JPH0243545A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the sufficient coloring density of the title material, even at the short time of developing the photosensitive material which provides a specified 5-pyrazolone magenta coupler layer and contains silver chloride of >=70mol%, with a specified color developer. CONSTITUTION:The photosensitive material provides at least one layer of the 5-pyrazolone magenta coupler having a releasable group shown by formula I at the coupling position of a pyrazolone coupler and contains >=70mol.% of silver chloride, and is developed with the color developer which contains at least one kind of a compd. selected from an org. phosphonic acid compd. group or an aminopolycarboxylic acid compd. group, in an amount of >=3.0X10<-3>mol./l of the developer, for <=2min and 30sec. In formula I, L1 and L2 are each methylene or ethylene group, R1 is hydrogen atom or alkyl group, etc., R2 is a group capable of binding to a group A through carbon or oxygen atom, etc., A is carbon or sulfur atom, B is carbon or oxygen atom, etc., X is an atomic group necessary for forming a ring. Thus, the sufficient coloring density of the photosensitive material, even at the time of rapidly processing is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing a silver halide color photographic light-sensitive material containing a 2-equivalent 5-pyrazolone magenta coupler. More specifically, the present invention relates to a processing method for improving the color development processability of a silver halide color photographic light-sensitive material containing a 2-equivalent 5-pyrazolone magenta coupler.

(However, Ll and Lx are methylene or ethylene groups (prior art). A 5-pyrazolone type coupler is generally used as a magenta coupler to form a magenta color image in the subtractive color method. However, this 5-pyrazolone type coupler In the coupling reaction with the oxidation product of the developing agent, a side reaction occurs and the conversion rate to dye is low. When stored, there are problems such as fading or discoloration of the color image, and furthermore, staining occurs in the white background area.In order to improve these problems, as a coupler, for example, U.S. Patent No. 4,351,897 , No. 4,413
, 054 and JP-A No. 60-57839, a detachable group is introduced into the active position of a 5-pyrazolone coupler to improve the conversion rate to a dye and the stability of a color image. Although efforts have been made to improve the situation and improvements have been made, it is still far from sufficient.

However, the above-mentioned 5-
It has been revealed that pyrazolone couplers cause a decrease in color density when a large amount of divalent or higher polyvalent cations, especially alkaline earth calcium ions, is contained in a color developer. To prevent this, Japanese Patent Application Laid-Open No. 59-15763
No. 2 proposes a method of adding a chelating agent to silver halide color photographic light-sensitive materials, but when these compounds are used, color images cannot be stored under conditions of light, heat, or humidity. The storage stability of the film deteriorated, and yellow staining occurred particularly on the white background in unexposed areas. Furthermore, the method proposed in Japanese Patent Application Laid-Open No. 60-159850 requires high manufacturing costs and is difficult to put into practical use.

On the other hand, in JP-A-60-143337, aminopolycarboxylic acid, aminopolyphosphonic acid,
Techniques have been disclosed for preventing the reduction in color development caused by alkaline earth metals, particularly calcium ions, by adding chelating agents such as phosphonocarboxylic acids and hydroxyphosphonic acids.

On the other hand, in recent years, in order to meet customer demands and preserve the natural environment, development processing time has been shortened to less than 2 minutes and 30 seconds, development processing that does not substantially contain benzyl alcohol, and development processing that requires less or no washing with water. There is a strong need to be able to guarantee sufficient color density and image storage stability even in processes where the compositional ratio and composition amount of the processing solution changes significantly during washing and running conditions. 60-14333
No. 7 contains benzyl alcohol and is a process that cannot necessarily be called a rapid process, and is not in accordance with the recent trends described above.

Recently, an international patent has been published for an arylthio leaving type 5-pyrazolone coupler that has improved color development, less staining during processing, rapid processing, and improved light fastness of color images.

No. 88104795 is disclosed, and it is admitted that it is certainly an advanced coupler, but this coupler also contains polyvalent cations of divalent or higher valence contained in the color developing solution mentioned above,
In particular, it has been revealed that a large amount of calcium ions causes a decrease in color density.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a color developer that does not substantially contain benzyl alcohol, which does not suffer from the suppression of color development by polyvalent cations in the color developer, and which has a short development processing time. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material, which can obtain sufficient color density even in the case of the present invention.

(Means for Solving the Problems) In order to solve these problems, the present inventors have prepared at least one type of 5-pyrazolone magenta coupler having a leaving group shown in the following - Monanahi] at the coupling position, A silver halide color photographic light-sensitive material comprising at least one layer of silver chloride of 70 mol % or more, and at least one layer selected from the organic phosphonic acid compound group or the aminopolycarboxylic acid compound group of 3.0 x 10-'' mol/β or more This could be achieved by processing with a color developer containing a color developer for a processing time of 2 minutes and 30 seconds or less.

These will be explained in detail below.

(0)ll (However, L, Tori, represents methylene, ethylene group,
l and m represent 0 or 1. R+ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R2 represents a group connected to A through a carbon atom, oxygen atom, nitrogen atom, or sulfur atom.

A represents a carbon atom or a sulfur atom, n represents 1 when A is a carbon atom, and represents 1 or 2 when A is a sulfur atom, B represents a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom , and X represents an atomic group necessary to form a ring. R1 and R2 combine with each other to form a ring.
C is also good. When B is a carbon atom or a nitrogen atom, B and R2 may be bonded to each other to form a ring. ) The device tri in general formula (1) will be explained in detail below.

L and R2 represent a substituted or unsubstituted methylene or ethylene group. Substituents include halogen atoms (fluorine, chlorine, bromine, etc.), alkyl groups (e.g. straight chain and branched chain alkyl groups having 1 to 22 carbon atoms). , aralkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl),
Aryl groups (e.g. phenyl, naphthyl), heterocyclic groups (e.g. 2-furyl, 3-pyridyl), alkoxy groups (
For example, methoxy, ethoxy, cyclohexyloxy),
Aryloxy groups (e.g. phenoxy, p-methoxyphenoxy, p-methylphenoxy), alkylamino groups (e.g. ethylamino, dimethylamino), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), carbamoyl groups (e.g. N, N- dimethylcarbamoyl), anilino groups (e.g. phenylamino,
N-ethylanilino), sulfamoyl group (e.g. N.

N-diethylsulfamoyl), alkylsulfonyl groups (e.g. methylsulfonyl), arylsulfonyl groups (e.g.
tolylsulfonyl), alkylthio groups (e.g. methylthio, octylthio), arylthio groups (e.g. phenylthio, 1-naphthylthio), acyl groups (e.g. acetyl, benzoyl), acylamino groups (e.g. acetamide, benzamide), imido groups (e.g. succinimide). , phthalic acid imide, ureido groups (e.g. phenylureido, N,N-dibutylureido), sulfamoylamino groups (e.g. N,N-dipropylsulfamoylamino), alkoxycarbonylamino groups (e.g. methoxycarbonylamino), sulfones. It may have an amide group (for example, methanesulfonamide, etc.), a hydroxyl group, a cyano group, etc. Preferably it is a 1M methylene or ethylene group., i! and m represent O or 1, but preferably It is 0.

R1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; specifically, a hydrogen atom, a linear or branched alkyl group having 1 to 22 carbon atoms, an alkyl group such as an alkenyl group or a cycloalkyl group, or a phenyl group. , and aryl groups such as naphthyl groups, or heterocyclic groups such as 2-furyl, 2-thienyl, 2-pyrimidinyl, and 4-pyridyl groups, which further bear substituents as defined in L+, Li R1 is preferably a hydrogen atom and an alkyl group.

R2 represents a group connected to A through a carbon atom, oxygen atom, nitrogen atom, or sulfur atom; specifically, an alkyl group, an aryl group, a heterocyclic group (connected through carbon), an acyl group, an alkoxycarbonyl group, and a carbamoyl group. Groups linked via carbon atoms such as , etc.; Groups linked via oxygen atoms such as alkoxy, aryloxy, etc.; alkylamino group, anilino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide It represents a group connected through a nitrogen atom such as a group; and a group connected through a sulfur atom such as an alkylthio group or an arylthio group.

Like R1, these may further have the substituents defined for L+ and Lx, preferably Rs is an alkyl group, an aryl group, an alkylamino group, or an anilino group.

A represents a carbon atom or a sulfur atom, preferably a carbon atom.

n represents 1 when A is a carbon atom, and represents 1 or 2 when A is a sulfur atom.

B represents a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, preferably a carbon atom or a nitrogen atom,
More preferably it represents a carbon atom.

X represents an atomic group necessary to form a ring.

Preferably represents an atomic group constituted by atoms selected from carbon atoms, oxygen atoms, nitrogen atoms or sulfur atoms necessary to form a saturated or unsaturated 5-, 6- or 7-membered ring, more preferably an unsaturated ring. This ring represents an atomic group composed of atoms selected from carbon atoms, oxygen atoms, and nitrogen atoms necessary to form a saturated 5- or 6-membered ring, and this ring is further referred to as L+ as described above.

It may have the substituent defined in L8, and another ring may be fused to the ring containing X.

R6 and R3 may be bonded to each other to form a ring, preferably a 5- or 6-membered saturated or unsaturated ring, and L+ on these rings.

It may further have the substituent defined in L□.

When B is a carbon atom or a nitrogen atom, B and Rt may be bonded to each other to form a ring, preferably a 5- or 6-membered saturated or unsaturated ring, more preferably may form a 5- or 6-membered saturated ring, and these rings may further contain the substituents defined for L+ and L-.

A first preferred pyrazolone coupler can be represented by the following general formula.

R・, -Good- N YI In this - pattern hole, Yl represents R1 or Z, Rh,
R1 represents a substituted or unsubstituted substituent having an aryl or heterocyclic group and a secondary or tertiary group Ro represented by Rc (CHi)-sCRa, and i represents 0 or l.

Zl represents an oxygen atom, a sulfur atom, or NRt.

R1 represents a substituted or unsubstituted alkyl, aryl or heterocyclic group, Rc and Ra are halogen atoms, R1
R1 represents a group selected from the group consisting of
represents a hydrogen atom or a group defined by R-1Ra,
Rt represents a hydrogen atom and a group defined by R1. Z
2 represents an oxygen atom, a sulfur atom, or NRゎ, R1 represents a group defined in Rt, R1 represents a group defined in R2, Rc is bonded to at least one of R4 and Ro to form one or Rt may form two carbocycles or heterocycles, which may further have substituents.
, X and B are the above 'I! is synonymous with substituent, atomic group, and atom. R3 is anilino group, acylamino group,
It represents a ureido group, a carbamoyl group, an alkoxy group, an allyloxycarbonyl group, an alkoxycarbonyl group, or an N-heterocyclic group, and preferably these groups contain an oil-solubilizing group.

R4 is a substituted or unsubstituted aryl group, preferably a substituted phenyl group, more preferably 2゜4.6-)
It is a lychlorophenyl group.

A more preferred pyrazolone coupler of this type can be represented by the following general formula. In this hole Rh, Rs, Ra, Rc, Ra.

R, , X and B have the same meanings as the above substituents.

i represents 0 or 1.

A second preferred pyrazolone coupler can be represented by the following general formula.

1' to N, It, N□8° In this hole, Rs represents a substituted or unsubstituted alkyl, aryl or heterocyclic group.

R+, Rs, Ra, X and B have the same meanings as the substituent atomic groups and atoms described above. Preferably R1 is ~N
It is a group represented by H-Y□, and R4 is a 2°4.6-dolichlorophenyl group. Y8 is substituted or unsubstituted,
Represents an aryl, arylcarbonyl or arylaminocarbonyl group.

A third preferred pyrazolone coupler can be represented by the following general formula. R1, R1 in this hole
, R4 and X have the same meanings as the above substituents and atomic groups. Y represents substituted or unsubstituted methylene, ethylene group or >NR; eRf has the same meaning as the above substituent. This preferred pyrazolone coupler can be represented by the following general formula. R in this hole
R, R and R4 have the same meanings as the above substituents - Ra, R? represents an alkyl group or an aryl group, R@ represents the above-mentioned L+ −[, a substituent defined in this book, D represents a methylene group, an oxygen atom, a nitrogen atom, or a sulfur atom, n is 0 in the case of a methylene group. represents an integer of 2 from , but otherwise does not represent l,
p represents an integer from 0 to 3.

In the following, the term "coupler part" refers to the part excluding the coupling-off group, and the term "coupler" refers to the whole including both the coupler part and the coupling-off group.

"Coupler moieties" are pyrazolone couplers well known and used in the photographic industry that react with oxidized color developing agents to form dyes, particularly magenta dyes. Examples of preferred pyrazolone coupler portions include, for example, U.S. Pat.
No. 2915, No. 4336325, No. 4199361, No. 4351897, No. 4385111, No. 60-170854, No. 60-194452, No. 6
0-194451. U.S. Patent No. 4,407,936, No. 34
No. 19391, No. 3311476, British Patent No. 13573
'72, U.S. Patent No. 2600788, U.S. Patent No. 290857
No. 3, No. 3062653, No. 3519429, No. 3
No. 152896, No. 2311082, No. 234370
3 and 2369489 or the inventions cited in these patents.

In these patents, when a part of the pyrazolone coupler is substituted with a coupling-off group, it can be replaced with a coupling-off group represented by the general formula (1) of the present invention.9 The pyrazolone coupler of the present invention is ,
It can also be used in combination with other pyrazolone couplers such as those described in the above patents.

An example of a preferred "coupler moiety" can be represented by the following general formula. In this hole, Q.sub.R1.sup. represents a coupling-off group of the present invention, and R.sup.9 represents anilino, acylamino, ureido, carbamoyl, alkoxy, allyloxycarbonyl, alkoxycarbonyl or N-heterocyclic group.

R8° is a substituted or unsubstituted aryl group, preferably a phenyl group having at least one substituent selected from a halogen atom, alkyl, alkoxy, alkoxycarbonyl, acylamino, sulfamide, sulfonamide, and cyano group.

The carbon and nitrogen atoms of these substituents are unsubstituted or
R9 is preferably an anilino group, more preferably an anilino group represented by the following general formula. This-
In the pattern hole, Ro Ro is an alkoxy group having 1 to 30 carbon atoms, an aryloxy group, or a halogen atom (preferably a chlorine atom).

Rrx and R13 are each a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, fluorine atom), a) L'+)
Lllx (4M is an alkyl group having 1 to 30 carbon atoms),
Alkoxy group (e.g. alkoxy group having 1 to 30 carbon atoms)
, acylamino group, sulfonamide group, sulfamoyl group, sulfamide group, carbamoyl group, diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkanesulfonyl group, arenesulfonyl group, alkylthio group, 0 representing an arylthio group, an alkoxycarbonylamino group, an alkylureido group, an acyl group, a nitro group, and a carboxy group, such as R1! and R.I.
Each S may be a hydrogen atom or a ballast group.

R. is preferably a substituted phenyl group. Examples of substituents include halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), alkyl groups having 1 to 22 carbon atoms (e.g. methyl group, ethyl group, propyl group, t-butyl group, tetradecyl group), and 1 to 22 carbon atoms. -22 alkoxy groups (e.g. methoxy, ethoxy, dodecyloxy), carbon number 1-2
sRl which is an alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group), an acylamino group (e.g. α-[3-pentadecylphenoxy]-butyramide group) and/or a cyano group of 3. is more preferably 2.4. G-trichlorophenyl group.

To explain Rrx and RI3 in more detail, they are hydrogen atoms, halogen atoms (e.g. chlorine atoms, bromine atoms,
fluorine atom), a linear or branched alkyl group having 1 to 30 carbon atoms (e.g. methyl group, trifluoromethyl group, ethyl group, t-butyl group, tetradecyl group), 1 to 30 carbon atoms
alkoxy group (e.g. methoxy group, ethoxy group, 2-
ethylhexyloxy group, tetradecyloxy group), acylamino group (e.g. acetamido group, benzamide group, butyramide group, tetradecaneamide group, α-(2,
4-di-t-pentylphenoxy)acetamido group, α
-(2,4-di-t-pentylphenoxy)butyramide group), α-(4-hydroxy-3-t-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2-oxy- 5-tetradecyl-virolin-1-yl group, N-methyltetradecanamide group, t
-butylcarbonamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, p-dodecylbenzenesulfonamide group, N-methyltetradecylsulfonamide group, hexadecanesulfonamide group) ), sulfamoyl group (e.g. N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N,N-dimethylsulfamoyl group, N-[3-(dodecyloxy)propylphusulfamoyl group, N -(4-(2,4-di-1-pentylphenoxy)butyl]sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, N-dodecylsulfamoyl group), sulfamide group (e.g. N-methylsulfamoyl group), famid group, N-octadecylsulfamide group)
, carbamoyl group (e.g. N-methylcarbamoyl group,
N-octadecylcarbamoyl group, N-[4-(2,4
-di-t-pentylphenoxy)butyl]carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, N
, N-dioctylcarbamoyl group), diacylamino group (e.g. N-succinimide group, N-phthalimide group,
2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, N-acetyl-N-dodecylamino group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-dodecyloxyphenoxy carbonyl group), alkoxycarbonyl group having 2 to 30 carbon atoms (e.g. methoxycarbonyl group, tetradecyloxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, dodecyloxycarbonyl group), alkoxysulfonyl group having 1 to 30 carbon atoms ( For example, methoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, 2-ethylhexyloxysulfonyl group), aryloxysulfonyl group (e.g. phenoxysulfonyl group, 2゜4-di-
t-pentylphenoxysulfonyl group), carbon number 1-3
0 alkanesulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexadecanesulfonyl group), arenesulfonyl group (e.g. benzenesulfonyl group, 4-nonylbenzenesulfonyl IIs, p-1 luenesulfonyl group) , an alkylthio group having 1t+x to 22 carbon atoms (e.g. ethylthio group, octylthio group, benzylthio group, tetradecylthio group, 2-(2,4-di-t-pentylphenoxy)
ethylthio group), ruthio group (e.g. phenylthio group, p-tolylthio group), alkoxycarbonylamino group (e.g. ethoxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group), alkylureido group (e.g. N-methylureido group, N,N-dimethylureido group, N-methyl-
N-dodecylureido group, N-hexadecylureido group/N,N-dioctadecylureido group, N,N-dioctyl-N'-ethylureido group), acyl group (e.g. acetyl group, benzoyl group, octadecanoyl group) , p~
dodecaneamide benzoyl group, cyclohexanecarbonyl group), nitro group, cyano group, and carboxy group.

To explain in more detail the alkoxy group and aryloxy group of RI +, the alkoxy group includes methoxy group, ethoxy group, propoxy group, butoxy group, 2-methoxyethoxy group, 5ec-butoxy group, hexyloxy group, 2-ethylhexyloxy group. group, 2-(2,4-di-t-pentylphenoxy)ethoxy group, and 2-dodecyloxyethoxy group, and the aryloxy group is phenoxy group, α- or β-naphthyloxy group, and 4-tolyloxy group.

- A monomer containing a pyrazolone coupler with a leaving group surrounded by a hole (!) can be copolymerized with a non-chromogenic ethylene-like monomer that does not couple with the oxidation products of the aromatic-grade amine developer. You can make it.

Acrylic acid, α
-chloroacrylic acid, α-alkylacrylic fa (e.g. methacrylic acid) and esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, (-butylacrylamide, diacetone acrylamide, methacrylamide, methyl Acrylate, ethyl acrylate, n-probyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n -butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, 5-aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N- vinyl
Examples include 2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more types of non-color-forming ethylenically unsaturated monomers used here can be used together. For example, lobe tyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, and methyl acrylate. diacetone acrylamide, etc.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Next, coupling separation 1 (
Specific examples of Q) will be shown, but the invention is not limited to these.

Q-1) Q-6) Q-2) Q-7) Q-3) Q II) Q-22) C1+.

Q-20) Q-26) n) Q-29) Q-blade) CH.

・F1+v(t) Q Q-32) Q-45) Q-46) xlls Q (M l) (M ll Cl.

Book Q-56) CH3 Q-59) Next, specific examples of the coupler of the present invention will be shown, but the coupler is not limited thereto.

<M (M-4) CH.

L (M-5) (M (F, i-9) (M-1-9 )(!.

CH.

Hs CH3 (M-7) (M (M-12) Hs C11+ CH3 Off (M (M-14) (M (M-18) (M-15) (M-16) (M (M (M (M-22) (M-25) (M C small H.

C mushroom H5 CM.

(M-23) (M-24) CM-27) Cz)Is C,H.

CH3 (M-29) (M (M-33) (M-34) (M-31) (M-32) (M (M-36) (M (M-41) (M-42) HI (M (M-40) (M-43) (M H2 (M (M-49) (M (M-47>(M-48>) (M-51) (M M-58) <M M-60 ) M-61) H3 M~63) M-64) NHC-C-CHs The magenta coupler of the present invention usually contains I X 10-'' mole-1 mole, preferably l
It can be used in the range of Xl 0-'' mol to 8 X 1 O-' mol. The coupler of the present invention can also be used in combination with other types of magenta couplers.

The magenta coupler addition layer of the present invention may be any silver halide emulsion layer, but is preferably a green-sensitive silver halide emulsion layer. The amount of silver used in this green-sensitive silver halide emulsion layer is preferably from 0.1 to 0.3 glcd.

The magenta coupler of the present invention can be synthesized by the method described in WO3B104795 or in accordance therewith.

Next, the group of organic phosphonic acid compounds used in the color developer in the present invention will be explained.

The organic phosphonic acids used in the present invention include alkylphosphonic acids, phosphonocarboxylic acids, aminopolyphosphonic acids, etc.
Any organic phosphonic acid can be used. The general formula is shown below.

- Monka (■) B-AI -Z-Ax -c General formula (III) In general formulas (II) and (III), A and ~A are respectively substituted or unsubstituted alkylene groups, and Z is an alkylene group ,
Cyclohexane group, phenylene group, R (R is alkylene 1&) or >N At (A
t is hydrogen, hydrocarbon, lower aliphatic carboxylic acid, lower alcohol -COOM, -POCOM! (M represents hydrogen, alkali metal, ammonium), B. C, D, E.

At least one of F and G is one PO and Ml.

-Crest hole (IV) OOC- CCH*-CH)- C- (CHg)-
PO (OM)ztlE R": -COOM. PO (OM)xR2: hydrogen, alkyl group of C. to C, - (cttz)
+t' COOM, phenyl group, R■: hydrogen, -C
OOM.

M: hydrogen, alkali metal, ammonium, mho or l n': integer from 1 to 4 q: 0 or 1 However, when m; O, R''--PO (OM)i.

General formula (V) R”N (C Ht POs Mg) x R14:
Lower alkyl group, aryl group, aralkyl group, nitrogen-containing 6
Member ring group [as a substituent -01(, -OR" (RIS: C. to C. alkyl group), -PO□Mt, -C Hz P
O,1Mt.

N (CIIiPOsMg) t , C O O
Mz.

-N　(CH, COOM□)〕 M: Hydrogen, alkali metal, ammonium.

-Crest hole (Vl) H RF'l RRm X z Y Rth. R11, hydrogen, lower alkyl group, -COOH
.

NJt (J is H.OH, lower alkyl group, -ci
H4 0H) R*l dihydrogen, lower alkyl group, OH, NLt (L is H, OH, -cH,, -C.HS.

-C yo Ha OH, -P (h Mx) X, Y, Z: OH, COOM, POs Mt
.

M: Hydrogen, alkali metal, ammonium.

n is 0 or an integer of 1 or more, m is 0 or 1-maximal formula (■) 0M R”-0-P-OR” Rz*. Rs*, hydrogen, alkali metal, ammonium, 01-cog substituted or unsubstituted alkyl group, alkenyl group, cyclic alkyl group.

General formula (■) QI Q寞R”: C+ to Ctt alkyl group, C I”” C +
g alkoxy group, 01-C1. monoalkylamino group, 08~Cl! dialkylamino group, amino group, C
, ~Ct4 allyloxy group, C. ~C. 4, an arylamino group and an amyloxy group.

Q, ~Qs Ni OH, ct ~ Cza alkoxy group, aralkyloxy group, allyloxy group, OMs (Ms is a cation), amino group, morpholino group, cyclic amino group, alkylamino group, dialkylamino group, arylamino group , represents an alkyloxy group.

General formula (D0 R31, R3-hydrogen, lower alkyl group, imine (lower alkyl group, may be substituted with CHz CHt C00N a), M: hydrogen, alkali metal, ammonium, n: 2-16
an integer of

General Formula (X) Specific examples of the compounds represented by -Momonana (■) to (X) above include, but are not limited to, the following.

R14~R3&: hydrogen, alkyl group [-O as a substituent
H, OCn' Hz n' +H (n': 1 to 4)
, POs Mz.

CHI PO3M, -NRt (R is an alkyl group)
, -N CCHz PO3Mt)t, M: hydrogen, alkali metal, ammonium.

- Compounds represented by Mongan (I[I) are preferred.

0OH HOOC-C-1( PC)sH CHI Po, Hz 03Hz CHI C0OH HOOCCH*C-C00H PO KoH intention 0sHx HOOC-CB atmosphere HOOCCHI CB-C:OOH [ 0sHz HOOC-C-Cool CHt POs Hs CaH啼-C1l-COOH PO, H□ CHI C00H CH-COOH CH,C00H CH□ HCsfh C□H.

C-PO,H.

COOH ot Hl po, Hl 0sHy CHl po, Hffi Hz Ox P-C-PO3Ht Hz 03P P.O., H.

CHt OOK 0OH 1(, N CHl GHz O-P-(OH)2 ox 03 P-C-PO3Hl ;I HOOC-CH-CHg 0-P-(OH)zHOC
Hg CH(OH)-CHt OP(ONa) Window HI HOCHt Cut 0-P-(OH)mHOCHg
CH-0-P-(ONa)mHa 0H HO-CHt -CHCHw OP (OH)sH HOOC-CHx CHt NHC HOH C1,0 P-(OH)x tb OH OH OH CHs CHs OH OH ((CHs)m N ) x P (N (CHs)s ) x Cb Hz CHt o-p-o-p OCIit Cb I(S aO Na C, Hs o-p 0-P-0-C, H.

OH OH OH OH OH Oct+, a+s O +1111 HO-P -C-□P OH OH OH OH CII.

The amount of these organic phosphonic acid compounds added is 1X10-' mol or more per color developer IE, preferably 5X10
−' mole or more, more preferably 2×10 4 mole/1 or more. These organic phosphonic acid compounds act as anti-settling agents for calcium and magnesium in color developing solutions, or as chelating agents to improve the stability of color developing solutions. It may be used in combination with other types of chelating agents described below. In this case, the total amount of the chelating agents is the amount added above.

Next, specific examples of the aminopolycarboxylic acid compounds used in the color developing solution in the present invention will be shown.

Nitrilotriacetic acid Nitrilotripropionic acid Diethylenetriamine Pentaacetic acid Trans Cyclohexanediamine Tetraacetic acid 1,2-Diaminopropane Tetraacetic acid Glycol ether diamine Tetraacetic acid Ethylenediamine Diorthohydroxyphenylacetic acid N,N'-bis(2-hydroxybenzyl)ethylenediamine-N ,N'-diacetic acidhydroxyethyliminodiacetic acidpenzylamine diacetatebenzylethylenediamine triacetic aciddiaminopropanoltetraacetic acidethylenediaminenibropionic acidhydroxyethyliminodiacetic aciddiaminopropanetetraacetic acid triethylenetetraminehexaacetic acidhydroxyethyliminodiacetic acidThese aminopolycarboxylic acids The amount of the organic phosphonic acid chelating agent added is the same as that of the organic phosphonic acid chelating agent, and two or more types may be used in combination, and most of these compounds may be used in combination with other types of chelating agents. is a commercially available product and can be easily obtained. The chelating agent mentioned above may also be a sodium, potassium or ammonium salt.

Specific compounds are not limited to these, but ethylenediaminetetraacetic acid is excluded.

The chelating agent is preferably an organic phosphonic acid compound.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino)aniline D-64--amino-3-methyl-N-ethyl- N-(
β-(methanesulfonamide)ethylcoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p~phenylenediamine D-94-amino-3-methyl- N-ethyl N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6).

Moreover, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per developer solution IZ,
More preferred is a concentration of about 0.5 g to about 10 g.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

However, when benzyl alcohol is removed for the purpose of reducing pollution load, etc., it is preferable not to substantially contain sulfite ions in order to improve the color development of the color developer, and in such a system, the effect of the present invention is is particularly remarkable. "Substantially not containing" as used herein means 0.5 g/j of sodium sulfite per 12 color developing solutions.
Below, preferably 0.2 g/l or less, more preferably,
It does not contain it at all.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids of No. 9, hydrazines and hydrazides described in No. 61-170756, No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or 61-18
It is preferable to add various sugars of the 6560th anniversary, and
In combination with the above compounds, Japanese Patent Application No. 61-147823,
Monoamines described in No. 61-166674, No. 61-165621, No. 61-164515, No. 61-170789, No. 61-168159, etc.;
No. 1-173595, No. 61-164515, No. 61
-Diamines described in No. 186560, etc., No. 61-16
No. 5621, and polyamines described in No. 61-169789, polyamines described in No. 61-188619,
nitroxy radicals described in No. 61-197760,
It is preferable to use the alcohols described in No. 61-186561 and No. 61-197419, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
The aromatic polyhydroxy compounds described in Nos. 746 and 544 may be contained as necessary, especially alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, or aromatic polyhydroxy compounds. Addition is preferred.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffering agents. Examples of El buffering agents include carbonate, phosphate, borate, tetraborate, hydroxyl ammonium, α-borate, glycyl salt. , N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-
2-methyl-1,3-propanediol salt, valine [,
7C) Phosphorous salts, trishydroxyaminomethane salts, lysine salts, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are
These buffers have excellent buffering capacity in the high pIIsJI region of 9.0 or higher, 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 bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably 1 or more, particularly 0. 1 morph 1~
Preferably it is 0.4 mol/e.

In addition, various calcinates other than those mentioned above may be used in combination with the color developer as an anti-settling agent for calcium and magnesium, or to improve the stability of the color developer. Methylenephosphonic acid, ethylenediamine N,N,N',N'-tetramethylenesulfonic acid, 2-phosphonobutane-1,2,4-)
Recarboxylic acid, l-hydroxyethylidene-1,1-diphosphone Two or more of these chelating agents may be used in combination as necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.

Any development accelerator can be added to the color developer if necessary. Benzyl alcohol can be used as a typical color development accelerator. However, it is preferable that the color developer of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, preparation properties, and prevention of color staining.

Here, "substantially" means that it is contained in an amount of 2 ml or less per developer solution, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50137726, JP-A-44-30074, JP-A-44-30074; Quaternary ammonium salts represented in No. 56-156826 and No. 52-43429, etc., U.S. Patent Nos. 2 and 4
No. 94,903, No. 3,128゜182, No. 4.23
No. 0,796, No. 3,253.919, Special Publication No. 1977-
No. 11431, U.S. Patent No. 2,482,546, No. 2
．． 596.926 and 3,582.346, etc., Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, US Pat. Polyalkylene oxides such as those disclosed in U.S. Pat.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole. Representative examples include nitrogen-containing heterocyclic compounds such as , 2-thiazolylmethyl-benzimidazole, imidazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4,4°-
Diamino-2,2°-disulfostilbene compounds are preferred, the amount added is 0 to 5 g/Il, preferably 0.1 g
~4g/l.

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

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds to 2 minutes 30 minutes
The time period is preferably 30 seconds to 1 minute and 30 seconds. It is preferable that the amount of replenishment is small, but it is 20 to 600 ml per 1 d of photosensitive material.
1 is appropriate, preferably 50 to 300 ml. More preferably 60ml to 200ml, most preferably 60mJ! ~150mff1.

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

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained below.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular organic complex salts of iron (III) (e.g. amine polyamides such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. Preferable examples include complex salts of carboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; and hydrogen peroxide.

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution, aminopolycarboxylic acids useful for forming organic complex salts of iron (III),
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron cm) ti! Salt is preferred because of its high bleaching properties.

These ferric ion complex salts may be used in the form of complex salts7, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. may be used in excess beyond forming
Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/E, preferably 0.05 to 0.50 mol/E! It is.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. Specification No. 812, JP-A-53-95
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or halides such as iodine and bromide ions are preferred because they have 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) or an iodide (eg, ammonium iodide) can be included.

If necessary, one or more inorganic substances having pH$1 binding capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. acid,
Organic acids and their alkali metal or ammonium salts or lfM such as ammonium nitrate, guanidine, etc.
Inhibitors 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, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; or ethylene. Bisthioglycolic acid, 3,6-cythia 1
．． These are water-soluble silver halide solubilizers such as thioether compounds such as 8-octanediol and thioureas, and these can be used as a mixture of two or more thereof. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. It is preferred to use salts, especially ammonium thiosulfate salts.The amount of fixing agent per 1j is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The posJt range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and the fixing solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. (e.g., potassium metabisulfite, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
It is preferable to contain 2 to 0.05 mol/E gold, and more preferably 0.04 to 0.40 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, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary.

The silver halide color photographic light-sensitive material used in the present invention is preferably subjected to water washing and/or stabilization treatment 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, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
a+of the 5ociety or Motio
n Picture and Television
Engineers) No. 64@, P, 248-253
(May 1955 issue), the number of stages in the normal multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5E to 1! The following is possible, and the effects of the present invention are remarkable; however, due to the increased residence time of water in the tank, problems such as bacteria propagation and generated floating matter adhering to photosensitive materials occur. As a solution to such problems in the processing of color light-sensitive materials, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazoles described in JP-A No. 7-11542, chlorinated sodium isocyanurate described in JP-A No. 61-120145, and Japanese Patent Application No. 10548-1988
Benzotriazole, copper ion, etc. described in No. 7, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, Sanitation technology complete volume "Sterilization of microorganisms, sterilization, and antifungal technology", Japanese antibacterial and antifungal science supplementary section "Antibiotics" It is also possible to use fungicides listed in the "Encyclopedia of Antifungal Agents".

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

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 Hp that has been passed through dye stabilization.
Examples include buffering agents and ammonium compounds for adjusting to H. 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, optical brighteners, and hardeners may be added. In the processing of the photosensitive material of the present invention, stabilization is performed without going through a water washing step (if it is directly carried out, it is recommended to
No. 8543, No. 58-14834, No. 60-220345
Any of the known methods described in No. 1, etc. can be used.

In addition, it is also preferable to use chelating agents such as ■-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, magnesium and bismuth compounds, and the washing liquid used after desilvering treatment in the present invention. A so-called rinsing liquid can also be used as a stabilizing liquid.

The pH of the water washing step or stabilization step of the present invention is 4 to 1O, preferably 5 to B. Although the temperature can be set variously depending on the use and characteristics of the photosensitive material, it is generally 15 to 45°C, preferably 20 to 40°C.

Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing processing time, preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or photosensitive material In? 2 F or more, preferably 500 m1' 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. An example of this is to flow the overflow of washing water, which has been reduced by a multi-stage countercurrent system, into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid.

The total process time of the desilvering process, water washing and stabilization process of the present invention is 2 minutes or less, preferably 30 seconds to 1 minute 30 seconds.

The total time here refers to the time from when the silver halide color photographic light-sensitive material comes into contact with the first bath in the desilvering process until it comes out of the last bath in the water washing or stabilization process. Hollow time for is included.

Here, [the total processing time of desilvering treatment, water washing treatment, and stabilization treatment is 2 minutes or less] refers to the treatments performed up to the J, v1 silver treatment and drying steps (more specifically, water washing and/or stabilization treatment). For example, the sum of the processing times such as (1) R silver - water washing, (2) desilvering -> stabilization, (2) desilvering - water washing - stabilization, etc. is 2 minutes or less.

The color photographic material of the present invention can be constructed by coating a support with at least one pre-malignant silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer. In general color photographic paper, these light-sensitive emulsion layers are coated on a support in the order listed above, but they may be coated in a different order. A subtractive color method can be achieved by incorporating a silver halide emulsion sensitive in the wavelength range and a so-called color coupler that forms a complementary color relationship with the light to which the light is exposed, i.e., yellow for blue, magenta for green, and cyan for red. Color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

Silver halide emulsions used in the present invention include 1. Those made of silver chlorobromide or silver chloride, which do not substantially contain silver iodide, can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, even if the halogen composition of the emulsion differs between grains. Although they may be equal, if an emulsion having an equal halogen composition among the grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the halide root grains, and cores inside the silver halide grains.
A particle with a so-called laminated structure in which the halogen composition and a surrounding shell (-layer or multiple layers) have different halogen compositions, or a structure having parts with different halogen compositions in a non-layered manner inside or on the particle surface (layers on the particle surface) In this case, particles having a structure in which portions of different compositions are joined on the edges, corners, or surfaces of the particles can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than grains with a uniform structure, and it is also preferable from the viewpoint of pressure resistance, when the silver halide grains have the above-mentioned structure. The boundaries between parts with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to compositional differences, or may be caused by active continuous structural changes. It may be something you have.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. This ratio can vary widely depending on the purpose.

For light-sensitive materials suitable for rapid processing, so-called high silver chloride emulsions containing a high silver chloride content are preferably used. The silver chloride content of these high silver chloride emulsions is 70 mol% or more, and 90 mol%
It is preferably at least 95 mol%, and more preferably at least 95 mol%.

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer exists inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized layer is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. , a corner or a surface, and one preferable example is one in which the grain is epitaxially grown on a part of the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken) is 0.1μ. ~2μ is preferred.

In addition, the particle size distribution of these particles is preferably monodisperse with a coefficient of variation (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. In this case, a wide latitude can be obtained. For this purpose, it is preferable to blend the above monodispersed emulsions in the same layer or to apply them in multiple layers.

The silver halide grains contained in photographic emulsions are formed in regular shapes such as cubes, tetradecahedrons, or octahedrons.
It is possible to use a material having a crystal shape, an irregular crystal shape such as a spherical shape or a plate shape, or a compound shape thereof. Moreover, it may be made of a mixture of crystals having various crystal forms.

In the present invention, it is preferable that the particles having the above-mentioned regular crystal form be contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, emulsions in which tabular grains with an average asparagus (-ratio (circular diameter/thickness) of 5 or more, preferably 8 or more) account for more than 50% of the total grains as a projected area can also be preferably used. .

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chemie et Ph1sique by es
Photographique (Pau1Monte1
Publishing, 1967), G, F, Kuchiuffin, Ph.
otographic Emulsion Che+5
istry (published by Focal Press, 1966) % Making and Coating Photo by V, L, Zelilvan et al.
rapic Emulsion (Focal Pre
tliI can be produced using the method described in (Published by Ss Publishing Co., Ltd., 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which PAg in a liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds to be added varies widely depending on the purpose, but is preferably from 10-9 to 10-'' mol based on the silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding chemical sensitization methods, sulfur sensitization represented by the addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding the compounds used for chemical sensitization,
Those described in the lower right column on page 18 to the upper right column on page 22 of the specification of JP-A-62-215272 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Examples of the spectral sensitizing dye used at this time include F, H, Written by Harser 11ete
roeyelic coi+pounds-Cyani
ne dies and related compo
unds (John Wllley & 5ons
[New York, London] Publishing, 19
Examples include those described in 1964).

Examples of specific compounds include the above-mentioned Japanese Patent Application Laid-Open No. 62-21527.
Those described in the upper right column of page 22 to page 38 of the specification of Publication No. 2 are preferably used.

Various compounds or their precursors may be added to the silver halide emulsion used in the present invention for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. be able to. These are commonly called photographic stabilizers. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

In color light-sensitive materials, yellow couplers, magenta couplers, and cyan couplers, which develop yellow magenta and cyan colors, respectively, by coupling with oxidized products of aromatic amine color developers are commonly used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Among them, yellow couplers have the following general formula (Y-
Those represented by 1) and (Y-2) are preferred.

[Y l〕

(Y-2) For details of the pivaloylacetanilide type yellow coupler, see U.S. Pat.
It is described in column 15, line 8 to column 8, line 39, and in column 14, line 50 to line 1941141 of the specification of 4°623.616.

For details on benzoylacetanilide type yellow couplers, see U.S. Pat.
No. 3,501, 4. 046. No. 575, 4.1
It is described in No. 33,958, No. 4,401゜752, etc.

Specific examples of pivaloylacetanilide type yellow couplers include compound examples (Y-1) to (
Y-39), among them (Y-1),
(Y-4), (Y-6).

(Y-7), (Y-15), (Y-21),
(Y-22), (Y-23), (Y-26)
, (Y-35), (Y-36), (Y-3
7), (Y-38), (Y-39), etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623,616
Compound examples (Y-1) to (Y-33) in columns 9 to 24fjl
Among them, (Y-2), (Y-7
), (Y-8), (Y-12).

(Y-20), (Y-21>, (Y-23).

(Y-29) etc. are preferred.

Other preferred examples include US Pat. No. 3,408.
Typical specific example (34) described in column 6 of specification No. 194
Compound examples (16) and (19) described in column 8 of the specification of the same No. 3,933,501, compound examples (9) described in columns 7 to 8 of the specification of the same no. 4,046,575 , 4,133
, No. 401.752 Specification No. 5 to 641111, Compound Example 1 described in No. 401.752 Specification No. 5a, and the following compounds a) to h). Can be done.

Among the above-mentioned couplers, those having a nitrogen atom as a leaving atom are particularly preferred.

Other magenta couplers that can be used in combination with the pyrazolone magenta coupler used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrozolone and pyrazolotriazoles. An example is a coupler. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same 2nd and 3rd
No. 43,703, same No. 2. 600. 788, 2,908,573, 3.062.653, 3,152,896 and 3.936,015
It is written in the number etc. As a leaving group for double-sided 5-pyrazolone couplers, U.S. Patent No.
The nitrogen atom leaving group described in No. 4, 3 of U.S. Pat.
The arylthio group described in No. 51.897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As pyrazoloazole couplers, U.S. Patent No. 2,
369,879, preferably pyrazolo(5,1-c)(1,2,4) triazoles as described in U.S. Pat. No. 3,725,067, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (
Examples include pyrazolopyrazoles described in June 1984). Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula (M-1)
, (M-2) or (M-3).

Among pyrazoloazole couplers, U.S. Pat.
Preferred are the imidazo(1,2-b)pyrazoles described in U.S. Pat. -Riazoles are particularly preferred.

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2,3 or 6 position of the pyrazolotriazole ring as described in JP-A No. 61-65245, and as described in JP-A-61-65246 pyrazoloazole couplers containing a sulfonamide group in the molecule, birazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent (Publication) No. 226.849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No.

Specific examples of these couplers are listed below.

/ / As cyan couplers, phenolic cyan couplers and naphthol cyan couplers are the most representative in the city.

As a phenolic cyan coupler, US patents 2 and 3
No. 69,929, No. 4,518.687, No. 4,51
1.647 and 3,772,002, etc.
There are compounds (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position; typical examples include Canadian Patent No. 625,
Coupler of Example 2 described in '822, U.S. Pat. No. 3.7
Compound (1) described in No. 72.002, compound ([-4) and (+-5) described in No. 4,564゜590, compound (11, ( 2),
Examples include (3), (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772,162, No. 2,895.826, No. 4,
No. 334,011, No. 4,500゜653 and JP-A-5
There are 2,5-diacylaminophenol couplers described in U.S. Pat.
, the compound aη described in 4.557.999, 4.557.999,
Compounds (2) and (2) described in No. 565.777, No. 4
Compound (4) described in , No. 124.396, No. 4,61
Examples include the compound (1-19) described in No. 3゜564.

As a phenolic cyan coupler, U.S. Pat.
, No. 372.173, No. 4,564,586, No. 4,
430,423, JP-A No. 61-390441, and Japanese Patent Application No. 61-100222, there are compounds in which a nitrogen-containing heterocycle is fused to a phenol nucleus. Coupler ill and (3) described in No. 327,173, compound (3) and Ql described in No. 4,564,586, compound (11 and (3)) described in No. 4,430,423, and The following compounds may be mentioned.

01l Cz Hs C&H1311 In addition to the above-mentioned types of cyan couplers, diphenylimidazole cyan couplers such as those described in European Patent Application Publication EP 0,249,453A2 can also be used.

H3 C4H? Other examples of phenolic cyan couplers include U.S. Pat. No. 4,333,999, U.S. Pat.
, 444.872, 4,427.767, 4,
No. 579,813, European Patent (BP) 067.689B
There are ureido couplers described in U.S. Pat. No. 1, etc., and representative examples thereof include coupler (7) described in U.S. Pat. , coupler 04 described in No. 4,444,872, coupler described in No. 4,427,767 (
3), coupler (6) described in No. 4,609,619
(24), couplers (1) and (10) described in European Patent No. 4,579,813, European Patent No. (BP) 867.689B
Coupler (45) and (50) described in No. 1, JP-A-61
Coupler (3) described in No.-42658 can be mentioned.

Examples of naphthol-based cyan couplers include those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2,313,586);
Those having an alkylcarbamoyl group at the 2-position (for example, U.S. Pat. Nos. 2.474.293 and 4,282.312)
), those having an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 14523-1983), and those having a carbonamide or sulfonamide group at the 5-position (e.g., JP-A No. 1983-14523).
No. 237448, No. 61-145557, No. 61-1
53640), and those with an aryloxy leaving group (
For example, US Patent 3. 476.563), those with substituted alkoxy leaving groups (e.g., U.S. Pat. No. 4,296,1
No. 99), and those having a glycol M leaving group (for example, Japanese Patent Publication No. 60-39217).

These couplers can be contained in the dispersed emulsion layer in the coexistence of at least one type of high boiling point organic solvent. Preferably, high boiling point organic solvents represented by the following formulas (A) to D) are used.

Formula (A) WI w, -o-p=.

W.

Examples of the formula (B) W, Coo Wt include the following compounds.

2 (D) 'W, -0-W.

(In the formula, Wl, Wz and W are each substituted or unsubstituted alkyl group, cycloaxyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, W4 is WI, OW
, or S WI, where n is an integer from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other; ).

For details on these high boiling point organic solvents, please refer to JP-A-62
-Page 137, lower right column to 144 of publication specification No. 215272
Other types of high-boiling organic solvents that can be effectively used in the couplers of the present invention listed in the upper right column of the page include N,N-dialkylaniline derivatives. Among these, those in which an alkoxy group is bonded to the bolt position of the N,N-dialkylamino group are preferred.This type of high-boiling point organic solvent can cause magentastin to appear on the white background of color prints over time. It is also useful for preventing fog caused by development. The amount used is 10 mol% to 500 mol% per coupler.
is common, and preferably ranges from 20 mol% to 300 mol%.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as organic antifading agents for cyan, magenta and/or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, Is gallic acid, methylenedioxybenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkyl Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are U.S. Patent No. 2,360.290,
No. 2,418,613, No. 2,700.453, No. 2,701,197, No. 2,728.659
No. 2. 732. No. 300, No. 2,735,
No. 765, No. 3,982.944, No. 4,430
, 425, British Patent No. 1,363.921, U.S. Patent No. 2,710.801, U.S. Pat. is U.S. patent cylinder 3°432.
No. 300, No. 3.573,050, No. 3,574
, No. 627, No. 3,698,909, No. 3.76
No. 4,337, JP-A No. 52-i52225, spiroindanes are described in U.S. Patent No. 4,360.5139, and p-alkoxyphenols are described in U.S. Patent No. 2.735.
．． No. 765, British Patent No. 2.066.975, JP-A-59-10539, JP-A-57-19765, etc., hindered phenols are described in US Patent No. 3°700.4.
No. 55, JP-A No. 52-72224, U.S. Patent No. 4,2
28.235, Japanese Patent Publication No. 52-6623, etc., gallic fII derivatives, methylenedioxybenzenes, and aminophenols are each disclosed in U.S. Patent No. 3,457,079.
No. 4,332.886, Special Publication No. 56-2114
No. 4, etc., hindered amines are disclosed in U.S. Patent No. 3,33.
6°135, British Patent No. 4,268.593, British Patent No. 1.32. No. 889, same No. 1. 354. Ether and ester derivatives of phenolic hydroxyl groups are described in Japanese Patent Publication No. 313, No. 1,410.846, Japanese Patent Publication No. 1420/1982, Japanese Patent Publication No. 114036/1982, No. 59-53846, Japanese Patent Publication No. 59-78344, etc. US Patent Tube 4.155,7
No. 65, No. 4,174.220, No. 4,254,
No. 216, No. 4.264,720, Japanese Unexamined Patent Publication No. 1983-1
No. 45530, No. 55-6321, No. 58-1051
No. 47, No. 59-10539, Special Publication No. 57-3785
No. 6, U.S. Patent No. 4,279,990, Special Publication No. 1973-
No. 3263, etc., metal complexes are disclosed in U.S. Patent No. 4.050,
No. 938, No. 4,241゜155, British Patent No. 2,
No. 027,731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers, usually in an amount of 5 to 100% by weight, and adding them to the bright light layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer.

Among the above antifading agents, spiroindanes, hindered amines, and the like are particularly preferred.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers.

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

A preferred compound (F) has a second-order reaction rate constant with p-anilidine of 2 (in trioctyl phosphate at 80°C) of 1. Ojl/mol・sec ~I
X I O-'l/mo I-s e c (7) range [
[" is a compound that reacts. Note that the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (F) can be represented by the following symbol (FI) or (FI[).

General formula (FI) R1-(A), -X General formula (FII) R2-C=Y ■ In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n is Represents 1 or O. A represents a group that reacts with the aromatic amine developer to form a chemical bond, X represents a group that reacts with the aromatic amine developer and leaves, B represents a hydrogen atom, an aliphatic group, It represents an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (FII). Here R1, X, Y
and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (FT) and (FII), see JP-A-63-158545 and JP-A-62-2.
No. 83338, Japanese Patent Application No. 158342, No. 1983, Japanese Patent Application No. 1983
It is described in specifications such as No. 3-18439.

On the other hand, more preferable compounds (G) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound are listed below - Monana ( Gl).

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and 2 is a nucleophilic group or a nucleophilic group that is decomposed in a photosensitive material to release a nucleophilic group. The compound represented by -Monken (Gl), which represents a group, is 27! Nucleophilicity of l<Rear5on ^CH
31 values (R, G, Rear son + eta I
l,, J, Am, Chesi, Soc.
, 9 0. A group in which 3 1 9 (196 days) is 5 or more or a group derived therefrom is preferred.

For specific examples of the compound represented by the general formula (G[),
No. 48, No. 62-229145, JP-A No. 63-184
No. 39, No. 63-136724, No. 62-21468
No. 1, No. 62-158342, etc.

Further, details of the combination with the above-mentioned compounds (G) and (F) are described in Japanese Patent Application No. 18439/1983.

Similarly, it is preferable to use an amine compound in order to prevent staining and other side effects caused by the formation of color pigments due to the reaction between the color developing agent or its oxidized product in the film and the coupler during storage after processing. A more preferable one can be represented by the following symbol (FC).

- Monana (FC) Roo R01 \ / Fake R, Toshikichu, Ro. represents a hydrogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfonyloxy group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a heterocyclic group, an aliphatic group, an aromatic group, and a heterocyclic group. R61 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

Rag represents an aliphatic group, an aromatic group, and a heterocyclic group, where at least two of Roo and RoRa are bonded to each other to form a monocyclic or multicyclic heterocycle [
7 is fine.

For specific examples of compounds represented by the general formula (FC), U.S. Pat.
No. 79, No. 4.585,728, JP-A-58-10
No. 2231, No. 59-229557, etc.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include: Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the gelatin manufacturing method can be found in Arthur Weiss, The Macromolecular Chemistry of Gelatin, (Academics)・Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films, vinyl chloride resins, and the like, and these supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 5 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%)'(R+). The coefficient of variation of the occupied area ratio (%) is the standard deviation of Rm relative to the average value of R1 (l)
It can be determined by the ratio S/π. The number of target unit areas (n) is preferably 6 or more, so the coefficient of variation s/R can be determined.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), color image stabilizer (
Cpd-1) 4.4g and color image stabilizer (Cpd-7)
0.7g to 27.2cc of ethyl acetate and solvent (Sol
v-3 > 8.2 g was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 3 cc of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in 1115 cc of gelatin aqueous solution. On the other hand, silver chlorobromide emulsion (grain size 0.85μ, coefficient of variation 0.07
containing 111 mol % of bromide localized on a part of the particle surface as a proportion of the whole particle), the following two types of blue seductive coloring dyes were added at 2.0 x 10-' mol each per 111 mol. After addition, sulfur sensitization was performed.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

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-3,5-dichloro-5-1-lyazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer 03 H (7.0 x 10-' mol per mol of silver halide) S
Oi SCh HN (Cz Hs).

(2.0×10 each of the above two types per mol of silver halide)
-'mol)ctiis de Cs1L+(
For the red-sensitive emulsion layer, the following compound was added to 1 mole of silver halide
2.6XlO-' moles were added per mole.

(4°0XIO” mol per mol of silver halide) and also 1-(5-methylureidophenyl)5-mercaptotetrazole for the pre-malignant emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, respectively. 8 per mole of mole
．． 5 x 10-' moles, 7.7XIO-' moles, 2.
5 x 10-' moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating M (g/M). The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminated paper [The polyethylene on the first layer side contains a white pigment (Tilt) and a blue dye (ulmarine)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion Oo 30 gelatin 1.86 yellow Coupler (ExY) 0.82 Color Image Stabilizer (Cpd
-1) 0.19 color image stabilizer (Cpd-7
) 0.03? Container (Solv-3)
0. 35 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Sol
v-1>0.16 Solvent (Solv-4
) 0.08 Fifth layer (green-sensitive layer) Silver chlorobromide emulsion (grain size 0.40μ, coefficient of variation 0.0
9 cubes and contains 1 mol% of silver bromide locally on a part of the grain surface as a proportion of the whole grain)
0.20 gelati 7 1
．． 24 magenta coupler (ExM) 0.2
9 Color image stabilizer (Cpd-3) 0.09 Color image stabilizer (Cpd-4) 0.06 Solvent (
Solv-2) 0.32 Solvent (So
lv-7) 0.16 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (tJV-1) 0.47 Color mixing inhibitor (Cpd-5) O-05 solvent (Solv
-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (grain size 0.36μ, coefficient of variation 0.1
Gelatin cyan coupler (Ex C) Color image stabilizer (Cpd-6) Color image Stabilizer (Cpd-7) Color image stabilizer (Cpd-9) Solvent (Solv-4) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (3o1v -5> Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin 1, 33 0, 17 0, 03 (Ex Y) Yellow coupler (Ex C) Cyan coupler 1 :3:6 Mixture (weight ratio) (Cpd Color image stabilizer (Cpd Color image stabilizer) (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer CI.

(tJV-1>UV absorber (Solv-1) melt medium (Solv-2) melt medium (SOIV solvent COOCs H+t (CI□).

C00C* H+t (Solv-3) Solvent (Solv-6) Solvent (SOIV-7) The silver halide color photographic light-sensitive material prepared as in 7F below is designated as sample number 01.

Next, the magenta coupler of the third layer, the green-sensitive layer, was replaced with the coupler of the present invention, M-1, 2, 7, 9, 10, 12, 43, 60.
, 62 were replaced in equal molar amounts to prepare samples 02 to io.

The following experiment was conducted to evaluate the photographic performance of these prepared samples.

First, apply a photosensitive needle (Fujifilm KKfiFW) to the above sample.
H type, light source color temperature 3200''K) was used to provide stepwise exposure for sensitometry through a three-color separation filter. At this time, the exposure time was 0.1 seconds, and the exposure time was 250
The exposure amount was adjusted to match that of CMS.

After exposure, color development processing was performed using the following processing steps and processing solution composition.

1 work per month■ i-skin anus-dish color development 35℃ 45 seconds bleach fixing
30~36℃ Stable for 45 seconds ■ 30~3
7℃ 20 seconds stable 0 30~37℃ 2
Stable for 0 seconds■ 30-37℃ Stable for 20 seconds
■ Dry at 30-37℃ for 30 seconds
70 to 85°C for 60 seconds (4 tank countercurrent system with stability ① to ② was used.) The composition of each treatment liquid is as follows.

Sadan Nitanseioka (A) Wed 800
mA! Ethylenediaminetetraacetic acid 2.0g Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate
25gN-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-4-aminoanili 5. Ogne sulfate N,N-diethylhydroxyl 4.2g Amine 5.6-dihydroxybenzene 1.2.4-trisulfonic acid 0.3g Optical brightener (
4,4'-Diaminostyl/system) Add water to pH (25℃) 20% of the pH (25°C) Sodium sulfite 1 ethylenediaminetetraacetic acid (I[l) ammonium ethylenediaminetetraacetic acid 2 Add sodium water to pH (25°C) Substituent formalin (37%) Formalin-sulfite adduct 5-chloro-2-methyl-4=isothiazolin-3-one 2.0 1 000 m 1 10.10 400 mt ) 100mj! 8g 5g 3g 1 000mJ 5.5 0.1g 0.7g 0.02g 2-methyl-4-inchazoliso-3-one 0.01g sulfur
o, o o s Add water to 1000ml pH (25℃
) 4.0 Subsequently, 2.0 g of ethylenediaminetetraacetic acid in the color developer (A) was replaced with a chelating agent, which is a component of the present invention,
so that its concentration is 1.0×10-” mol/l,
It was prepared using the compounds shown in Table 1 without any other changes. Finally, color developer CF) was prepared without adding a chelating agent, but by adding Cag 4 ions to 300 ppm. Processing was carried out using these color developers in the same manner as previously described.

The density of the mazenk color image of the developed color image obtained as described above was measured, and its characteristic curve was obtained. From these characteristic curves, the sensitivity point (exposure that gives a reflection density of fog → -0,5, log E) + j! The density value was read at the exposure amount of ogE=0.5. These results are shown in Table 1.
Shown below.

Table 1) From the results in Table 1, it is clear that the color developer does not contain a chelating agent,
In the color developing solution (F) to which Cag * ions were added at a concentration of 300 pPm, it was observed that color development was inhibited by Cat'' ions in both the couplers of the present invention and the comparative couplers. It can be seen that the coupler is less affected by this effect.

In addition, color developers (A) to (E) using chelating agents are also available.
), the chelating agent (ethylenediaminetetraacetic acid) used for comparison has a weak chelating effect, so color developer (A)
Although color development is increased to some extent compared to color developer (F), it cannot be said to be sufficient.On the other hand, color developers (B) to (E) using the chelating agent of the present invention are compared to color developer (F). It can be seen that the color development is improved compared to liquid (A). Furthermore, as a chelating agent, the degree of improvement in color development is greater with organic phosphonic acid compounds compared to the comparative chelating agent and color developer ([E)] and color developer (B).
) to (D).

Example 2 Samples 01 to 1O prepared in Example 1 were exposed under the same exposure conditions, and developed using the processing steps and processing solution compositions shown below.

Next, the chelating agent of the color developer (G), the compound of the present invention (
The color developing solution (H
) was processed in the same way.

The density of the obtained magenta color images was measured to obtain respective characteristic curves. From these characteristic curves, the density values were taken according to the method described in Example 1, and the color developer (+
4) Density value (D)/Concentration value (D) of color developer (G)
The color development property was examined by taking the ratio of o). Table 2 shows the results obtained.
Shown below.

Processing process〉 Temperature〉 Processing time〉 Color development 35℃ 45 seconds Bleach fixing 35℃
Wash for 45 seconds 0 Wash for 30 seconds at 35°C Wash for 30 seconds at 35°C ■
35°C Drying 75°C Monji Juni (G) Water Compound of the present invention (68) Triethanolamine Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-amino Aniline sulfate N,N-bis(carboxymethyl)hydrazine fluorescent whitening agent (WHITEX4B, manufactured by Sumitomo Chemical) Add water to pH (25℃) Keiwata Sadayuki 30 seconds 60 seconds 8 00 m 1 3, 0 g 8, 0g 1,4g 5g 5,0g 5,0g 1,0g 000ml 10.05 Water 700
ml ammonium thiosulfate solution 100ml (7
00g/l) Ammonium sulfite 18g ferric ethylenediaminetetraacetic acid 55g ammonium dihydrate ethylenediaminetetraacetic acid dinato tribarium ammonium chloride bromide 40g glacial acetic acid
Add 8g water
1000mlP100°c)
5. 5 Washing solution Tap water was treated with an ion exchange resin to reduce calcium and magnesium to 3 ppm or less, and was used (electrical conductivity at 25° C. was 5 μs/cya).

table I squeezed it enough to keep it from wearing.

The moisture content of the magenta color image obtained as described above was measured.
From the characteristic curve, the density value was read in the same manner as above, and the ratio with the density value (D, ) of the color developing solution (G) was determined to evaluate the color development property.

The results are shown in Table 3.

From the results in the table above, it can be seen that Samples 02 to 10 using couplers as constituent elements of the present invention are clearly less susceptible to color development inhibition by Ca'' ions than Sample O1, which is a comparative coupler.

Next, the color developer (G) has a Ca'' ion concentration of 300.
It was added so that it became ppm. At this time, the color developing solution became cloudy, but the processing was carried out in that state. Furthermore, chelating agent (68) was added to (26), (31), diaminopropanoltetraacetic acid, ethylenediaminetetraacetic acid, etc. in equimolar amounts so that Ca'' ions were 300 ppm as above, and treatment was performed. Table 3 (Continued) As a result of Table 3, the chelating agent of the present invention shows that compared to the comparative chelating agent, the degree of decrease in color development due to Al- ions is small; In comparing organic phosphonic acid-based chelating agents and aminopolycarboxylic acids, it is clear that organic phosphonic acid-based chelating agents are superior.

Example 3 Using samples 01.02 and 06 prepared in Example 1,
Exposure was applied in the same manner, and processing was carried out by adding the concentration and type of chelating agent in the color developer (A) as shown in Table 4. From the characteristic curve of the obtained magenta color image, the density value was determined according to the method evaluated in Example 1. These results are summarized in Table 4.

From the results in Table 4, it was observed that for the chelating agents used for comparison, the coloring properties of both the comparative coupler and the coupler of the present invention varied greatly depending on the concentration of the chelating agent added, indicating that the concentration dependence was large. Recognize. On the other hand, the chelating agent of the present invention has a concentration of 5 to 10XIO-'mol/e
In this case, almost no change in concentration is observed, but with the comparative coupler, the change in concentration is somewhat large.Also, when the concentration of the chelating agent is less than lXl0-3 mol/1, a concentration dependence is observed, and the color density is decreases with decreasing drug concentration. From these facts, it can be said that in the combination of a coupler and a chelating agent, which are constituent elements of the present invention, the concentration of the chelating agent is preferably 2×10 −” mole/1 or more.

Subsequently, when similar experiments were performed with chelating agents (25), (26), (28), and (31), the same trend as with chelating agent (68) was observed, and the concentration of the chelating agent was 2×10−” molar. It was found that it is desirable that the value is /1 or more.

(Effects of the Invention) By carrying out the present invention, sufficient color development can be obtained even in rapid development processing.

Procedural amendment (1 meal 2

Claims (1)

[Scope of Claims] At least one 5-pyrazolone magenta coupler having a leaving group represented by the following general formula [I] at the coupling position
A silver halide color photographic light-sensitive material consisting of 70 mol% or more of silver chloride and at least one layer of seeds is prepared by adding at least one species selected from the organic phosphonic acid compound group or the aminopolycarboxylic acid compound group to 2.0 x 10^ −＾3mol/
1. A method for processing a silver halide color photographic light-sensitive material, characterized in that processing is carried out using a color developer containing at least 1 liter of silver halide for a processing time of 2 minutes and 30 seconds or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼General formula (I) (However, L_1 and L_2 represent methylene and ethylene groups. l and m represent 0 or 1. R_1 is a hydrogen atom,
Represents an alkyl group, aryl group or heterocyclic group. R
_2 represents a group connected to A through a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. A represents a carbon atom or a sulfur atom. n represents 1 when A is a carbon atom, and represents 1 or 2 when A is a sulfur atom. B represents a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. X represents an atomic group necessary to form a ring. R_1 and R_2 may be combined with each other to form a ring. If B is a carbon atom or a nitrogen atom, B and R_
2 may be bonded to each other to form a ring. )