methanesulfonyloxy, toluenesulfonyloxy),
Amide group (e.g., dichloroacetylamino group, methanesulfonylamino group, toluenesulfonylamino group), alkoxyΦdicarbonyloxy group (e.g., ethoxycarbonylamino group, (andyloxycarbonyloxy group, !'), 7!J-ruoxycarbonyloxy group (
(e.g., phenoxycarbonyloxy group), aliphatic or aromatic thio group (e.g., phenylthio group, tetrazolylthio group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), N-hetero@ (e.g., l- Examples include pyrazolyl group, l-benz, triaglyl group, aromatic azo group (eg, phenylazo group, etc.). These leaving groups may include photographically useful groups.

In the general formula <, c-1), R''Jt may be a dimer or a multimer of -i'L or more in R2.

Specific examples of the cyan coupler represented by the general formula (C-1) are listed below, but the present invention is not limited thereto.
'x not.

(C-λ) LL (U-J) (C-≠) (cr) tJLh2UH4LH4U(J(JR (C-7) H (C-//) α (C-tco) (tneetJ) (c-tr) (L"-/7) (C-/r) (C-/ri) (C-co0) (C-λ1) (C-co1) (X:)13 The above general formula ( The cyan coupler represented by C-I) is
Tokukai Sho tP-IttPjt issue, Tokuko Sho≠ter//! 72
It can be synthesized based on the description in No.

General formula (using cyan coupler represented by C-N,
For how to use it, please refer to the coupler description below.

General formula (II) will be explained in more detail below.

In the formula, R5 is a hydroxyl group, alkoxyl group, aryloxy group, amino group, sulfo group, phosphonic acid group, sulfonyl group, ureido group, acyl group, alkylthio group, arylthio group, carbamoyl group, sulfamoyl group, acylamino group, sulfone At least one amide group, halogen group, cyano group, and nitro group, and a linear or branched alkylene group (for example, cohydroxytrimethylene &, /-methoxypentamethylene group, etc.) containing one or more types of interleaved Table of contents. Also R6, R, R8
and R may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or t? I
t represents an unsubstituted aryl group.

The alkyl group and the aryl group include a frame, a hydroxyl group, an alkoxyl group, an aryloxy group, a carbonyl group, an amino group, a sulfo group, a phosphonic acid group,
Preferred are a sulfonyl group, a ureido group, an acyl group, an alkylthioamide, an arylthio group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamide group, a halogen group, a cyano group, and a nitro group. A single alkyl group or aryl group may be substituted with two or more types of these substituents. Among the functional groups contained in the formula, carboxyl groups, phosphonic acid groups, and sulfo groups are salts of alkali metals (e.g., sodium, potassium, etc.) or positive atoms (e.g., H2O, Ca2, etc.). (Also, the amino group can be used for hydrochloric acid, nitric acid,
Phosphoric acid May form salts with various acids such as oxalic acid and acetic acid.

In the general formula (IN, R is preferably a hydroxy #-substituted alkylene group, an alkoxy-substituted alkylene group,
These are an amine-substituted alkylene group, a sulfo-substituted alkylene group, and a ureido ha alkylene group. Also, R, R,
R8 and It5 are preferably a hydrogen atom, a free alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, etc.); It is a substituted alkyl group.

Further, R, R, R in general formula (n).

The total number of carbon atoms in R8 and R9 is preferably 30 or less, more preferably 0 or less.

The amount of yO added to the compound represented by the general formula (n) according to the present invention is preferably 0.00% per liter of color developer. /
1-20g, more preferably Q.

j-10fl.

Typical examples of the compound of general formula (n) in the present invention are listed below, but the present invention is not limited thereto.

H ■ It-(1) H2N CH2CHC)12-N
)12C)i 20H Width u(to 31Hz-(CH213-CH-N)12C)1
20) I II-(Mon H2N -(CH2)4-CH-NH2
(HOCH2CH2su21'1iCH2CHC) to 12+CM2CH20H)2(HOC)12 CH2su2N
(CH2)4-CH-N+CH2CH20f() 2(
HO2CCHz2NCH2CHCH2N(-CH2C
O2H)2) 102cc) 12 to HCH2CHcH2Hc)12co2HNa02C-CI(2C82CO2
Nazu(Na02SCH2+2NCHzCHCHzN(-CM
zsOaRa)2(CH30CH2CH2+2N CH
2CHCH2N (CH2CH20C)i3 ) 2(
CH30CH2CH2su2N (CH2)4 CHN
(CH2CH20CH3) 2(C)130cH2c
H2-)-2NCH2CHC)12N(CH2CH20
CH3) 2 (HOCH2CH Gakuden CH2CHCH2N
(CH2CH20)1 ) 2n-(/7 J NHC8H (HOCH2CH2J2 NCH2CHC)i2N+
CH2CH20H)211-(/r) ■ To (HO2CCH2)2 To CH2CHCH2 (C112
CO2H)2CH3C+0t2CH2 to CH2CHCH
2 to cl(2CH2o(,"1-13■-(ko j; 1-(J/) ■-(3) H2N CH2CHC)12 C) iC) 12 to H2■
-<33) ■-(3hiro) H3 n-(,?j) The compound according to the present invention can be easily obtained as a commercial product. Also, Organic 5 synthesis
), /(7 to l, /j≠, 321.jtjlr:fJJ
.

It can also be easily synthesized according to No. 370 and roo.

The color developing solution used in the invention contains a known aromatic primary amine color developing crude drug.

Preferred examples are p-phenylenediamine derivatives. Representative examples are shown below, but the invention is not limited to these.

]) -iN, N-diethyl-p-phenylenediamine D-,2,2-amino-yo-diethylamine toluene D-32-amino-yo-(N-ethylhelaurylamino)toluene D-≠ ≠-[ He ethyl he (β-human axyethyl) aminocoaniline D-j comethyl ≠ - [he ethyl he [β-
hydroxyenalfamino]aniline D-A μmamino-3-methyl-h-ethyl-N-
[β-(methanesulfonamide)ethylno-aniline D-7N-(u-abano-yetyl-inophenylethyl)methanesulfonamide D-1r N,N-dimethyl-p-7 22-diamine D- ta μmamino-3-methyl-he-dithyl-hemethoxyethylaniline 1)-/Q Hiro-amino-3-methyl-heether-
to-β-ethoxyethylaniline I)-// Hiro-amino-3-methyl-to-ethyl-to-β-butoxyethelaniline Among the above p-phenylenediamine fatty conductors, particularly preferred are Hiro-amino-3-methyl-to- Ethyl-N-(β-(
methanesulfonamidecanityl]-aniline (exemplified compound D-6).

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, Wtrite salt, and p-toluenesulfonate. The aromatic-grade amine developing agent used is preferably about 0, tg to about 09, preferably about 00, per liter of developer solution. g to about 1077.

If necessary, any development accelerator can be added to the color developer. However, the color developer of the present invention needs to be substantially free of benzyl alcohol in order to prevent cyan staining during low replenishment processing.

Here, "substantially not containing benzyl alcohol" means that the benzyl alcohol content per liter of color developer is 2 d or less. Preferably, it does not contain any benzyl alcohol.

In addition, as compounds for directly collecting the color developing agent, various hydroxylamines, Japanese Patent Application No. 1987-irtzz
Hydroxamic acids described in No. 1, t/-1117172
No. and phenols described in No. t/-2032413,
al-irr'y≠7 α-hydroxytons and α-aminoketones described in No. 1, and/or +1-iro
It is preferable to add each of the saccharides listed in the Tit No.

Among them, Tokkō 6-12 Hiro 037, 42-/2170
31, same 4/-1/j! The nohydrazines described in No. 31 etc. are excellent preservatives and are most preferably used in the present invention.Other preservatives include sodium sulfite, potassium sulfite, sodium monosulfite, potassium bisulfite, and sodium metasulfite. , a sulfite such as potassium metasulfite, or a carbonyl sulfite adduct can be added as necessary. Addition to these color developers]
The length is i, og 71 or less, preferably 0. j&/l or less, and more preferably, it does not exist as long as the stability of the liquid is maintained. In particular, when using the compound of the present invention in a developer that does not contain benzyl alcohol, it is preferable that the amount of sulfite ion added is small in terms of stability and/or photographic properties.

Furthermore, JP-A No. 7-4/-Ko 14CR and the same! 7
-137≠ Various metals described in No. 2, JP-A-Shoj Tar 1r
Salicylic acids described in OS-RR No. JP-A-Sho! Hiro-3!1
Alkanolamines described in No. 32, JP-A No. 6-ta μ
3≠Polyethyleneimines described in No. 3, U.S. Watch No. 3.
7≠6. If necessary, the aromatic polyhydroxy compound described in No. 1 may be contained. In particular, aromatic polyhydroxy compounds, triethanolamines, and patent application Sho A/-2
The addition of the tjlμ2 compound is preferred.

The color developer used in the present invention preferably has a pH of 2
~/, 2, preferably ~ii, o, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
Hedimethylglycine salt, leucine salt, norleucine salt, guanine salt, 31-hiro-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, λ-amino-comethyl-/, 3-propanediol salt, valine salt, florin salt , trishydroxyamine methane salt, lysine salt, etc. can be used. Particularly soluble in carbonates, phosphates, tetraborates, hydroxybenzoates, pH 2.0
These buffers have excellent buffering capacity in the above high p I-1 region, have no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and are inexpensive. It is particularly preferable to use

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium carbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, Sodium Tetraborate (Borax), Potassium Tetraborate, Sodium O-hydroxybenzoate (Sodium Salicylate), Potassium O-Hydroxybenzoate, !-Sulfo-Hydroxybenzoate #flJium (t-Sodium Sulfosalicylate) , potassium j-sulfo-2-hydroxybenzoate (!-potassium sulfosalicylate)
etc. can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mol/l or more, particularly 0.1 mol/l-
0.4 Amol/! It is particularly preferable that others,
Various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as the aminopolycarboxylic acids described in JP-B-4CT-IO-4L-2 and Hirohiro-30-32; 6-273μ
No. 7, Special Public Shojj-3F! ! No. 2 and West German Tokuo No.-1λ
, No. 27,632, organic phosphonic acids, JP-A-Sho! Ko 1O2726, Koj3-≠2730, Koj Hiro-l
Ko//λ7, same 71-/kot Koda 1 and same! -6
! Phosphonocarboxylic acids described in t9!06, etc., and other % Kaisho sr-/yzraz issues, same! r-203144
Examples include compounds described in No. 10 and Tokuko Shoyo 3-Hiro Oori No. 00. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenecyabane tetrafifi, N,N,N-trimethylenephosphonic acid, ethylenecyabane-N,N,N'.

to′-tetramethylenephosphonic acid, trans-cyclohexanediaminetetraacetic acid, /,! -Diaminobuo＠＠y
4g 11. f Recall ether diamine tetraacetic acid, ethylene diamine orthohydroxyphenyl acetic acid, λ
-phosphonogtan-l, λ, ≠-tricarboxylic acid, l-
Hydroxyethylidene-7,/-diphosphophone m, N, N
'-bis(,2-hydroxybenzene)ethylenediamine-N,N/-dicarboxylic acid These chelating agents may be used in combination in combinations of two or more, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
Hit 0. It is about /1-109.

For color developers, optional development accelerators may be used.
-191r7, 31-7126, 37-191
r7, 4L Tata 0/ri and US Special 7FF No. 3. r
/3.2 Thioether compounds represented by Hiroshi No. 7, etc.
Tokukai Shoyo Koguri T22 and Mukai 10-/ta! ! p-phenylenecyamine compound represented by Hirogo, JP-A-Shoj
O-/37m, special public Akira! Lt Hiro-30071A, JP-A Shojbu-/jAr24 and the same! 2-Hiro 3 Hiro λri number,
μ-class ammonium salts represented by U.S. Clock No. 2.
Hirohiro, No. 703, same J, 72r.

irx No. 41,230,72, No. 3,213.
No. 21, Tokusho≠/-ii≠37, American Watch No. 2.
≠lrko,! ≠ No., same co,! rit, ri 2 and 3
．． Amine-based compounds described in It2.3 Hiro, etc., Japanese Patent Publication No. 37-16011, Japanese Patent Publication No. 2-2!20/No. /Ko 31, Koko 3tri and U.S. special ff No. 3, j
Polyalkylene oxides such as those listed in Nos. 32 and 10/, others/-722-3-pyrazolidones, imidasoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as potassium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. , organic antifoggants include, for example, benzotriazole, t-
Nitrobenzimidazole! - ditroisoindazole! -Methylbenzotriazole,! - Nitrobenzotriazole,! Typical examples include nitrogen-containing heterocyclic compounds such as -chlorobenzotriazole, corchiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent brightener, Hiro, Hiro I-
Diamino-2,2'-disulfostilbene thread compounds are preferred. The amount added is O-yol/1fkl, μo, ig
~≠g/13.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color imager of the present invention is 20-! 00C, preferably d30-≠O0C. Processing time is 20 seconds! minutes, preferably 30 seconds to λ minutes.

Although it is preferable to replenish less, the amount of replenishment is preferably λO-/lamg per m22 of light-sensitive material. Historically, the longest is 2! M~100m1.

Next, the desilvering step in the present invention will be explained.

Generally, any process such as a bleaching process-fixing process, a fixing process-bleach-fixing process, a bleaching process-bleach-fixing process, or a haze-fixing process may be used for the desilvering process. In the present invention, the effects of the present invention will be more pronounced if the process time of the desilvering step is shortened. That is, 2 minutes or less, more preferably 1 to 1 seconds.

Deiron removal process The fishing white liquor, bleach-fix solution, and fixer used in the desilvering process will be explained.

As the bleaching agent used in the whitening solution or bleach-fixing solution, any bleaching agent can be used, but in particular iron (
Organic complex salts of 1) (e.g., complex salts with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentate #1, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids) or ethanoic acid, tartaric acid, malic acid Organic acids such as; persulfates; hydrogen peroxide and the like are preferred.

Among these, organic complex salts of iron (Ill) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complexes of iron(1)? To enumerate, ethylenediaminetetraacetic acid, diethyleneditriamine/pentacarboxylic acid, 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotrihydroacid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron(1) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentamic acid, cyclohexanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

These ferrous ion complex salts are used in the form of complex salts,
Good, aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids with ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. A ferrous ion complex salt may be formed in one solution using a chelating agent such as Further, the chelating agent may be used in excess of the amount required to form the ferrous ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount of 71D added thereto is preferably 0.02 to 0.0 mol/l. ! It is 0 mol/l.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or pre-bath thereof. For example, the US% total is 3rd. tri3. Specification of RJT, German Special Edition No. 1, 2, RI, Specification of JP-A No. 430, Research Disclosure No. 17/2
Compounds having a mercapto group or a disulfide bond described in the ``Li issue'' (July issue of ``Li 7r''), and Tokko Akihiro t-rr
.

No. Tokukai Akira! No. 20132, same j3-32731
The thiourea thread compounds described in US Pat. No. 3.70, U.S. Percent Total No. 141, or halides such as iodine and bromide ions are preferred because of their excellent bleaching properties.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (
For example, a rehalogenating agent such as ammonium iodide) may be included. If necessary, one type of boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, thorium phosphate, citric acid, citric acid (Rf thorium, tartaric acid, etc.) with a pH buffering capacity. The above inorganic acids, organic acids, and alkali metal or ammonium salts thereof.
Corrosion inhibitors such as guanidine and the like can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, that is, thiosulfur #! Kado IJ Ram,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thio7anate and ammonium thiocyanate; thioether compounds such as ethylene bisthioglycolic acid, 3,6-cythio, r-octanediol, and thioureas; It is a water-soluble silver halide dissolving agent, and one or more of these can be used in combination. Also, Tokukai Show 1! -/! ! It is also possible to use a special bleach constant *i, which is a combination of the fixing agent described in No. 31≠ and multiple halides such as potassium iodide. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. In consideration of the fixing agent per 1 liter, 0.3 to 2 mol is preferable, more preferably 1 mol.
Actually O0! ~1.0 mol. The pi-1 region of the bleach-fix solution or fix solution is preferably 3 to io, and even more! 〜ri is particularly preferable.

The bleach-fix solution VC can also contain various other fluorescent brighteners, antifoaming agents, surfactants, and universal solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g. cadmium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ] These compounds contain sulfite ion-releasing compounds such as sulfite ion-releasing compounds.
It is preferable to contain 02 to 0!0 mol/l, and more preferably 00 to 01 mol/l.

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

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

Aqueous solution and/or stabilization In the treatment of the present invention, aqueous solution and/or stabilization treatment is generally not performed after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, λ depending on the material used such as the coupler, the purpose, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and various other conditions. The relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is determined by Jour Cal Ogza Society Og Motion Picture and Television Engineers (Journal).
alof the 5ociety of Mo
tion Picture and Televisi
on Engineers) Part A! Volume, P, 2 hiro
It can be obtained by the method described in -2 to 3 (l!! year! month number). Usually, the number of stages in a multistage countercurrent system is
t is preferable, and 2 to Hiroshi is particularly preferable.

According to the multi-stage counter-current method, the amount of washing water can be greatly reduced, for example, by 0.5 ml per m2 of photosensitive material. ! l-/l or less is possible, and the effect of the present invention is remarkable, but there are problems such as increased residence time of water in the tank, bacteria propagation, and the generated suspended matter adheres to the photosensitive material. occurs. Power of the present invention 2 - As a solution to such problems in countries where photosensitive materials are processed, the method for reducing calcium and magnesium described in Japanese Patent Application No. 1987/-/3/632 can be used extremely effectively. be able to. In addition, chlorine-based disinfectants such as iso, thiazolone compounds and thiabendazole described in JP-A No. 17-11171, chlorinated sodium iso-7anurate described in JP-A No. 4/-/20/≠S, Benzotriazole, copper ion, etc. described in No. 10-47 of 1974, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, Sanitary Technology Gold Wire "sterilization, sterilization, and antifungal technology of microorganisms", Nippon Antibacterial Prevention It is also possible to use the fungicides described in Kogaku Kinsen's "Encyclopedia of Antibacterial and Antifungal Agents."

Historically, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used in the washing water.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound represented by formalin, or BA suitable for dye stabilization.
Examples include buffering agents and ammonium compounds for adjusting p)i. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, fluorescent brighteners, and hardeners may be added.In the processing of the photosensitive material of the present invention, when stabilization is directly performed without going through a water washing step, JP-A-77
-11113, 11'-/4Cj3, to-22
03 Hiromu! The known methods described in No. 1, etc. can be used in combination.

In addition, it is also a preferred embodiment to use chelating agents such as l-hydroxy7ethylidene/,/-diphosphonic acid and ethylenediaminetetramethylenephos*y acid, and magnesium and bismuth compounds.

In the present invention, a so-called rinsing solution is also used as a washing solution or a stabilizing solution used after the desilvering treatment.

pHtl in the water washing step or stabilization step of the present invention is ≠ ~ 10, preferably! ~t. Although the temperature can be set variously depending on the use and characteristics of the photosensitive material, it is generally 15 to 4 Lt'.
c is preferably λO~≠00C. Although the time can be set arbitrarily, the effect of the present invention is significant even if it is short, and it is preferably 30 seconds to minutes, preferably 30 seconds to minutes. Even if the amount of replenishment is small, it is preferable from the viewpoints of running costs, reduction in emissions, ease of handling, etc., and the effects of the present invention are also large.

The preferable amount of mirror replenishment is 005 to 50 times the amount brought in from the front bath per unit area of the photosensitive material, preferably "!L<ex
3 times to ti, o times. Or photosensitive material 1rIL2
per liter or less, preferably zooy or less. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. As an example of this, it is possible to reduce the amount of waste tL by flowing the overflow of washing water reduced by the multi-stage countercurrent method into the bleach-fixing bath that is the previous bath, and adding concentrated liquid to the bleach-fixing bath. can give.

The method of the invention can be applied to any processing step. For example, it can be applied to the processing of color direct-positive photosensitive materials, color positive films, color negative films, color reversal films, etc., with color beno ff-, color reversal beno- preferable.

Next, details of the silver halide color photographic light-sensitive material processed in the present invention will be explained.

The light-sensitive materials processed in the present invention must contain various color couplers. Here, the term "color coupler" refers to a compound that can generate a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. It is preferable that the color coupler has a ballast group or is polymerized so that it has diffusion resistance. A bifunctional color coupler in which the coupling active position is a hydrogen atom and the ellipse is also substituted with a leaving group is preferred because the amount of coated silver can be reduced and the effect of the present invention is large. Couplers in which the coloring dye has an appropriate diffusivity, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

Yellow couplers that can be used in the present invention include U.S. Clock No. 3.11 Or, /Reference, U.S. Clock No. 3. Hirohiro 7, Ri 2r
No. 3. 33. No. 101 work done by Hiroshi, 0 λ,
Oxygen atom separation type yellow coupler described in No. 620 etc. or Tokko Sho! r-io7i issue, American Watch News, 110/, 7! rλ No., $324.021
No. 7, RDIIrOjJ
F 1st. ≠Ko 2, No. 0.20, West German Application Publication No. 2, 2/
Ri, Ri No. 17, Sai No. 2.21, 1.36/, Sai No. 2.
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 32, JRZ and No. 4/-33,112. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, and -10,000 α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Couplers of pyrazoloazole threads such as pyrazolones and pyrazolotriazoles may be mentioned. ! - As for the pyrazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an annulamino group are preferable from the viewpoint of the hue and coloring density of the coloring dye. , same No. 2゜3
'A3.703, same No. 2,400,711, same No. 2
．． No. 901.173, No. 3,062. tjJ No. 3. l! It is described in Ko, Ryt No. 3 and No. 3゜234.01j. Two equivalents! - As a leaving group for pyrazolone couplers, US % Liver No. 310, 1. Nitrogen leaving group or US% liver number ≠, 3
! /, and the arylthio group described in Ir No. 7 are preferred. In addition, the ballast group described in European Watch No. 73.43 [T! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, U.S. Watch No. 3.
3t, f7, birazolobenzibadazoles, preferably pyrazolo(j, /-cJ(/, 2.4'JIJ azoles, research・Disclosure 2 ≠ Coco 0 (/
The pyrazolotetrazoles described in Research Disclosure 2≠230 (Ir., June 1999) and the pyrazolopyrazoles described in Research Disclosure 2≠230 (Ir., June 1999) are mentioned.

Ranked 11th and 7th in Europe in terms of low yellow sub-absorption and light fastness of the coloring dye. Ibadashi (/,
2-bJ pyrazoles are preferred, European Watch No. 11,
Pyrazolo [/.

j-bJ (/ , 2.4AJ triazole is particularly preferred).

In the present invention, other high-equivalent couplers may be used in combination as necessary, and granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusivity. Such dye-diffusive couplers are available from US Pat.
tt, No. 237 and British Watch No. 2. A specific example of a magenta coupler can be found in the Icoj, J70 issue, and the European Watch No. t,
Examples of yellow, magenta or cyan couplers are described in No. Jr. 70 and German Published Application No. 3.23μ, 533.

The dye-forming couplers and the above-mentioned special couplers may form secondary or higher polymers. Typical examples of polymerized dye-forming couplers are U.S. I, azi, r2
No. o and p, oro.

It is described in the lti issue. Specific examples of polymerized magenta couplers are described in British Watch No. 2,10λ, 773 and US Special IFF No. μ, 3t7,21λ.

Two or more of the six couplers used in the present invention can be used together in the same photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in combination with different couplers. It is also possible to introduce more than one layer.

Standard usage of color couplers is in the range 0.00/'fg to 1 mole per mole of photosensitive silver halide, preferably 0.01 to 0.5 mole dO for yellow couplers and 0.01 to 0.5 mole for magenta couplers. 0.003 to 0
．． 3 mol, or 0.00 to 0 for cyan coupler
．． It is 3 moles.

The couplers useful 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-water dispersion method is U.S. Clock No. 2,322.027.
It is written in the number etc.

Further, the process and effects of the latex dispersion method, as well as specific examples of latex for impregnation, are given by Tokuo Daihiro, L. Tata, USA.

No. 363, West German watch application (01, Sun No. 2.!Hiroshi/.

No. 27μ and No. 2. ! 4c/, Ko3Q issue, etc.

The silver halide emulsion of the light-sensitive material used in the present invention may have a halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride. For example, color page/
When performing rapid processing or low replenishment processing such as, silver chlorobromide emulsion or silver chloride emulsion containing 10 mol% or more of silver chloride is preferable, and moreover, when the content of silver chloride is to-ioomolar. is particularly preferred. In addition, when high sensitivity is required and fog during production, storage, and/or processing must be kept particularly low, silver bromide f! -0 mol%
Silver chlorobromide emulsions or silver bromide emulsions (which may contain silver iodide in an amount of 3 molar or less) are preferred, and further contain 70 molar or less silver iodide.
It is preferably mol% or more. Silver iodobromide and silver chloroiodobromide are preferable for color light-sensitive materials for photography, and the silver iodide content is preferably 3 to 1 molar.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

The average grain size distribution of the silver halide grains used in the present invention may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size It is preferable to use a so-called monodispersed silver halide emulsion having a density within 2θ%, particularly preferably within 1%.Also, in order for the light-sensitive material to satisfy the target gradation, substantially Two or more types of monodispersed silver halide emulsions with different grain sizes (preferably those having the above-mentioned fluctuation rate as monodispersity) are mixed in the same layer or in separate layers in an emulsion layer having the same color sensitivity. It is possible to apply a multilayer coating.Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be mixed or layered for convenience.

The silver halide grains used in the present invention have regular shapes such as cubes, octahedrons, dodecahedrons, and dodecahedrons.
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
It may have a crystalline form (ular), or it may have a composite form of these crystalline forms. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of t to 2 or more occupy 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used.

These various emulsions may be either a surface latent image type in which latent defects are mainly formed on the surface or an internal latent image type in which latent defects are formed inside the grains.

The photographic emulsion used in the present invention is RES EARC) I
DISCLO8URE vol, / 701 tem
/%/ 7Ap3 (1, 11, III) term (/P7r,
It can be adjusted using the method described in /, 2).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 171. Volume, A77G Ko 3 (/ri7ri, January and February)
and Volume 117 of the same publication, published in November, and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures 1 Chemical sensitizers Page 23 Right column 2 Sensitivity enhancers
Same as above 3 Spectral sensitizer 23~λhiro page 6≠r page right column~4 Supersensitizer 6hiro page right hand column 5 Brightening agent
, 2≠Page 6 Anti-fog agent λhiro~2! Page O≠R Page right column Stabilizer 7 Cover - 2t Page 8 Organic solvent Page 21 9 Light absorbing agent, 2! - Page 2 2 ≠ Page right column - Filter dye 610 Left column 1O Ultraviolet absorber 11 Stain inhibitor 2T Page Right column 4jO Page Left - Right column 12 Dye image stabilizer Page 25 13 Hardener page 26 Tri page Left column 14 Binder page 26 Same as above 15 Plasticizer, lubricant page 27 Tro page right column 16 Coating
Fabric aids, pages 2t-27 Same as above Surfactant 17 Stannac Page 27 Same as above
Stopping agent 2: Photo AFJ optical material used in the invention 'p- is a commonly used plastic film, (cellulose sulfate, cellulose acetate, polyethylene terephthalate, etc.), an available fork holder such as paper, fc is glass, applied to a rigid support such as For details on the support and coating method, please refer to RESEARCH DISCLOSURE tyg
Volume, Item/'7+p3, X7 item (p,,27)X■
It is described in the section (p, uJ') (/77r, July issue).

In the present invention, reflective supports are preferably used.

A "reflective support" increases the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer.Such reflective supports include titanium oxide, titanium oxide, This includes those made by temporarily molding a hydrophobic resin containing dispersed light-reflecting substances such as zinc, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing gold dust dispersed in a light-reflecting substance as a supporting body. .

(Five Examples of Contributions) Hereinafter, specific examples of the invention will be shown, and two inventions will be further described. A multilayer photographic paper with layers and grooves was prepared.

The coating solution was prepared as follows.

(Preparation of coating liquid for the first layer) Yellow coupler (ExY-1) and (εXY-2)
1.0.2 g, 9.1 g and color image stabilizer (
Cpd-1) 4.4 g, 27.2 cc of ethyl acetate and 7.7 cc of high induction point solvent (S o Iv-1)
(8.0 g) was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 3 cc of 10% sodium dodecylbenzenesulfonate. This emulsified dispersion and emulsions EMI and EM2 were mixed and dissolved, and gelatin: a degree was added to AI! to obtain the following composition. 1 section and apply the 1st layer coating solution i! Ill. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1-oxy-3,5-cycloS-)
Riazine sodium salt was used.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The number is the coating amount (g1m2')
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [white pigment (Tio,) on the polyethylene layer side]
Contains blue dye. ] 1st layer (blue sensitive layer) Monodisperse silver chlorobromide emulsion (EMI) spectrally sensitized with a sensitizing dye (ExS-1) Spectral sensitized with a 0.13 sensitizing dye (ExS-1) Monodispersed silver chlorobromide emulsion (EM2), 0.13 gelatin 1.86 yellow coupler (ExY-2) 0.44 yellow coupler (ExY
-2) 0.39 color (elephant stabilizer (Cpd-1)
0.19 solvent (Solv-1)
0.35 second layer (color mixture prevention layer) Gelatin 0.99 color mixture prevention agent (Cpd-3>0.08 third layer (green sensitive layer) Spectral sensitization with sensitized color chart (ExS-2, 3) Monodisperse silver chlorobromide emulsion ('EM4) spectrally sensitized with 0.11 gelatin 1. 80 Magenta Cub 5
' (Ex xM -1) 0.39 color image stabilizer (
Cpd-4) 0.20 color image stabilizer (Cpd
-5) 0.02 color image stabilizer (Cpd-6
) 0.03 solvent (So I v-2)
0.12 solvent (S o 1 v-3)
0.25 Fourth layer (ultraviolet absorbing layer) Gelatin 1.60 Ultraviolet absorber (Cpd-7/ Cpd-8/Cpd-'9 = 3/2/, 6: weight ratio > 0.70 Color mixing prevention coral (Cp d-10) Monodisperse silver chlorobromide emulsion ( EM5) Monodisperse silver chlorobromide emulsion spectrally sensitized with 0.07 sensitizing dye (ExS-4,5>) (EMS) 0.16 gelatin 0.92 cyan coupler (Fox l turtle/'8- !White color image stabilizer (Cpd-8/Cpd-9/Cpd-42=3/4/2: weight ratio) O,17 dispersion polymer (Cpd-8/Cpd-9/Cpd-42=3/4/2: weight ratio)
p d -11) 0.28 Solvent (Solv-2
) 0.20 Sixth calendar (ultraviolet absorbing layer) Gelatin 0.54 Ultraviolet absorber (Cpd-7/Cpd-9/cpct-12=115/3:, i amount ratio') 0.21
Solvent (Sol v-2) 0.08
7th layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol, degree of modification 17%) 0.17 Ryusuke paraffin 0.03 In addition, at this time, as an irradiation prevention dye (Cpd -13
, Cpd-t4) was used.

Furthermore, as emulsifying and dispersing agents and coating aids, Alkanol
facx F-L 20 (manufactured by Dainippon Ink Co., Ltd.) was used. As a stabilizer for silver halide, (Cpd-1
5,16) was used.

Details of the emulsion used are as follows.

Emulsion name Particle size (μ) Br content (in mol) Impairment coefficient EMI 1.0 80
0.08EM2 0.75 80
0.07EM3 0.5 8
3 0.09Eν14 0.4
83 0.10EMS 0.5
73 0.09 The structural formula of the compound used is as follows.

ExM-1 Shil'IkoEx x Y-2 (Y-21) ExM-1 (M-6) X5-1 ■ S mouth JN (CJs) s xS-2 ExS-3 ExS-4 pd-1 pd -2 pa-3 ll pa-7 pd-8 pd-9 Cpd -10 []H 口H Cp d -11 士C)1. -C) I soup - (n = 100-1000)
C0N) IC, Ht (t) Cp d -12 Solv-1 dibutyl phthalate.

5olv-2) licresyl phosphate 5olv-3)
Lioctyl phosphate Solly 4 Trinonyl phosphate cpa -13 C9d -14 Cpd-/j Cpd-/6 The photosensitive material obtained above was treated with the following processing solution and in the processing step of 2 of the processing tank for color development. Successive processing was carried out until a supplementary image corresponding to twice the volume was obtained.

air :'1 8 Table page The composition of each treatment liquid is as follows.

However, the replenishment amount of color developer is A2Q rut /
m, B/Ojml1m22. C71m2l1
Three cases of m22 are shown.

Color developer tank liquid replenisher water
r o orttt
r o omt ethylenediamine-~, A 3
．． 09 j, to O9, N', N'-te B
3.09 3.3fl tramethylene phospho C3
, Oj;i 3. j9-Hydroxyethyl phosphate A 2. Og Ko, O
Iden/,/-Jiho B, 2.0g 2.2
g Sulfonic acid C2, Og 2.29 Potassium bromide A o, zg -B
o,zzg-CO,! 99 - Potassium carbonate 30g30g Fluorescent brightener
A /, jfl 2.0g (Wi
(ITEX≠B Bj, jg λ, μg manufactured by Sumitomo Chemical) C1, jg λ, to Rig, N-diethyl human A Hiromu, jp 1.390 xylamine B Hiromu 1. ．． 29c +L
, rg t, rg benzyl alcohol (irw 2 mouthfuls (see Table 1) diethylene glycol (10N/u, 2
m1) (see Table 1) Compound 11 A 4C7mmo113
mmol! (See Table 1.)
! rmmolC447mmol 4jmmol 3-methyl-≠-ami A j, jg 7. !
i no hehe ethiru N Bj, tg ♂, Og
-(β-Methanesul Cr, 9r, 39honidoether) Add water 10100O1000ml
00Okoj 'C) A 10.2j 10
．． AOB 10.2j 10. t3 CIO, Koz io, t-bleach fixer tank solution replenisher water
1100rttl
≠ooml thio @L#! Ammonium (70%), 2OO door l 300r
ul sodium sulfite cop hiroo
g iron diaminetetraacetate (all ammonium to, jfl i2o!
! Ethylenediaminetetraacetic acid dipotassium jfl 107/9 sips of water 10100O1000 punishment p
H (koj 'C) t, 70 4.30 Wash water (tank fluid and replenisher are the same) Ion exchange water (calcium, magnesium each 3 pp or less) The above color photographic paper was exposed to light through an optical wedge, and each continuous Treated before and after treatment. Changes in the maximum cyan density (Dmax) (ΔDmax) and changes in the minimum cyan density (Dmin) (ΔDmin) before and after continuous processing were determined. Furthermore, the color photographic paper processed after continuous processing is
The color development of the cyan dye after storage was determined as a percentage of the color before storage. The results are shown in Table 1.

As is clear from Table 1, in the comparative color photographic paper and C-port, ΔD
Although max is small, ΔI)min and fading of cyan dye are poor (/16/-1). However, it can be seen that good results can be obtained if the configuration of the present invention is followed. (/16ri~/7) (/%λ!~Kota).

In particular, it should be noted that when the replenishment amount is less than 1 m2 of ioo, the photographic performance deteriorates significantly outside of the present invention.
,7. r). It can also be seen that benzyl alcohol is not preferable when it is ■ (A62/).

2 ko, ko 3, 2μ).

Cyan coupler for tatami comparison (C-i) α (C-port) α Example 2 A multilayer photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

A coating solution was prepared as follows.

(Preparation of coating solution for the first layer) Yellow coupler (ExY-/)/9, color image stabilizer (cpct-/) Hiro, acetic acid tin A, 27.
2QC and high boiling point solvent (Solv-/J7, 7CC
3 (1,093 rough 104 mol. 1 v 10% sodium dodecylbenzenesulfonate
% gelatin aqueous solution was emulsified and dispersed in 1 rzcc. This emulsified dispersion and emulsions EM7 and EMt were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. l-oxy-3,j-dichloro-5-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-/)fjr: was used as a thickener.

(Layer structure) The composition of each layer is shown below. The number is the amount of coating (&1m22
) to the front. For silver halide emulsions, coating h1 in terms of silver is shown.

Support polyethylene laminate paper [The polyethylene on the first layer side contains white content (Ti02) and bluish dye. ] Layer - (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (ExS-/) 0. /! Sensitizing dye (
Monodisperse silver chlorobromide emulsion (EMr) spectrally sensitized with ExS-/) Gelatin i, rt Yellow coupler (ExY-i) o, r Co-color image stabilizer (Cpd-
2) o, i-solvent (Solv-/)
0.31 Second layer (color mixing prevention layer) Gelatin O, Tata color mixing prevention agent (Cpd-710, Or Third layer (green sensitive layer) Monodisperse spectrally sensitized with sensitizing dye (ExS-λ, 3) Silver chlorobromide emulsion (EM) O0/co-sensitizing dye (E
xS-2, 3) Monodisperse silver chlorobromide emulsion spectrally sensitized (EM/0) 0.2 hi gelatin/, 2 hi magenta coupler (ExM-/) (7, J5' color stabilizer ( cp
ci-hiro) 0.2 evening color image stabilizer (cpct
-ri 0. /, 2 solvent (Solv-2)
0-2j Fourth layer (ultraviolet absorbing layer) Gelatin / , tO ultraviolet absorber (cpct-47 cpct-7/Cpd-4 = 3/2/l: weight ratio J O, 70 color mixing inhibitor (Cpd-ta) 0-OS solvent (Solv
-3) 0.112 Fifth layer (red sensitive layer) Monodisperse chlorobromide emulsion (EM//) spectrally sensitized with sensitizing dye (ExS-Hiroshi, 5) 0.07 sensitizing dye (
Monodisperse silver chlorobromide emulsion spectrally sensitized with ExS-g, jJ (EM/co) o, it gelatin
O, Takocyan coupler (second
(See table) Color image stabilizer (Cpd-7/cpa-f/Cpd-/0=3/Da/Koni weight ratio 0./7 Dispersion polymer (Cpd-//) o, Solv-/ )
0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.2 Hiro ultraviolet absorber (Cpd-4/ Cp d -r / Cp d -/ 0 =//j/
3: weight ratio) 0.2/solvent (Solv-4
<) 0. Or 7th layer (protective layer) Gelatin 7.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) O.'7 Liquid paraffin 0.03 In addition, at this time, as an irradiation prevention dye, ( Cp d −/2,
cpa-/3) was used.

Furthermore, each layer contains Alkanol
x F-/20 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-/Hiro,/j) was used as a silver halide stabilizer.

Details of the emulsion used are as follows.

Emulsion base shape Particle diameter ψ) Br content (molel I)
Coefficient of variation “EM7 Cube /, /
/, 0 0.10EMr Cube o, r
i, o o, t.

EMta Cube O0≠r i,t
o, ori EMIO cube 0. jll /,!
0.0riEM// Cube O0hiro, t
/,! 0.02EM/ko cube o,
The 474 construction formula of the compound proboscis using i≠/, A O, 10 semi-uniform size is as follows.

xY-1 xS-I xS-2 , Ex S -3 xS-4 Cpd-1 cpa-3 H cpa-s し1j3Uli cpa-6 Cpd-7 Cpd-8 Cpd-9 H Cp d -11 Cp d - 12 SO3X SOjKC
pd -13 Cp d -14 ll Cp d -15 Solv-/ Dibutyl phthalate 5olv-,2
Trioctyl phosphate 5 olv-7 Trinonyl phosphate 5 olv-da Tricresyl phosphate Using the color photographic paper obtained as described above, a running process was carried out until three times the tank capacity of the color developer was replenished in the following processing steps. Natsuta is doing the test.

However, the composition of the color developer was changed as shown in Table 2.

Processing process Temperature Time Replenishment amount Color development
350C≠! Seconds λ Table Reference Marking @ 3r'C4
(j seconds 100ntl1m22 rinse/300C
20 seconds - rinse 2 io 0c 20
sec - Rinse 3 30 °C 20 seconds 200
mt/rn2 drying 700C 30 seconds rinsing was performed using a 3-tank countercurrent system from rinse 3 to rinse 1.

The composition of each treatment liquid is as follows. However, the replenishment amount of color developer is A, / I 0ral 7m,
8,90m11m22,C,Arml1m2)3
Case I) is shown below.

Color developer tank liquid replenisher water r0
0yrl room ethylenediamine-to, A j, 09 3. !
Go to 17 N1. NI-Te B 3-09 3.
711 Tramethylene phospho C3,09j, phosphoric acid sodium chloride A/, g o, igB
/, yoy - C/, 79 - Potassium carbonate 30ji 30f
l Fluorescent brightener hi, ty 2.0
9(WHITEX ≠13 B/, tl
2. ≠9 Sumitomo Chemical l81) C1, tf/
Ko, Riy ~, N-bis (carbo A 7.o
g y, igoxymethyl)hydra B 7. O
g ta, 111 jin c 7.
og io, tg compound ■ (Table 2) A
#7mmon j3rnmo113447mmol
YofmmoAIC37mmol jJmmol Benzyl alcohol (/rrd 20go)
(See Table 2) Diethylene glycol (torttt tz
rst) (see Table 2) 3-Methyl-≠-ami Ar, og 7. i
g agate to ethyl B t, λ9 7. tj
l-(β-methanesul C!, Hirog r, tg
(honamide ethyl) Add aniline sulfate water 1000 1000 1000 punishment pH (λr 'C) A io, io i
o, r.

B io, io io, ri C10,1010,! ? Label fixer (tank solution and replenisher are the same) EDTAFe (
■) NH4・λ820 tOgEDTA−λN
a-λH201 thorium thiosulfate (70%) thorium sulfite rR: thorium itg ice vinegar @
7fl water vm
1ooo pH (2yo'c)
Yo,! Rinse liquid (tank liquid and refill liquid are the same) EDTA-CoNa-2H2U O, 4!
Add pH water to 10OORIpH
7,.

The above color photographic paper was exposed to light through an optical wedge, processed before and after each successive process, and cyan △
Dmin and ΔDmax'Ik were determined. Further, the color photographic paper treated with the continuous processing solution was stored in a dark room at t0°C for 12 weeks, and the residual rate of cyan dye after storage was determined in percentage. The results are shown in Table 2.

As is clear from Table 2, by using the cyan coupler of the present invention, color fading is suppressed, and even when low replenishment treatment is performed, changes in (44~r)ΔDmin and ΔDmax are small. It is also seen that when benzyl alcohol is used, the stain after treatment increases (waste~//J.

Claims (2)

[Claims] (1) A silver halide color photographic light-sensitive material having a layer containing at least one cyan coupler represented by the following general formula (C-I) containing at least one compound represented by the following general formula (II). In the method of processing with a color developer that does not substantially contain benzyl alcohol, the replenishment amount of the color developer replenisher is 20 ml to 200 m2 per 1 m^2 processing of the color light-sensitive material.
1. A method for processing a silver halide color photographic material, characterized in that: l. General formula (C-I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents an alkyl group, cycloalkyl group, aryl group, amino group, or heterocyclic group. R^2 represents an acylamino group. Or represents an alkyl group having 2 or more carbon atoms.R^3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.R^3 may also be combined with R^2 to form a ring. .Z^1 represents a hydrogen atom, a halogen atom, or a group that can be separated in reaction with an oxidized product of an aromatic primary amine color developing agent.) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( In the formula, R^5 represents a substituted alkylene group, R^6, R^7
, R^8, and R^9 are the same or different and each represents a hydrogen atom, an alkyl group, or an aryl group. ) (2) The processing method according to claim 1, wherein the replenishment amount of the color developer replenisher is 25 ml to 100 ml per 1 m^2 of the color photosensitive material.