JPS59185335A - Dye image forming method - Google Patents

Abstract

PURPOSE:To improve storage stability of a dye image by incorporating an anilino-type magenta coupler and a specified cyan coupler in a photosensitive material and controlling pH of the final processing soln. used for a color development to a specified value. CONSTITUTION:An anilino-type magenta coupler and a cyan coupler represented by general formula I are used for a photosensitive material, and its processing is stabilized by controlling pH of the final processing soln. used for color development to 2.0-6.5. A dye image obtained by color developing a silver halide color photosensitive material using said magenta coupler and said cyan coupler and stabilizing it is prevented from yellow staining caused by the unreacted magenta coupler, and superior in color fading resistance both in the light and the dark, thus enhancing long time storage stability of the dye image in good balance. In formula I , R1, R2 are each alkyl, aryl, alkylamino, arylamino, or heterocyclic, or R2 may form a 6-membered hetero ring condensed with the phenol ring of formula I together with R3; R3 is H or halogen; Z1 is H or a group capable of being released from the cyan coupler of formula I by its reaction with the oxidized product of a color developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. BACKGROUND OF THE INVENTION Technical Field The present invention relates to a method for forming a dye image, and more particularly to a method for forming a dye image in which image storage stability is improved.

2-C Prior Art and its Problems As is well known, in subtractive color silver halide photographic materials, dye images are created when the imagewise exposed silver halide photographic materials are color developed. By reducing exposed silver halide grains, they are oxidized, and the oxidized color developing agent undergoes a coupling reaction with cyan, magenta, and yellow dye image-forming couplers, thereby forming the silver halide particles.

The fundamental properties required of these cyan, magenta, and yellow dye image-forming couplers are that they not only form a dye image, but that the dye image formed from each of these dye image-forming couplers is resistant to heat and moisture. It has good fastness to light, that is, excellent resistance to fading, and fastness to light, that is, excellent resistance to light fading. One example of this is that it has excellent overall image storage stability, such as the fact that coloring is less likely to occur.

In other words, it is important to achieve a well-balanced solidification of dye images formed from cyan, magenta, and yellow dye image-forming couplers, as well as to prevent discoloration and coloring of dye images and unexposed areas. There is.

When a photographic image consisting of nine dye images formed from these cyan, magenta, and yellow dye image-forming couplers is stored for a long time in an album, etc., the most noticeable discoloration and blue color is the blue color in the unexposed areas. ,
In addition, in the dye painting A1, the black area is discolored to brownish brown, and the green area is discolored to yellow-green. One of the large pots of blue and yellow color changes is caused by light yellow contamination caused by magenta couplers remaining unreacted in unexposed areas or dye images and being decomposed by light.
yellow stain). Therefore, as one of the methods to prevent these discolorations and blue color, for example, for light yellow contamination in uncolored areas, the final processing solution used in color development process 1, that is, the stable solution that is usually kept in the neutral range, has been used. It is known that this yellow coloring can be reduced by lowering the pH of the final processing solution such as a chemical bath, that is, by shifting it to an acidic side. The details are described in "Study on Standard Setting" (edited by the Japan Wedding Photography Association). However, when the pH of the final processing solution used for color development processing is lowered, the black part changes to brown and the green part turns yellow. Not only does discoloration to green become more likely to occur, but also there is a risk that the fading resistance of dye images formed from cyan dye image-forming couplers that are commonly used may deteriorate.
If the pH of the final processing solution used in this color development treatment is raised to make it more basic, the change in the black and green areas will be prevented, but light yellow contamination in the unexposed areas will increase, and furthermore, the cyan coupler will become more basic. A new disadvantage arises in that the fastness to light deteriorates, and in the past, it has been difficult to comprehensively improve the discoloration and color staining caused by these unreacted magenta couplers, as well as the dark fading and light fading properties of cyan couplers. had become extremely difficult.

■Object of the Invention The first object of the present invention is to provide a method for forming a dye image that can prevent discoloration and color staining during storage of the dye image, and improve the image storage stability of the dye image in a well-balanced manner. A second object of the present invention is to maintain good fading resistance of a dye image formed from a cyan dye image-forming coupler, and to prevent unreacted magenta coupler from forming a dye image. It is an object of the present invention to provide a method for forming a dye image that can prevent light yellow staining caused by the dye.

The above object of the present invention is to provide a silver halide emulsion layer 8 containing at least one magenta coupler selected from anilino-type magenta couplers and at least one cyan coupler among cyan couplers represented by the following general formula El). After imagewise exposure of a silver halide photographic material having a silver halide emulsion layer on a support, this
When a silver halide photographic light-sensitive material is subjected to a color development process including color development to form a dye image, the pH of the final processing solution used in this color development process is adjusted to 2.0 to 65.
This is achieved by ζ.

General formula [1] (wherein, R1 represents an alkyl group, an aryl group, an alkylamino group, an arylamino group, or a heterocyclic group. R2
represents an alkyl group, an aryl group, an alkylamino group, an arylamine group or a heterocyclic group. Also, R2 is R3
6 that is linked to and fused to the phenol ring in general formula [1]
may form a membered heterocycle. R3 represents a hydrogen atom or a halogen atom. Further, R3 may be linked with R2 to form a 6-membered heterocycle condensed to the phenol ring in the general formula El). zl represents a hydrogen atom or a group capable of separating from the cyan coupler represented by the general formula [1] by reaction between the cyan coupler represented by the general formula El) and the oxidized surface of the color developing agent. ) I Detailed Description of the Invention In the present invention, the alkyl group represented by R1 of the cyan coupler represented by the general formula (11 (hereinafter referred to as the cyan coupler according to the present invention)) is, for example, an ethyl group, n-
It is a straight chain or branched alkyl group having 1 to 24 carbon atoms, such as a propyl group, an i-propyl group, a t-butyl group, a t-pentyl group, an n-octyl group, and an n-octadecyl group. The aryl group represented by R1 is, for example, a phenyl group,
Naphthyl group, etc. The alkylamino group represented by R is, for example, a methylamino group, n-propylamine group, i
- A linear or branched alkylamino group having 1 to 24 carbon atoms, such as a propylamine group, t-butylamino group, n-octylamino group, or n-octadecylamino group. The arylamino group represented by R1 is, for example, a phenylamino group or a naphthylamino group. The heterocyclic group represented by R1 is, for example, a 5-membered or 6-membered negative heterocyclic group such as a furyl group, a pyrrolyl group, or a pyridinyl group. When the group represented by R1 has a substituent, examples of the substituent include a halogen atom (e.g. fluorine, chlorine, bromine),
Alkyl groups (e.g. straight chain or branched alkyl groups such as methyl, ethyl, i-propyl, t-butyl, benzyl, etc.), aryl groups (e.g. phenyl, tolyl, naphfA4 etc.1, nitro groups) , cyan group, hydroxyl group, alkylsulfonyl group (e.g. linear or branched alkylsulfonyl group such as evaethylsulfonyl group, n-butylsulfonyl group), arylsulfonyl group (e.g. evaphenylsulfonyl group), carboxy group, Alkylcarbonyl groups (for example, straight-chain or branched alkylcarbonyl groups such as methylcarbonyl group and t-butylcarbonyl group),
7'J-/l/l/carbonyl J, tif benzoyl group], alkoxy groups (e.g., methoxy, ethoxy, t-butyloxy, etc.), straight-chain or branched alkyloxy groups (1.71 J-ruoxy groups (e.g., phenoxy basis)
, alkylamino groups (e.g. linear or branched alkylamino groups such as N,N-dimethylamino group and N-butylamino group), arylamino groups (e.g. anilino group), alkyloxycarbonyl groups (e.g. methoxycarbonyl group, n-butyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group), alkylcarbonyloxy group (e.g. straight chain or branched acetoxy group, glopionyloxy group, etc.) alkylcarbonyloxy groups), arylcarbonyloxy groups (e.g. benzoyloxy groups), alkyloxysulfonyl groups (e.g. linear or branched alkyloxysulfonyl groups such as methoxysulfonyl groups and ethoxysulfonyl groups), aryloxysulfonyl groups (e.g. evaphenoxysulfonyl group)
, alkylsulfonyloxy groups (e.g. (f linear or branched alkylsulfonyloxy groups such as methylsulfonyloxy group, ethylsulfonyloxy group), arylsulfonyloxy groups (e.g. if phenylsulfonyloxy group), alkylacylamino groups (e.g. acetylamino group, propionylamino group, etc.) linear or branched alkylcarbonylamino group), arylacylamino group (e.g. benzoylamino group), alkylcarbamoyl group (e.g. methylcarbamoyl group, ethylcarbamoyl group, etc.)
straight-chain or branched alkylcarbamoyl group), arylcarbamoyl group 11jif phenylcarbamoyl group),
Alkylsulfonamide group (for example, a straight chain or branched alkylsulfonamide group such as methanesulfonamide group)
, arylsulfonamide groups (e.g. benzenesulfonamide group), alkylsulfamoyl groups (e.g. linear or branched alkylsulfamoyl groups such as evamethylsulfamoyl group), arylsulfamoyl groups (e.g. phenylsulfamoyl group), moyl group), alkylaminosulfonamide groups (e.g. linear or branched alkylaminosulfonamide groups such as N,N-dimethylaminosulfonamide groups), arylaminosulfonamide groups (e.g. N-phenylaminosulfonamide groups), Alkylureido group (
For example, a straight chain or branched alkylureido group such as a methylureido group), an arylureido group (for example a phenylureido group), an alkyloxalyl group (for example a straight chain or branched alkyloxalyl group such as a methyloxalyl group)
, an aryloxalyl group (for example, a phenyloxalyl group), and the like. One or more of these substituents can be introduced into the group represented by R1.

In the present invention, R1 is preferably an alkyl group, an aryl group, an alkylamino group, or an arylamino group, and particularly preferably an alkyl group or a phenyl group. When this alkyl group has a substituent, preferred substituents include a fluorine atom (preferably fluorine), and when the aryl group has a substituent,
Preferred substituents include a halogen atom (more preferably chlorine and fluorine), an alkyl group (especially preferably a halogenoalkyl group), a cyano group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, and an arylsulfamoyl group. Examples include a moyl group, an alkylureido group, an arylureido group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, and an arylcarbonyloxy group.

The alkyl group represented by R2 in the general formula
- A linear or branched alkyl group having 1 to 24 carbon atoms, such as an octyl group, an n-dodecyl group, or an n-octadecyl group. The aryl group represented by R2 is, for example, a phenyl group or a naphthyl group. The alkylamino group represented by R2 is, for example, a methylamine group, ethylamino group, n
-propylamino group, l-propylamino group, n-butylamino group, i-butylamino group, t-butylamino group, t-pentylamino group, n-octylamino group, n-
It is a straight chain or branched alkylamino group having 1 to 24 carbon atoms such as a dodecylamino group and an n-octadecylamino group. The arylamino group represented by R2 is, for example, a phenylamino group or a naphthylamino group. The heterocyclic group represented by R2 is, for example, a 5- or 6-membered heterocyclic group such as a furyl group, a pyrrolyl group, or a pyridinyl group. When the group represented by R2 has a substituent, examples of this substituent include those selected from the above-mentioned substituent group when the group represented by R1 has a substituent.

In the present invention, preferable groups represented by R2 in general formula [1] include alkyl groups and aryl groups, and a more preferable group is a group represented by the following general formula [111].

General formula (II) + R4-X +-R5 General formula [111l, where n represents O or an integer of engineering, and R4 is an alkylene group [e.g., α-ethylmethylene group, α-butylmethylene group, α -dodecylmethylene group, α-butylethylene group, α-dodecylmethylene group (however, the carbon at the α position of the ethylene group refers to the carbon directly bonded to the acylamino group)], or an arylene group (e.g. phenylene group). represent.

X represents a divalent group, for example -〇-1-Coo -1
-0CO-1-8O2-1-S-1-NH8O2-1-
8O2NH-1-CON)I-1 or -NHCO- group, preferably 10- or 18O2- group.

R5 is an alkyl group (e.g. n-butyl group, n-octyl group, n-nonyl group, n-dodecyl group, n-octadecyl group, pentadecyl group, foam-IJ decyl group, t-octyl group, t- (nonyl group, etc.), or an aryl group (eg, phenyl group). These alkyl groups and aryl groups may have single or multiple substituents, for example, typical substituents for phenyl groups include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxyl group, cyan group, nitro group, alkyl group (e.g. methyl group, ethyl group, butyl group, octyl group, dodecyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, octoxy group, etc.), alkyl sulfur Famoyl groups (e.g. butylsulfamoyl group, octylsulfamoyl group, etc.), arylsulfamoyl groups (e.g. phenylsulfamoyl group, xylylsulfamoyl group, tolylsulfamoyl group, mesitylsulfamoyl group, etc.) ), alkyloxycarbonyl groups (e.g. methyloxycarbonyl group, butyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. evaphenyloxycarbonyl group, xylyloxycarbonyl group, tolyloxycarbonyl group, mesityloxycarbonyl group) Alkylsulfonamide group (e.g. methylsulfonamide group,
ethylsulfonamide group, butylsulfonamide group, benzylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, xylylsulfonamide group, tolylsulfonamide group, mesitylsulfonamide group, etc.), alkylcarbonyl Mention may be made of oxy groups (eg ethylcarbonyloxy), aryl groups (eg benzoyloxy) or aminosulfonamide groups (eg N,N-dimethylaminosulfonamide). Two or more phenyl groups may be introduced into these substituents. R
Preferred groups represented by 5 include an unsubstituted phenyl group or a substituent such as an alkyl group, an alkylsulfonamide group, an alkoxy group, an alkylsulfamoyl group, an aminosulfonamide group, an alkyloxycarbonyl group,
A phenyl group having an aryloxycarbonyl group can be mentioned.

In the present invention, the halogen atom represented by R3 in general formula [11] is, for example, chlorine, bromine, or the like.

In addition, as a 6-membered heterocycle condensed with the general formula (phenol ring t in 13) formed by R2 and R3 connected together, (R' is a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a phenyl group, etc.). (R-R-R) group).

The group which can be separated by the reaction between the cyan coupler represented by the general formula (1) represented by 21 in the general formula El) and the oxidized product of the color developing agent is well known to those skilled in the art, and typical examples include is, for example, a nitrogen atom (e.g. fluorine, chlorine, bromine), an alkoxy group (e.g. methoxy group,
ethoxy group, octoxy group, etc.), oryloxy group (e.g. phenyloxy group, etc.), cyclohexyloxy group,
An arylazo group (e.g., phenylazo group, etc.), a thioether group (e.g., benzylthio group, etc.), or a heterocyclic group (
Examples include oxazolinopediazolyl, triazolyl, tetrazolyl, etc.), aralkylcarbonyloxy groups, and the like. Preferred examples of zl include a hydrogen atom, a chlorine atom (preferably a chlorine atom), an alkoxy group or an alkoxy group.

In the present invention, particularly preferred cyan couplers represented by the general formula [1] are compounds represented by the following general formula (I).

In general formula [1], R6 is a halogen atom (e.g. chlorine, fluorine), an alkylsulfonamide group (e.g. methanesulfonamide group, ethanesulfonamide group), an arylsulfonamide group (e.g. benzenesulfonamide group), an alkylsulfonamide group (e.g. benzenesulfonamide group), moyl group (e.g. methylsulfamoyl group, ethylsulfamoyl group), arylsulfamoyl group (e.g. phenylsulfamoyl group), cyano group, alkyloxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), aryl Oxycarbonyl group (e.g. phenoxycarbonyl group), or alkyl group (e.g. methyl group, ethyl group, t-butyl group, dodecyl group, octadecyl group, benzyl group, phenethyl group, trifluoromethyl group, pentafluoroethyl group, etc.) represents.

R7 represents an alkyl group (eg, methyl group, ethyl group, t-butyl group, n-butyl group, n-dodecyl group), preferably a straight chain or branched alkyl group having 1 to 12 carbon atoms.

R8 is an alkyl group (e.g. methyl group, ethyl group, butyl group, pentyl group, octyl group, dodecyl group), an alkylsulfonamide group (e.g. methylsulfonamide group, ethylsulfonamide group, butylsulfonamide group, benzylsulfonamide group) ), alkylsulfamoyl group (
For example, butylsulfamoyl group, octylsulfamoyl group), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, octoxy group), alkylaminosulfonamide group (e.g. N, N-dimethylaminosulfonamide group, N- methylaminosulfonamide group), alkyloxycarbonyl group (e.g. ethoxycarbonyl group,
butoxycarbonyl group) or aryloxycarbonyl group (eg phenoxycarbonyl group).

2, "represents a hydrogen atom or a halogen atom (for example, chlorine, fluorine).

k and l each represent an integer from O to 5. Below,
Typical specific examples of cyan couplers according to the present invention will be listed, but the present invention is not limited thereto.

(11 (2) (3) FI (4) 0 Sweet (5) (6) (7) (8) (■0) 0■ (111 (12) H (13) 0■ (14) (15) 23 - (17) 24- (21) (22) H (23) (24) TI (25) OR (27) (28) (29) (30) (31) 27- (33) (34) (35) H (36) H 28- (37) (38) l (39) 0) 1 (40) (41) (42) In the present invention, the anilino-type magenta coupler (hereinafter referred to as magenta coupler according to the present invention) (, s) is preferably a 3-anilino-5-pyrazolone type magenta coupler, particularly preferably a 3-anilino-5-pyrazolone type magenta coupler represented by the following general formula (ff).

The following is a blank general formula [1v] 9C/1 In the formula, R9 represents a hydrogen atom, a 710gen atom, or an alkoxy group having 1 to 8 carbon atoms.

Represents an elementary atom or an acyl group. Further, R11 and R12 may be linked together to form a 5-negative heterocycle together with the nitrogen atom to which they are bonded. ), an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfonamide group, an alkylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylcarboxylic acid ester group, or an arylcarboxylic acid ester group. z2 is a hydrogen atom or a general formula [ffl
represents a group that can be separated from the real magenta coupler shown in m represents an integer from O to 4. ] In the present invention, the halogen atom represented by R9 in the general formula [[] is, for example, fluorine, chlorine, bromine, or iodine, and the alkoxy group is, for example, methoxy group, ethoxy group, n
- A straight chain with 1 to 24 carbon atoms such as propyloxy group, i-propyloxy group, n-butyloxy group, j-butyloxy group, t-butyloxy group, n-octyloxy group, t-octyloxy group, or It is a branched alkyloxy group, and R9 is preferably a halogen atom, and R9 is preferably a chlorine atom. In RIO of the general formula (IT), the acyl group represented by R11 and R12 in Table 11 -N 1 to 12 alkylcarbonyl groups), arylcarbonyl groups (e.g. benzoyl group, naphthoyl group), cycloalkylcarbonyl groups (e.g. cyclohexycarbonyl group), heterocyclic carbonyl groups (e.g. 4-pyridylcarbonyl group), When R11 and R12 are linked together to form a 5-negative heterocycle with the nitrogen atom to which they are bonded, examples of this heterocycle include, for example, a cono-phosphate group (e.g., an octylcono-phosphate group, a dodecylsuccinimide group). alyarucono-phosphoric acid imide group, alkenyl succinimide group, aryl succinimide group)
Examples of the alkylsulfonamide group represented by RIO include a straight-chain or branched alkylsulfonamide group having 1 to 12 carbon atoms, such as a methanesulfonamide group, an ethanesulfonamide group, and a butanesulfonamide group. The arylsulfonamide group represented by a certain QRIO is, for example, a phenylsulfonamide group or a naphthylsulfonamide group. The alkylsulfamoyl group represented by RIO is a linear or branched alkylsulfamoyl group having 1 to 12 carbon atoms, such as a methylsulfamoyl group, an ethylsulfamoyl group, or an octylsulfamoyl group. Examples of the arylsulfamoyl group represented by 0RIO include evaphenylsulfamoyl group and naphthylsulfamoyl group. The alkylcarboxylic acid ester group represented by RIG is, for example, an ethylcarboxy group or an octylcarboxy group. The arylcarboxylic acid ester group that can be used in RIO is, for example, a phenylcarboxy group, a naphthylcarboxy group, or the like. General formula [1
v], RIO is preferably an alkylacylamino group, an alkylcarbamoyl group, an arylacylamino group, an arylcarbamoyl group, or an alkylsuccinimide group, and particularly preferably an alkylacylamino group or an alkylsuccinimide group. m represents an integer from θ to 4, preferably 1 or 2. The reaction between the magenta coupler represented by the general formula [1v] represented by 22 in the general formula [■] and the oxidized product of the color developing agent results in the reaction of the general formula [■].
Groups that can be separated from the magenta coupler represented by IVl include, for example, alkylthio groups such as benzylthio groups, arylthio groups such as phenylthio groups, alkyloxy groups such as benzyloxy groups, aryloxy groups such as phenoxy groups, alkylsulfo groups, and phthalyl groups. It is an acid imide group. General formula [1
] 22 is preferably a hydrogen atom, an alkylthio group, or an arylthio group.

The magenta coupler according to the present invention has the general formula [
In addition to those represented by [V], two of the coupler residues constituted by the moiety excluding 22 of the coupler of the general formula [IVl (these two coupler residues may be the same or different) may be formed by linking via a linking group such as an alkylene group such as a methylene group.It can be a so-called bis coupler.Furthermore, as the magenta coupler according to the present invention, this n2 In addition to these,
For example, U.S. Pat. Nos. 3,277,155 and 3,4
It can be a 4-equivalent type or 2-equivalent type coupler, or a polymeric coupler, such as those described in 58,315 Sokama specification.

Typical examples of the magenta coupler according to the present invention are shown below, but the invention is not limited thereto.

Margin below +11 l e (2) C/ Shil (3) t (41 l C/? (5). .

Shir (6) (7) (8) r/ Z (9) p (1010CH3 CI! (11) Shir (12) Z 39- (13) Z (4) CI! -40= (16) C/ C/ +17I C/ C/? (18) I 42- (Engineering 9) (23) (24) 43- C1! (26) (27) C/ 44 - Silver halide photographic material according to the present invention may be any support as long as it has at least a silver halide emulsion layer containing the magenta coupler according to the present invention and a silver halide emulsion layer containing the cyan coupler according to the present invention on the support; There are no particular restrictions on the number and order of the silver oxide emulsion layer and the non-photosensitive layer.Typical examples include color photographic paper, color positive or negative film, color slide, or black and white photographic exposure using a dye image. It is particularly suitable for color photographic paper.Usually, most of the silver halide emulsion layer and non-photosensitive layer are hydrophilic colloid layers containing a hydrophilic binder. As the hydrophilic binder, gelatin or gelatin derivatives such as acylated gelatin, guanidylated gelatin, phenylcarbamylated gelatin, phthalated gelatin, cyanethanolated gelatin, and esterified gelatin are preferably used.

The magenta coupler according to the present invention and the cyan coupler according to the present invention can be prepared using the same methods as those used for ordinary magenta dye-forming couplers and cyan dye-forming couplers. A silver halide photographic material is formed by coating a support with a silver emulsion layer. This silver halide photographic material may be a single color silver halide photographic material or a multicolor silver halide photographic material. In the case of multicolor silver halide photographic materials, the magenta coupler and cyan coupler according to the present invention are:
Usually contained in a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, respectively, but silver halide sensitive to the three primary color regions of non-sensitized emulsions or streaks other than green or red. It may also be contained in the emulsion layer.

Each structural unit forming a dye image in the present invention is
The layer is a single pore emulsion layer or a multilayer emulsion layer that is sensitive to certain areas of the pattern.

When the magenta coupler and cyan coupler according to the present invention are added to a silver halide emulsion, it is usually about 0.1 to 2.0 mol, preferably 0.3 to 2.0 mol per mol of silver halide.
Add in a range of 1.0 mol.

When the silver halide photographic materials of the present invention are multicolor elements, the layers necessary for the photographic element, including the layers of image-forming units described above, can be arranged in various orders as known in the art. can do. A typical multicolor silver halide photographic light-sensitive material consists of a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having a cyan dye image-forming coupler (at least one cyan dye image-forming coupler). is a cyan coupler according to the present invention.

), a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer (at least one of the magenta dye image-forming couplers being a magenta coupler according to the invention); ), the yellow dye image-forming structural unit comprising at least one blue-sensitive silver halide emulsion layer having at least one yellow dye image-forming coupler is supported on a support.

The silver halide photographic material may have additional layers, such as non-photosensitive layers such as a filter layer, an intermediate layer, a protective layer, an antihalation layer, a subbing layer, an anticurl layer, etc.

The yellow dye image-forming couplers used in the present invention are:
Conventionally known ones may be used, for example, U.S. Pat. No. 2,778,
No. 658, No. 2,875,057, No. 2.908
, No. 573, No. 3,227,155, No. 3.22
No. 7,550, No. 3,253,924, No. 3.2
No. 65,506, No. 3,277.155, No. 3.
No. 341,331, No. 3,369,895, No. 3
．． No. 384,657, No. 3.40'8,194, No. 3.415,652, No. 3,447,928,
Same No. 3.551,155, No. 3,582,322, No. 3.725,072, No. 3,894,875
German Patent Publication No. 1,547,868
No. 2,057,941, No. 2,162,89
No. 9, No. 2,163,812, No. 2,213,4
No. 61, No. 2,219,917, No. 2,261,
No. 361, No. 2,263,875, Special Publication No. 1977-1
No. 3,576, JP-A-48-29,432, JP-A No. 48-
fi6,834, fi49-10,736, fi49-
Examples include those described in No. 122,335, No. 50-28,834, and No. 50-132,926.

Among these, pivaloylacetanilide 9-based yellow couplers are particularly preferably used.

These yellow dye-forming couplers and magenta dye-forming couplers are usually contained in the silver halide emulsion layer in an amount of about 0.1 to 2.0 mol per mol of silver halide.

Next, typical examples of yellow dye image-forming couplers preferably used in the present invention will be listed, but the invention is not limited thereto.

Yellow coupler (Y-1) α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)-ethoxycarbonyl]-acetanilide 9° (Y-2) α-benzoyl-2-chloro-5-[γ -(2゜4-:
)-t-amylphenoxy)-butyramidecyacetanilide.

(Y-3) α-hyhalylα-(4-(4-benzyloxyphenylsulfonyl)-phenoxy)-2-10rho5-[γ
-(2,4-di-t-amylphenoxy)-butyramide]acetanilide.

(Y-4) α-(2-methoxybenzoyl)-α-(4-acetoxyphenoxy)-4-chloro-2-(4-1-octylphenoxy)-acetanilide.

(Y-5) α-biparyl α-(3,3-:,)brole-2,4
-thioxoacetidin-1-yl)-2-chloro-5
-[α-(F'7'Syloxycarbonyl)-ethoxycarbonylcyacetanilide.

(Y-6) α-)i” Halyl α-(3-tetradecyl-1-succinimide)acetanilide.

(Y-7) α-(4,-)”7’Syloxyxnzoyl)-α-(
3-methoxy-1-succinimit'') -3,5
-dicarboxyacetanilide-dipotassium salt.

(Y-8) α-Hyvalyl α-phthalimy-2-chloro-5-
[γ-2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-9) α-2-furyl-α-phthalimide e-2-chloro5
-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-10) α-phthalimide 9-α-bivalyl 2-methoxy 4
-((N-methyl-N-octadecyl)-sulfamoyl]-acetanily-0 (Y-1,1) α-(3-octadecyl-1-succinimide)-α-
Pro-R neuroacetanilide.

(Y-12) α-(2,6-di-oxo-3-〇-propyl♂ is lysin-1-yl)-α-bivalyl-2-chloro5-[
γ-(2,4-di-t-amylphenoxy)butylcarbamoyl]acetanilide.

(Y-13) α-(1-4-2,4-dioxo-imidazolidin-3-yl)-α-hyhalyl-2-chloro-5-[γ
-(2,4-:)-t-amylphenoxy)butyramide]acetaniliP0 (Y-14) α-(3,3-:)methyl-1-succinimit9)-
α-pivalyl-2-chloro-5-[α-(2,4-di-
t-amylphenoxy)butylamide)” :] -acetanilide.

(Y-15) α-(5-benzyl-2,4]dioxo-3-oxazoyl)-α-pivalyl-2-chloro5-[γ-(2,
4-:)-t-amylphenoxylbutyramide 9]
-acetanilide.

(Y-16) α-(5,5-dimethyl-2,4-:)oxo-3-oxasoyl)-α-hyalovalyl-2-chloro5-[α
-(2,4-di-t-amylphenoxy)-butyramidecyacetanilide.

(Y-17) α-(3,5-)oxo-4-oxazinyl)-α-piparyl-2-chloro5-[γ-(2,4-di-t-amylphenoxy)-butyramidecyacetanilide.

(Y-18) α-[4,5-dichloro-3(2H)-pyridazone-2
-Irku α-benzoyl-2-chloro-5-[α-(
dodecyloxycarbonyl)-ethoxycarbonylcyacetanilide.

(Y-19) 4.4'-di(acetoacetamino)-3,3-dimethyldiphenylmethane.

Hydrophobicity of cyan dye image-forming couplers including the cyan coupler of the present invention, magenta dye image-forming couplers including the magenta coupler of the present invention, yellow dye image-forming cazolers, or photographic additives such as ultraviolet absorbers described below. The additives are dispersed in a hydrophilic binder aqueous solution according to a conventionally known method and then incorporated into the silver halide emulsion layer or the non-photosensitive layer. As a method for dispersing these hydrophobic compounds, for example, Japanese Patent Application Laid-Open No. 49-74
No. 538, No. 51-59943, No. 54-32552
Sekiyo Bulletin, Research Disclosure Magazine, 1976
The latex dispersion method or the oil-in-water dispersion method described in A14850, August 2013, pages 77-79, etc., can be used. As the oil-in-water type dispersion method, conventionally known methods for dispersing hydrophobic compounds such as couplers can be applied. Specifically, a hydrophobic compound is dissolved in a high boiling point organic solvent with a boiling point of 175C or higher and a low boiling point solvent such as ethyl acetate or butyl acetate added as necessary, and a hydrophilic compound such as gelatin containing a surfactant is dissolved. The mixture is mixed with an aqueous solution containing a photosensitive binder, emulsified and dispersed using a dispersion means such as a high-speed rotating mixer, a colloid mill, or an ultrasonic dispersion device, and then mixed into a hydrophilic colloid layer such as a silver emulsion layer or a non-photosensitive layer. Contain. The high boiling point organic solvent used for this removal is as follows:
9 organic acid amides, carbamates, esters, ketones, urea derivatives, etc., especially dimethyl phthalate, diethyl phthalate), 9-probyl phthalate), -i-tylphthalate, -), 9-n-octyl Phthalate, phthalate esters such as diisooctyl phthalate, cyamyl phthalate, dinonyl phthalate, diisodecyl phthalate, tricresyl phosphate, triphenyl phosphate, )IJ-(2-ethylhexyl) phosphate, trisononyl phosphate, etc. phosphoric acid esters of One or more phenol derivatives such as ester, succinate, maleate, phthalate, citric acid ester, )-tert-amylphenol, n-octylphenol, etc. can be used in combination.

The silver halide used in the silver halide emulsion used in the present invention includes any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver chlorobromide, and silver chloroiodobromide. It will be done. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide.

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of the (100) plane to the (111) plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Furthermore, these silver halides may be produced by any of the neutral method, ammonia method, and acidic method, and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, conversion method, etc. Manufactured silver halide grains are also applicable.

It is preferable that soluble salts are removed from the silver halide emulsions used in the silver halide photographic materials according to the present invention, but those in which soluble salts are not removed can also be used. It is also possible to use a mixture of two or more silver halogenide emulsions prepared separately.

A silver halide photographic emulsion in which silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, nogradium, iridium, and platinum can be used.

In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can also be used together.

As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds can be used.

As selenium sensitizers, active and inactive selenium compounds can be used.

Examples of reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfite 9, silane compounds, iminoaminomethanesulfinic acid, human 9 radinium salts, and hydrazine derivatives.

The silver halide according to the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
No. 270,378, No. 2,442,710, No. 2
, 454,620 and 2,776,280 can be cited as typical examples.

The silver halide emulsion layer and non-photosensitive layer of the silver halide photographic light-sensitive material according to the present invention may contain various other photographic additives. For example, antifoggants, dye image fading inhibitors, color stain inhibitors, fluorescent whitening agents, 1F agents for charging, hardeners, surfactants, and plasticizers are described in Research Disclosure No. 1.7643. , wetting agents, ultraviolet absorbers, and the like can be used as appropriate.

In the silver halide photographic light-sensitive material according to the present invention, each constituent layer such as an emulsion layer and a non-photosensitive layer containing various photographic additives as described above is subjected to corona discharge treatment,
It is produced by coating on a support that has been subjected to flame treatment or ultraviolet irradiation treatment, or by coating it on the support through a subbing layer or an intermediate layer. Advantageously used supports include:
For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflector, such as glass plates, polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films. , polycarbonate film, polystyrene film, etc.
These supports 59- are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. It is also possible to simultaneously coat two or more layers by the methods described in U.S. Pat. No. 2,761,791 and U.S. Pat. No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily, but for example, the blue-sensitive emulsion layer, the blue-sensitive emulsion layer,
The arrangement may be a green-sensitive emulsion layer, a red-sensitive emulsion layer, or a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer sequentially from the support side.

In the dye image forming method of the present invention, the pH of the final processing solution used for color development is 2.0 to 6.5. Here, the final processing solution usually refers to the final processing solution used for color development. Refers to the processing solution used in the final processing step of each processing step including the color development that constitutes the color development processing according to the present invention, and pH -6〇- refers to the hydrogen ion concentration of this processing solution. (H”).

In addition to the color development described above, the color development treatment according to the present invention includes appropriate processing steps such as bleaching, fixing or bleach-fixing, stabilization, hardening, neutralization, black and white development, reversal, stopping, washing, and rinsing. Can be implemented in combination. Preferably, the color development treatment according to the present invention includes, for example, the following (1) to
Each of these processes is composed of a series of continuous processing steps, as illustrated in (7).

(1) Color development - bleach fixing - 1 (2) Color development - bleach fixing - m (3) Color development - bleach fixing - one water wash - ffl (4) Color development - bleach fixing - water washing - m (5) Color development Development - washing with water, bleaching, washing with constant water, color development (6) Color development - washing with water, bleaching, washing with water, constant coloring, washing with water, color development with water, color development - washing with water, washing with water, reversing, color development, bleaching, constant coloring with water, 1 The processing step surrounded by the water washing area [decoy] in each of the color development treatments (1) to (7) above is the final treatment step, and in each of the color development treatments (1) to (7) above. In this case, the stabilization step is the final treatment step, and in this case, the pH of the treatment liquid used in the stabilization step (hereinafter referred to as stabilization bath) is 2.0 to 6.
5, preferably 3.0 to 5.5.

Such a stabilizing bath can be used as long as it is a buffer solution whose pH is adjusted to a range of 2.0 to 6.5, and various buffers can be used. acid salt, borax, phosphate, monocarboxylate, dicarboxylate, polycarboxylate, oxycarboxylate,
Examples include amino acids, aminocarboxylate salts, primary phosphates, secondary phosphates, tertiary phosphates, sodium hydroxide, potassium hydroxide, and the like. Furthermore, various chelating agents can be added in the same manner, and specific examples of the chelating agents include aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, alkylidenephosphonic acid, polyphosphate, and birophosphate. , metaphosphoric acid, and gluconate. In addition, commonly used additives such as a fluorescent brightener, a surfactant, an inhibitor, a second agent, a preservative, an organic sulfur compound, an onium salt, a hardening agent, and various metal salts can be added.

Although this stabilization step can be carried out using a single stabilizing bath, it is preferably carried out using a treatment bath composed of multiple baths. In this case, the silver halide photographic material being conveyed is replenished in a certain amount per unit area from the latter processing bath, and the overflow liquid generated by the replenishment of the latter bath is sequentially introduced into the earlier bath. By using the (backflow) method, the later the stabilizing bath is, the less likely it is to be contaminated by the stabilizing bath, fixing, or processing solution used for bleach-fixing. As a result, the stability of the dye image during storage is improved without a water washing process, and at the same time, silver is recovered from the stabilizing bath flowing from the first stage column and the pollution load is harmless. can be efficiently carried out. When using such a multistage countercurrent stabilizing bath, the pH of the final bath should be at least 2.0 to 6.5.
, preferably 3.0 to 5.5. In addition, the number of tanks used in a multi-stage countercurrent stabilization bath is closely related to the relationship between the amount of fixing or bleach-fixing solution brought in by the silver halide photographic material being processed and the amount of replenishment of the stabilizing bath. Therefore, the smaller the ratio of the amount of replenishment to the amount brought in, the more tanks are required.

Generally, when the amount of replenishment is 3 to 5 times the amount brought in, stabilization using 9 to 10 tanks is required, and when the amount is 50 times, treatment using 3 to 4 tanks is sufficient. Processing temperature is 15-6
0C1 is preferably in the range of 20 to 45C.

In addition, from the viewpoint of rapid processing, a short treatment time is preferable, but usually 20 seconds to 10 minutes, more preferably 1 to 5 minutes. is preferably long.

The color developing agents used for color development in the color development process according to the present invention include p-amine phenol, p-
Any aromatic primary amine color developing agent can be used, such as phenylene diamine or p-sulfonamide 9-aniline. For example, 3-acetamido-4-
Amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylanilic acid m
, N, N-diethyl-P-phenylenediamine, 2
-aminotoluene, N-ethyl-N-(β-methanesulfonamihiethyl)-3-methyl-4-aminoaniline, 4-amino-N-ethyl-3
-Methyl-N-(β-sulfoethyl)aniline, 2-methoxy-4-phenylsulfonamide aniline, 2.6
-1 promoter 4-amine phenol and the like. Other useful typical color developing agents are found in Meese and James, The Theory of the Photographic Process, 3rd edition, 1966, Macmillan Company, New York, pp. 278-311, U.S. Pat. No. 3,813,244 and No. 3,791,827
You can refer to the specification of No. Aromatic primary amine color developing agents that give particularly good results in the present invention include 4-amino-N,N-diethylaniline hydrochloride, 4-amino-N,N-diethylaniline hydrochloride,
-amino-3-methyl-N.

N-1 ethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamivinityl)aniline sulfate hydrate 9ate, 4-amino-
3-Methyl-N-ethyl-N-β-human 90xyethylaniline sulfate, 4-amino-3-dimethylamine-N
, Nt ethylaniline sulfate hydrate, 4
-Amino-3-methoxy-N-ethyl-N-β-hydroxyethylaniline hydrochloride, 4-amino-3-(β-methanesulfonamidoethyl)-N,N-4ethylaniline dihydrochloride and 4-amino -N-ethyl-N-(2
-methoxyethyl)-m-toluidine 2P-)luenesulfonate.

These color developing agents may be contained in advance in the silver halide photographic light-sensitive material according to the present invention, either as the color developing agent itself or as its precursor.

Color developing agent precursors are compounds that can produce color developing agents under alkaline conditions, and include Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, phthalic acid imide 8 derivative precursors, and phosphoric acid amide 9 derivatives. Precursor, Sugar.

Examples include amine reactant precursors and urethane type precursors. Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat.
No. 2,507,114, No. 2.695,2
No. 34, No. 3,719,492, British Patent No. 803
, 783 specification, Japanese Patent Application Laid-open Nos. 135,628/1983, and 79,035/1984, Research Disclosure Magazine Nos. 15,159, 12,146, and 13
, No. 924. In this case, the color developing solution according to the present invention used for color developing the silver halide photographic light-sensitive material containing a color developing agent or its precursor may be a conventionally known alkaline processing solution (
What is called an activation bath or activator liquid. ) is used.

These aromatic primary amine color developing agents or their precursors need to be added in an amount that will provide sufficient color development during color development processing.

This amount varies depending on the type of silver halide photographic light-sensitive material, etc., but it is approximately 0 per mol of photosensitive silver halide.
．． The amount used is between 1 mol and 5 mol, preferably between 0.5 mol and 3 mol. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a silver halide photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc. and added. It can be added as an emulsified dispersion using a high boiling point organic solvent such as phate, or as a latex polymer impregnated as described in Research Disclosure No. 14850.

In addition to the above-mentioned aromatic primary amine color developing agent, the color developing solution used in the present invention contains alkali agents such as sodium hydroxide, potassium hydroxide, potassium carbonate, trisium phosphate, and boric acid. , pH buffering agents such as acetic acid, known development accelerators such as thioethers, 1-aryl-3-virazolitonones, N-methyl-p-aminophenols, polyalkylene glycols, hensyl alcohol, ethanol, phthanol. , various organic solvents such as ethylene glycol, diethylene glycol, acetone, N,N-dimethylformamide, development inhibitors such as nitro-nitzimidazole, preservatives such as sulfites, hydroxylamine, glucose, alkanols, amines, and phosphoric acid. Compound,
A water softener such as nitrilotriacetic acid is included as necessary.

The pH value of the color developer according to the invention is usually 7 or higher, most commonly about 9.5 to about 13.

■Specific Effects of the Invention According to the present invention, it is possible not only to satisfactorily prevent optical color contamination caused by unreacted magenta couplers, but also to
It is possible to form a cyan dye image that is excellent in both bright color properties and dark fading properties. Such specific effects of the present invention were completely unexpected in the past,
This was achieved for the first time by the dye image forming method of the present invention.

As described above, the method for forming a dye image of the present invention prevents photoresist staining during storage of dye images and unexposed areas obtained by color development processing of silver halide photographic light-sensitive materials, and also prevents staining of dye images during storage. This is a method that can improve the storage stability in a well-balanced manner.

(2) Specific Examples of the Invention The present invention will be explained in more detail with reference to specific examples below, but the embodiments of the present invention are not limited thereto.

Example 1 On a support made of polyethylene-coated paper, the following layers were sequentially coated from the support side to prepare a color photographic material, which was designated as Sample 1.

1st layer... The above exemplary yellow coupler (Y-13) was used as a yellow coupler at 0.85'/m", 3.5-N
)-t-butyl-4-hydroxy-benzoic acid-2-4-
G T-Amirou Hueni # 0.3 f/rr? , dioctyl phthalate) 0.35'/m", 2.4-di-
Octyl-hydroquinone 23■/lr? , blue-sensitive silver chlorobromide emulsion (in terms of silver) 0.4P/lr? , gelatin was applied at a rate of 1.6 t/ltl.

2nd layer... 2;4-) Octyl-hydroquinone at 75rv/prz, diisodecyl phthalate at 50ml, 4.4'-di(2-phenylamino-4=(sodium 4-sulfonate-phenylamino)) -triazinyl-6-amine)stilbene-2,2'-)sodium sulfonate at 12 m9/rr? , gelatin was coated to a thickness of 0.41 cm.

Third layer...the above-mentioned magenta coupler according to the present invention (
8) at 0.38 r/m', green-sensitive silver chlorobromide emulsion (in terms of silver) 34WT9/m', 1,4-di-octoxy-2,5-di-t-amyl-benzene at 0 .15r/W
? , gelatin 1.6? The coating was applied so that the coating amount was as follows.

4th layer...2-(guhydroxy-3',5'-di(-amyl)-phenyl)-incitriazole 3
504 rin, 2-(2'-human90ki71-c3',5'-di(t-butyl)-phenyl)-incitriazole at 350 m9/m', gelatin at 1
．． 4 fly? The coating was applied so that the coating amount was as follows.

Fifth layer: 350 m9/rr of the above exemplary cyan coupler (c) according to the present invention? , Red-sensitive silver halide emulsion was coated with silver amount of 500~/-, gelatin was coated with 1.75'/lr? It was painted so that

6th layer...2-(2'-hydroxy-3',5'-di(amyl)-phenyl)-benzotriazole at 150 my/n? , 2-(2'-hydroxy-3'
, 5'-di(t-butyl)-phenyl)-benzotriazole at 150 Tri/rr? , gelatin 0.6
P/W? It was painted so that

Seventh layer: Gelatin was coated at a coating density of 0.9 r/-.

Next, the coupler of the fifth layer was the same as that of Sample No. 1, except that the illustrative cyan coupler according to the present invention shown in Table 1 below and the comparative coupler 72- below were used in place of the coupler in Sample 1. Samples 2 to 4 were created.

The sample prepared as described above was exposed to red light through a light wedge using a sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd., model KS-7), and then subjected to color development treatment according to the processing steps below. Each cyan dye image was obtained. Note that the pH of the final stabilizing bath is 7.0.6.5.4.0.2.
The test was carried out for 0.1.0. An image storage stability test was conducted on the obtained cyan dye image sample in the following manner.

(1) Unexposed samples (white samples) of yellow stain samples 1 to 4 were stored in a dark place at 70C1 relative humidity of 80 parts for one week, and the increase in blue light absorbance was measured.

(11) Dark fading The change in density of a cyan dye image in a portion with an initial density of 1.0 after storage for 2 weeks at 77υ in a dark place was measured.

The results of each of the above tests are summarized in Table 1.

<Processing steps> 1. Color development 33C 3 minutes 30 seconds 2. Bleach fixing 33C 1 minute 30 seconds 3. Stabilization treatment 25r~30C 3 minutes 4, dry
Drying: Approximately 2 minutes at 75C to 80C <Processing liquid composition> A Color developer Benzyl alcohol 15 mA' Ethylene glycol 15 Potassium sulfite
2.01 Potassium Bromide
0.72 Sodium chloride 0
．． 22 Potassium carbonate 30. Or hydroxylamine sulfate 3. Of polyphosphoric acid (TPPS) 2.5
5'3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamide 9ethyl)-aniline sulfate 5.52 Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1 ．． or potassium hydroxide
2.0? Add water II! shall be.

B Bleach-fix solution ethylenediaminetetraacetic acid ferric ammonium dihydrate 601F ethylenediaminetetraacetic acid 3y ammonium thiosulfate (
701 solution) 100m/ammonium sulfite (4
0 coefficient solution) 27.5[/Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.

C stabilization bath glacial acetic acid 2*/boric acid
52 benzoic acid o, 52 with water 11
Then, adjust pl-1 to 7.0°6.5.4 with sodium hydroxide.
．． It was adjusted to 0.2°0.1.0.

Margin below = 75 - Table 1 76 - Comparative Cyan Coupler As is clear from Table 1, in Sample 4 using the comparative cyan coupler, when the pH of the stabilizing solution was lowered, the yellow stain decreased, but the dark fading property was low. On the other hand, it can be seen that in Samples 1 to 3, the generation of yellow stain can be prevented by lowering the pH of the stabilizing liquid without deteriorating the fading property.

Example 2 It has the same layer structure as Sample 1 in Example 1, except that magenta coupler (2), +91. (Sample 5 using lυ
．． 6.7, and a sample 8 using a comparative magenta coupler was exposed and developed in the same manner as in Example 1.

However, the pH of the stabilizing bath was 4.0. These samples were measured in the same manner as in Example 1 for the occurrence of yellow stains and the fading resistance of cyan dye images.

The results are shown in Table 2.

Comparative magenta coupler As is clear from Table 2, sample 8 using the comparative magenta coupler has a lot of yellow stain, but samples 5 to 7 of the present invention have less yellow stain and good fading resistance. .

Example 3 Sample 2, Sample 4, and Sample 8 of Example 1 were developed by the following processing method. An automatic developing machine was filled with the same color developing solution, bleach-fixing solution, and stabilizing bath as in Example 1, and the stabilization processing bath was used for one tank and six tanks, and for comparison, a conventional stabilizing bath was used instead of the stabilizing bath. This was carried out for those having a water washing (PL(7) treatment step.For those in which the stabilization treatment step was divided into 6 tanks, the stabilization treatment baths were arranged in the direction of flow of the silver halide photographic light-sensitive material from the first tank to The sixth tank is a stabilizing tank, and each tank is replenished from the final tank.
A multi-stage countercurrent system was adopted in which the overflow from the final tank flows into the previous stage tank, and this overflow liquid also flows into the previous stage tank.

The treatment temperature and treatment time of each treatment step were as follows.

Processing temperature Processing time 1, color development 33C 3 minutes 30 seconds 2, bleach fixing 33C 1 minute 30 seconds 3, stabilization 25'C to 30'C 3 minutes 4,
Dry? I'~80tZ' 2 minutes 79- The pH of the stabilizing solution in the stabilization treatment bath was measured, and the sample obtained after the treatment was examined for yellow stain, dark fading resistance, and light resistance in the same manner as in Example 1. In addition, the fading properties of magenta dye images and yellow dye images were also investigated. The results are shown in Table 3.

Margin 80 - As is clear from Table 3, in the samples obtained by the processing method of the present invention, the occurrence of yellow stains can be reduced without deteriorating the fading resistance of cyan dye images.

Furthermore, when stored in a dark place, the fading balance of cyan, magenta, and yellow is good, and yellow staining is less likely to occur.

In the sample obtained by the method of the present invention, when stored in the dark, the black part does not change color to brown, the green part does not change to yellow-green, or the white part does not change to yellow, and it remains sharp for a long period of time. You can maintain a clear image.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Representative Patent Attorney Ichinose Miyao Procedural Amendment (
Spontaneous) o5(5・”)'q” El Director General of the Patent Office Kazuo Wakasugi 1981 Patent Application No. 60361 2, Title of invention Method for forming a dye image 3, Relationship with the case of the person making the amendment Patent applicant residence Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo
Name (127) Roku Konishi Photo Industry Co., Ltd. 8, Contents of the amendment (1) Deleted "Although it is possible to carry out the process using one stabilizing bath" on page 64, lines 6-7 of the specification cylinder.

(2) On page 77, line 8 of the specification, "preferable" is changed to "although necessary."

(3) Table 1 on page 77 of the specification is replaced with Table 1 on Attachment 10.

(4) Replace Table 2 on page 79 of the specification with Table 2 on Attachment 20.

(5) "Sample of the present invention" on page 79 of the specification, lines 4-3 from the bottom is defined as "sample using the magenta coupler of the present invention."

(6) Attachment 3 in front of “of the present invention” on page 83 of the specification cylinder, line 8
Insert Example 4.

Above (Attachment 1) Table 1 (Attachment 2) Table 2 Below margins (Attachment 3) Example 4 Samples 1, 3 and 8 of Example 1 were developed by the following processing method. An automatic developing machine filled with the same color developing solution and bleach-fixing solution as in Example 1, one stabilization treatment bath filled with Example 10 stabilization bath (pH 4,0), stabilization treatment A bathtub with 6 tanks is refilled with replenishing liquid from the final tank, and the overflow liquid from the final tank is also flowed into the previous tank, using a multi-stage countercurrent system.For comparison, a bathtub with 6 stabilization treatment tanks The treatment was carried out on the samples that were supplemented with water from the final tank.

The pH of the final stabilization treatment bath was measured, and the sample obtained after treatment was examined for yellow stain and dark fading in the same manner as in Example 1. The results are shown in Table 4.

As is clear from Margin Table 4 below, in the samples obtained by the processing method of the present invention, the occurrence of yellow stains can be reduced without deteriorating the fading resistance of cyan dye images. Furthermore, a multi-stage countercurrent stabilizing bath produces fewer yellow stains than a single-bath stabilizing bath, and provides better image storage stability. In addition, in the samples obtained by the method of the present invention, especially the samples obtained by multistage countercurrent stabilization bath treatment, the white part does not turn yellow, the black part turns brown, and the green part turns yellowish-green. It can maintain clear images for a long time without discoloration.

that's all (3)

Claims (1)

[Scope of Claims] After imagewise exposure of a silver halide photographic material having a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support, the silver halide In the method of forming a dye image by subjecting a photographic light-sensitive material to a color development process including color development, the magenta coupler is at least one selected from anilino-type magenta couplers, and the cyan coupler is represented by the following general formula [11 A method for forming a dye image, characterized in that the pH of the final processing solution used in the color development treatment is at least one of the cyan couplers represented by the above general formula: 2.0 to 6.5. (+1.□ (In the formula, R1 represents an alkyl group, an aryl group, an alkylamino group, an arylamino group, or a heterocyclic group. R2
represents an alkyl group, an aryl group, an alkylamino group, an arylamino group or a heterocyclic group. Also, R2 is R3
may be linked with the general formula [6-membered heterocycle fused to the phenol ring in the mouth]. R3 is a hydrogen atom or ](
- R3, which represents an atom atom, may be linked with R2 to form a 6-membered compound ring condensed to the phenol ring in the general formula [11]. zl represents a hydrogen atom or a group that can be separated from the cyan coupler represented by the general formula [11] by the reaction between the cyan coupler represented by the general formula [1] and the oxidized product of the color developing agent. )