JPS62196657A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the dark color fading property and lightfastness of a cyan dye image by incorporating specific cyan couplers and compd. into a silver halide emulsion layer. CONSTITUTION:The cyan coupler expressed by formula I, the cyan coupler expressed by formula II and the compd. expressed by formula III are incorporated in the form of oil drops into the silver halide emulsion layer. In formulas, R4, R5 denote an alkyl group, etc., R6 denotes a hydrogen atom, etc., R7-R10 denote a hydrogen atom, halogen atom, etc. The cyan coupler expressed by formula I and the cyan coupler expressed by formula II are generally added to the emulsion layer in a 1X10<-2>-8X10<-1>mol range in total of both the couplers per mol of the silver halide. The compd. expressed by formula III Is used preferably at 1-1,000pts.wt., more particularly preferably 5-200pts.wt. per 100pts.wt. in total the cyan coupler expressed by formula I and cyan coupler expressed by formula II. The dark color fading property and lightfastness of the cyan dye image are thereby improved.

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which the fastness of a cyan dye image is improved. This invention relates to a silver halide photographic material which also has extremely excellent fastness. [Background of the Invention] In order to form a dye image using a silver halide photographic light-sensitive material, an aromatic primary amine color developing agent is usually used to develop the silver halide in the exposed silver halide photographic light-sensitive material. When the grains are reduced, they are themselves oxidized, and this oxidized product reacts with a coupler previously contained in the silver halide photographic light-sensitive material to form a dye. Generally, three types of couplers are used that form three dyes, yellow, magenta, and cyan, in order to perform color reproduction by the subtractive color method. Each coupler is usually dissolved in a substantially water-insoluble high-boiling organic solvent or in this solvent, if necessary, in combination with an auxiliary solvent, and added to the silver halide emulsion. The basic properties required of each coupler are firstly high solubility in high-boiling organic solvents, good dispersibility and dispersion stability in silver halide emulsions, and not easy precipitation, and spectral absorption properties. Examples include that a clear dye image with good color tone and a wide color reproduction gamut is formed, and that the dye image formed has fastness to light, heat, moisture, etc. In particular, for couplers used in color print materials, it is desirable to improve both the light fastness and dark storage stability (dark fading resistance) of the resulting dye image as much as possible due to the mission of preserving photographic images. . As the above-mentioned cyan coupler with improved dark fading property, the phenol 2- and 5-positions are substituted with acylamino groups.
, 5-diacylaminophenol cyan couplers are known, for example, U.S. Pat.
No. 9630 and No. 55-163537. However, although these 2,5-diacylaminophenol-based cyan couplers have significantly improved dark fading resistance of the resulting cyan dye images, many of them are significantly inferior in light fastness. Techniques for improving the light fastness of the aforementioned 2,5-diacylaminophenol cyan coupler are also known, such as the method described in Japanese Patent Application No. 59-79947. However, although this technique certainly improves light fastness, the degree of improvement is not only insufficient, but it also has the disadvantage of lowering color development. On the other hand, conventionally known 2-acylaminophenol-based cyan couplers have very low dark fading, but generally have high light fastness, so there is no technology to improve dark fading using this type of cyan coupler. Proposed. For example, dye image stabilizers described in JP-A-50-151149 and JP-A-54-48535, and JP-A-54
-104339 and U.S. Patent No. 4.540.657
Examples include techniques using high boiling point organic solvents as described in No. Specification S and the like. However, in order to obtain a certain degree of improvement effect, the dye image stabilizer generally causes precipitation of the coupler dispersion and a significant decrease in color development, which causes problems in manufacturing and other photographic performance. Ta. In the case of the high boiling point organic solvents mentioned below, even when used frequently, not only the effect of improving dark fading resistance is completely insufficient, but also the light fastness deteriorates significantly depending on the coupler used. That is, at present, no means has been found for simultaneously significantly improving the dark fading resistance and the light fastness of the cyan° dye image formed, and its development has been strongly desired. [Object of the Invention] The object of the present invention is to provide a silver halide photographic light-sensitive material in which the dark fading resistance and light fastness of cyan dye images formed without adversely affecting other photographic properties are simultaneously greatly improved. It is to provide. [Structure of the Invention] The present inventors have conducted intensive research in view of the above-mentioned current situation, and have found that the above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having a silver halide emulsion layer of at least 1 m long on a support.
At least one of the silver halide emulsion layers includes a cyan coupler represented by the following general formula [I] and a cyan coupler represented by the following general formula [I].
II] and the cyan coupler represented by the following general formula [
It has been found that the present invention can be achieved by using a silver halide photographic material containing the compound represented by 1[[ ] as oil droplets. General Formula [I] [Wherein R1 represents an alkyl group, an aryl group, a cycloalkyl group or a heterocyclic group. R2 represents an alkyl group or an aryl group. R3 is a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group. zl represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] General formula [I[] In the formula, R4 represents an alkyl group or an aryl group. R
5 represents an alkyl group. R6 represents a hydrogen atom, a halogen atom or an alkyl group. z2 is t! due to reaction with a hydrogen atom or an oxidized product of an aromatic primary amine color developing agent. Lfl12 represents a group that can be obtained. General formula [I[[] ~ Represents a simple bond or atomic group necessary to form a 6-membered ring. R7, R8, R9 and Rh. are hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxycarbonyl group, respectively.
It represents an alkylcarbamoyl group, an arylcarbamoyl group, an acyl group or a cyano group. Any two selected from Ry, Ra, Rs and Rto may be combined to form a ring, R7, R8,
'At least one selected from R9 and Rho may combine with the atomic group represented by Q to form a ring. ] [Specific structure of the invention] The cyan coupler represented by the general formula [I] will be explained. The alkyl group represented by R1 in the general formula [I] is, for example, a methyl group, an ethyl group, a butyl group, a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, or the like. The aryl group represented by R1 is, for example, a phenyl group, a naphthyl group, etc., and preferably a phenyl group. R1
The heterocyclic group represented by is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R1 is, for example, a cyclopropyl group or a cyclohexyl group. Each of these groups represented by R1 includes those having a single or multiple substituents. For example, typical substituents introduced into an aryl group include a halogen atom (for example, an atom such as fluorine, chlorine, or bromine). ), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, Siam L nitro group, carboxyl group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), aryloxy group ( (e.g., phenoxy group, etc.), alkylsulfonyl group (e.g., butylsulfonyl group, etc.), arylsulfonyl group (e.g., phenylsulfonyl group, etc.)
, alkylsulfonamide groups (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide groups (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl!
! (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.),
Alkyloxycarbonyl groups (e.g., methyloxycarbonyl groups, etc.), aryloxycarbonyl groups (e.g., phenyloxycarbonyl groups, etc.), aminosulfonamide groups (e.g., N.N-dimedylaminosulfonamide groups, etc.), acylamino groups (e.g., acetyl (amino group, etc.), acyl group (e.g., acetyl group, etc.), alkylcarbamoyl group (e.g., methylcarbamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), and the alkyl group represented by R1, cyclo The substituents introduced into the alkyl group and the heterocyclic group may also be the same as those mentioned above. Preferred groups represented by R1 include a phenyl group or a halogen atom, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, or a cyano group. It is a phenyl group having as a substituent. The alkyl group represented by R2 is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, octyl group, tridecyl group, and the like. The aryl group represented by R2 is, for example, a phenyl group or a naphthyl group. Each of these groups represented by R2 includes those having a substituent, and examples of the substituent to be introduced include the same substituents as those introduced into the group represented by R1 described above. The halogen atom represented by R3 is, for example, each atom such as fluorine, chlorine, or bromine; the alkyl group is, for example, a methyl group, ethyl group, propyl group, butyl group, or dooracyl group; and the alkoxy group is , for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc. R
3 is preferably a hydrogen atom or a halogen atom, particularly preferably a hydrogen atom. Typical groups that can be separated by reaction with the oxidized product of the aromatic primary amine color developing agent represented by Zl include, for example, a halogen atom, an alkoxy group, an aryloxy group, an arylazo group, a thioether, and a carbamoyl group. A particularly preferred example of oZ+ is a hydrogen atom or a chlorine atom, including an oxyoxy group, an imido group, a sulfonamide group, a thiocyano group, or a heterocyclic group (eg, oxasilyl, diazolyl, triazolyl, tetrazolyl, etc.). In the present invention, preferred cyan couplers represented by the general formula [I] are compounds represented by the following general formula [I]. Zl/ In the general formula [1'], R11 represents an alkyl group or an aryl group. Alkyl groups or aryl groups include those having single or multiple substituents, and typical examples of these substituents include halogen atoms (e.g. atoms such as fluorine, chlorine, and bromine), hydroxyl groups, carboxyl groups, Alkyl! l (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), cyan group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), aryloxy group (e.g.) engineered ), alkylsulfonamide groups (e.g., methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide groups (e.g., phenylsulfonamide group, naphdylsulfonamide group, etc.), alkylsulfamoyl groups (e.g., butylsulfonamide group, etc.), famoyl group, etc.), arylsulfamoyl N (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide groups (e.g. dimethylaminosulfonamide group etc.),
Alkylsulfonyl group (e.g. butylsulfonyl group, etc.)
, arylsulfonyl group (e.g. phenylsulfonyl group, etc.), acyl group (e.g. acetyl group, phenylcarbonyl group, etc.), aminocarbonylamide group (e.g. dimethylaminocarbonylamide group, etc.), carbamoyl group (e.g. methylcarbamoyl group, phenylcarbamoyl group) etc)
, sulfinyl group, etc. Preferred groups represented by Ru are an alkyl group when nl-0 and an aryl group when nl = 1 or more. A more preferable group represented by R11 is n
When t-0, an alkyl group having 1 to 22 carbon atoms excluding substituents (preferably a methyl group, an ethyl group, a propyl group,
butyl group, octyl group, dodecyl M), nl-1
In the above cases, a phenyl group or an alkyl group (preferably a t-butyl group,

[-amyl group, octyl group), alkylsulfonamide group (preferably butylsulfonamide group, octylsulfonamide group, dodecylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group), aminosulfonamide group ( Preferred is a phenyl group having one or more substituents (dimethylaminosulfonamide group), alkyloxycarbonylbutyloxycarbonyl group). R12 represents an alkylene group, preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. nl is O or a positive integer, preferably O or 1. X represents a divalent group, and examples of this divalent group include -〇-
, -CO-, -COO-, -OCO-, -SO2 NR
'-, -NR' 802 NR"-, -mo, -SO-
, -802-, etc. Here, R', R" represent an alkyl group, and R', R"
I+ also includes those having substituents. Preferably, X is 0-, -S-, -SO-, -SO2-. R'1% R'a and Z'1 have the same meanings as R1, R3 and zl in the general formula [I], respectively. Typical specific examples of the cyan coupler represented by the general formula [■] are shown below in the margins, but the invention is not limited to these. (to) C1□H25SO□■ C4H0(n) C4H0 (company) e4it9(2) ■-36 ■-39 t, :1゜M2stnl C4H, (company) ■-46 Below margin I ■-49 Next, the above general The cyan coupler represented by the formula [I[] will be explained. Examples of the alkyl group represented by R4 in the general formula [II] include methyl group, ethyl group, butyl group, hexyl group, tridecyl group, pentadecyl u1 heptadecyl group, and examples of the aryl group include phenyl group. Can be mentioned. The alkyl group and aryl group represented by R4 include those having a substituent, such as an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an acyl group, an ester group, a droxy group, a cyano group, Nitro group, carbamoyl group, carbonamide group,
Examples include an alkylthio group, an arylthio group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, and a halogen atom. R4 is preferably an alkyl group having 8 to 32 carbon atoms in total including substituents. The alkyl group represented by R5 preferably has 1 to 1 carbon atoms.
5 alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, amyl group). The halogen atom represented by R6 is, for example, a chlorine, bromine, or fluorine atom, and the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, or the like. R6 is preferably a chlorine atom. Typical groups that can be separated by reaction with the oxidized product of the aromatic primary amine color developing agent represented by Z2 include, for example, a halogen atom, an alkoxy group, an aryloxy group, an arylazo group, a thioether, and a carbamoyl group. Examples thereof include an oxyoxy group, an imide group, a sulfonamide group, a thiocyano group, and a heterocyclic group (eg, oxasilyl, diazolyl, triazolyl, tetrazolyl, etc.). A particularly preferred example of Z2 is a hydrogen atom or a chlorine atom. In the present invention, the cyan coupler represented by the general formula [U] is more preferably the following general formula % Formula % In the general formula [■'3 General formula [I'], R13 and R14 are the same or different, respectively. Hydrogen atoms, alkyl groups (e.g. methyl, ethyl, propyl, butyl, amyl, octyl, dodecyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, dodecyloxy, etc.), halogen It represents an atom (eg, an atom such as chlorine, bromine, or fluorine), an alkylsulfonamide group (eg, butylsulfonamide group, etc.), an alkylcarbonamide group (eg, methylcarbonamide group, etc.), a hydroxyl group, or a cyano group. The total number of carbon atoms in Ria and R14 is 8 to 1
6, more preferably R13 and R+4 are each a butyl group or an amyl group. is preferably a hydrogen atom, an ethyl group, or a butyl group. ml represents an integer of O to 2. R'5 and Z'2 have the same meanings as R5 and z2 in the general formula [[], respectively. Typical specific examples of the cyan coupler represented by the general formula [II] are shown below, but the invention is not limited to these.The following margins I [-1 n-2 ■-3 [-6 [-7 [- 8 ■-10 ■-11 ShiL ■-12 ■-13 ■-15 t ■-16 I [-19 ShiL ■-20 ■-21 J Below margin ■-27 LJ ■-33 E ■-36 ■- 37 Jj C!l Below margin o O(,l
(,10:
Engineering... # ■-48 l ■-49 ■-50 ■-51 ■-52 J ■-53 ■-54 ■-55 l ■-5 Nirara is British Patent No. 1.038.331, 543
, No. 040, Japanese Patent Publication No. 1973-36894, Japanese Patent Application Publication No. 1973-
No. 59838, No. 50-137137, No. 51-1
No. 46828, No. 53-105226, Zhou 54-
No. 115230, No. 56-29235, No. 56-1
No. 04333, No. 56-126833, No. 57-13
No. 3650, No. 57-155538, No. 57-204
No. 545, No. 58-118643, No. 59-3195
No. 3, No. 59-31954, No. 59-59656,
No. 59-124341, No. 59-166956,
U.S. Patent Nos. 2.369.929 and 2.423.7
No. 30, No. 2,434,272, No. 2,474,
No. 293, No. 2,698,794, No. 2,772,1
No. 62, No. 2,801.171, No. 2,895,8
No. 26, No. 3,253.924, No. 3.311,47
No. 6, No. 3.458.315, No. 3.476, 5
No. 63, No. 3,591.383, No. 3,737,31
No. 6, No. 3.758.308, No. 3,767.411
No. 3.772.002, No. 3.790.384, No. 3,880,661, No. 3.926.634,
4,004.929, 4,009,035,
4.012.258, 4,052,212,
4,124,396, 4,134,766, 4,138,258, 4,146,396,
4.149.886, 4,178°183,
4,205,990, 4.254,212,
No. 4,264,722, No. 4,288,532, No. 4,296.199, No. 4.296.200,
4,299,914, 4.333.999, 4.334.011, 4.386.155, 4
．． No. 401.752, No. 4,427.767, etc. The addition m of the cyan coupler represented by the general formula [I] and the cyan coupler represented by the general formula [II] is not limited, but generally the cyan coupler represented by the general formulas [I] and [II] is added per 11 moles of halogenated ff. The total amount of the cyan coupler represented by the general formula M] is preferably used in the range of 1 x 10-3 mol to 2 mol, and particularly preferably in the range of 1 x 10-2 mol to 8 x 10'' mol. [II
] When using a combination V of a cyan coupler represented by the formula [I], at least one of the cyan couplers represented by the general formula [I] and at least one of the cyan couplers represented by the general formula [II] They can be used in any combination in the formulation ω, but in such a way that the cyan coupler represented by the general formula [II] accounts for 30 to 99 mol%, more preferably 50 to 95 mol%, of all 1 of these cyan couplers. It is preferable to mix them. Next, the compound represented by the general formula [111] will be explained. In the general formula []11], among the groups represented by R7% Ra, Rs, and Rlo, examples of the halogen atom include atoms such as chlorine, bromine, and fluorine. The alkyl group may be linear or branched, and preferably has 1 to 40 carbon atoms including substituents! % (for example, methyl group, ethyl group, i-propyl group, 2-ethylhexyl group, lauryl group, stearyl group, etc.). This alkyl group includes those having a substituent, and in this case, the substituent is specifically a halogen atom (for example, an atom such as chlorine, bromine, or fluorine), an alkoxy group (for example, a methoxy group, a butoxy group, or a stearyl group). oxy group, etc.), aryl group (
(e.g., phenyl group, naphthyl group, etc.), aryloxy group (e.g., phenoxy group, etc.), arylthio group (e.g., phenylthio group, etc.), aralkylthio group (e.g., benzylthio group, etc.), amino group (e.g., piperidino group, dimethylamino group, etc.) , acyloxy group (e.g. acetoxy group,
benzoyloxy group, furanoyloxy group, cyclohexanoyloxy group, etc.), alkoxycarbonyl group (e.g., butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc.), cycloalkoxycarbonyl group (e.g., cyclohexyloxycarbonyl group, etc.) ), aryloxycarbonyl group (e.g. phenoxycarbonyl group, etc.)
, oxalyloxy group (for example, ethoxyoxalyloxy group, etc.), carbamoyloxy group (for example, hexylcarbamoyloxy group, etc.), sulfonyloxy group (for example, phenylsulfonyloxy group, etc.), amide group (for example, benzoylamino group, etc.), ureido group ( For example, phenylureido group, etc.), aminosulfamoyl group (eg, dimethylaminosulfamoyl group, etc.), and the like. R7, R
The cycloalkyl group represented by a, Rs and Rho is preferably a cycloalkyl group having 3 to 6 carbon atoms excluding substituents! (For example, cyclopropyl group, cyclohexyl group, etc.). This cycloalkyl group includes those having a substituent, and examples of the substituent include the above-mentioned substituent examples of the alkyl group and the alkyl group. Examples of the aryl group represented by R7, Ra, Rs, and Rlo include phenyl group, naphthyl group, etc. These groups also include those having substituents, and examples of the substituents include the above-mentioned groups other than aryl groups. Examples of substituents in alkyl groups and alkyl groups are mentioned. R7,
Examples of the alkoxycarbonyl group represented by R8, R9 and Rlo include methoxycarbonyl group and ethoxycarbonyl group; examples of the alkylcarbamoyl group include:
Examples of arylcarbamoyl groups include butylcarbamoyl groups, such as phenylcarbamoyl groups, and examples of acyl groups include acetyl groups and benzoyl groups.These groups include those with substituents, and their M Examples of substituents include the above-mentioned examples of substituents in alkyl groups. It represents a simple bond or atomic group necessary to jointly form a 3-membered ring to a 6-membered ring, but the atomic group represented by Q includes general formulas (■-2) to (I[ [
The atomic groups shown in -5) are particularly preferable. In the compounds represented by the general formula [1[[] according to the present invention, in particular the following general formulas (III-1), (I[-2)(
Compounds represented by III-3), (m-4) and (III-5) can be preferably used. General formula (I[l-1) General formula (I[l-2) General formula (DI-4) R general formula (DI-5) Above general formula (I[[-1> to (III-5) In, R7, Ra, Rs and Rho are respectively the same as R7, R8, R9 and Rlo in the general formula [1[1].R+s, R17, R18 and R+s are respectively the same as in the general formula [1[] R7, Ra,
Synonymous with Rs and R+o. General formula (I[[-1)
In to (III-5), Rh, Ra, R9, R+
Any two selected from o, R+s, R17, R+a and R+9 may be combined to form a ring. In the present invention, among the compounds represented by the general formula (DI-1), compounds represented by the following general formula (DI-6>) can be particularly preferably used. , R7° represents a hydrogen atom* or an alkyl group (e.g. methyl group, ethyl group, etc.), but R2° is preferably a hydrogen atom. Y is a simple bond or an alkylene group (
For example, −CHt−+CH2+, −f−CHt ts −
廿C) (t→T, etc.) 6 nl represents a positive integer, preferably 1-4. When Y represents a fullkylene group, and nI = 1, X represents a substituent; when n is 2 or more, X represents an n4-valent bonding group; when Y is a simple bond, X represents , has the same meaning as R, , R, SRs and R1° in the general formula [11]. Examples of the above substituents include furkyl groups (such as ethyl groups), cycloalkyl groups (such as cyclohexyl groups),
Aryl group (for example, phenyl group O0). Here, R21 is an alkyl group (for example, 1s
o-octyl group, etc.), an aryl group (e.g., 7-enyl group, etc.), a cycloalkyl group (e.g., cyclohexyl group, etc.), or a heterocyclic group (e.g., 7-ran, pyrinol, etc.),
These substituents may further have a substituent. As the bonding group for n+1 above, when n is 2,
For example, when n is 3, for example, l (hereinafter referred to as R22 and R2; is an alkylene group (e.g. -CH2, fcH2, etc.) or a). It also includes divalent groups formed by arbitrary bonding of arylene groups. R2 represents O or a positive integer. R23, R23 and R23 each represent a hydrogen atom or an alkyl group (e.g. methyl group, ethyl group, etc.). In general formula (III-6), when nl is 2 or more,
The groups represented by -Y-C-CH2 may be the same or different. Compound represented by general formula [111] according to the present invention ~6
It may be a polymer having a member ring in the molecule. In this case, it may be a homopolymer derived from a monomer having the above-mentioned ring in the molecule, or a copolymer derived from this monomer and another vinyl monomer. Among the compounds represented by the general formula [I[1] according to the present invention, one preferable group includes at least one nityl bond,
It has an ester bond (for example, -CO-1). Also, it is preferable that at least one hydrogen atom is bonded to the carbon atom directly connected to the oxygen atom in the ring. Typical specific examples of compounds represented by the general formula [■] are shown below, but the present invention is not limited thereto. Margin RR,'to'l HH to8 CHz H2O2C
H, CI H l 10' CHzOCiHs H+
++ cH2cI G (1 or less margin 118 (CHI). Day 9 (CHt) i llo (CH2) 412 ((
CHz)zc=cHz The following margin The compound represented by the general formula [■] according to the present invention may be purchased as a commercial product. Alternatively, it can be obtained by synthesizing a corresponding compound having a double bond in advance and then oxidizing the double bond with an oxidizing agent (for example, hydrogen peroxide). Further, the above-mentioned 6-membered cyclic ether compound is described in, for example, Journal of Organic Chemistry (J, O, C,), 3
Volume 6. 1116 pages (1971), Macromolecules (M
acromolecules), 1980. 2
The 5-membered compound can be prepared by the method described on page 52, for example in British Patent No. 8671918, Ann 623.
．． 191 (1959), and the four-membered one can be synthesized by the method described in German Patent No. 1.021,858. The amount of the compound represented by the general formula [1ffl] is the amount of the cyan coupler represented by the general formula [I] and the compound represented by the general formula [1ffl].
The amount is preferably 1 to 1000 parts by weight, and particularly preferably 5 to 200 parts by weight, based on 100 parts by weight of the total amount of cyan coupler represented by rl. In the present invention, at least one layer of the silver halide emulsion layer includes a cyan coupler represented by the general formula [I], a cyan coupler represented by the general formula [I[], and a cyan coupler represented by the general formula [1].
The compound represented by 111 is contained in the form of oil droplets, and as a method for adding these to silver halide photographic materials, there is, for example, an oil-in-water emulsion dispersion method. In the oil-in-water emulsion dispersion method, the cyan coupler represented by the general formula [I] and the cyan coupler represented by the general formula [I[] are preferably combined with a compound represented by the general formula [nI] and/or a compound as described below. The emulsified fraction is dissolved in a high boiling point organic solvent with a low dielectric constant, and then emulsified using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After that, it may be added to the desired silver halide emulsion layer. By this method, a cyan coupler represented by the general formula [I] according to the present invention, a cyan coupler represented by the general formula [nl] and a cyan coupler represented by the general formula [I[
The compound represented by [ ] can be contained in the silver halide emulsion layer as oil droplets. Further, a general high boiling point organic solvent can also be used in combination with the compound represented by the general formula [1 [[] according to the present invention. High boiling point organic solvents that can be preferably used include:
Compounds with a dielectric constant of 6.0 or less at 30°C, such as esters such as phthalates and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds with a dielectric constant of 6.0 or less at 30°C. etc. Particularly preferably, the dielectric constant at 30°C is 6.0 or less and 1.9 or more and 100
It is a high boiling point organic solvent with a vapor pressure of 0.5 n+mHa or less at °C. When these organic solvents are used together, general formula [II[]
It may be used in an amount of 10 to 100% by weight based on the compound represented by. Photographic additives (e.g. image stabilizers, anti-stain agents, etc.) include cyan couplers represented by general formula [II] and cyan couplers represented by general formula [II] as well as compounds represented by general formula [1 [[] It may be dissolved in the same oil droplet as above, or it may be dissolved in the above-mentioned low dielectric constant, high boiling point organic solvent and added to the silver halide emulsion layer. The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper. In particular, when a color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated. The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, silver halide emulsion layers containing magenta, yellow, and cyan couplers and non-silver halide emulsion layers are usually used as photographic power blurrs. It has a structure in which photosensitive tang is laminated on a support in an appropriate number of stones and in an appropriate order.
The government and stones may be changed as appropriate depending on the important performance and purpose of use. When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer, and a magenta dye image forming layer on the support. Particularly preferred is a layer, an intermediate layer, a cyan dye forming layer, an intermediate layer, and a protective layer. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention)
．． , ) include silver bromide, silver iodobromide as silver halide,
Any of those used in conventional silver halide emulsions can be used, such as silver iodochloride, silver chlorobromide, and silver chloride. The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
H,pA! It may also be produced by controlling and sequentially adding II. After growth, a conversion method may be used to change the halogen composition of the particles. When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary. The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains, such as cadmium cum salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt. or complex salts, iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding metal ions, and by placing them in an appropriate reducing atmosphere, reduction-sensitized nuclei can be added inside the particles and/or on the surface of the particles. Can be granted. In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643. The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers. The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions. The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
Sulfur sensitization method using activated gelatin, selenium sensitization method using selenium compounds, reduction sensitization method using reducing NyJ substance,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good. The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide is added during chemical ripening, and/or at the end of chemical ripening, and/or after chemical ripening Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the emulsion. As the binder (or protective colloid) for the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as cellulose derivatives, single or copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. The emulsion layer of the silver halide photographic light-sensitive material of the present invention contains a coupling reaction with an oxidized product of a primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) during color development treatment. A dye-forming coupler that forms a dye. - is used. The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, a mapping dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. As the magenta dye coupler, couplers represented by the following general formulas [A] and [3] can be preferably used. General Formula [A] In the formula, Ar represents an aryl group, R1 represents a hydrogen atom or a substituent, and R2 represents a substituent. Y is a hydrogen atom or a substituent that can be eliminated by reaction with the oxidized product of color development 1 mulberry, W is -NH-1-NHCO-
(N atom is bonded to the carbon atom of the pyrazolone nucleus) or -N
It represents HCONH-, and m is an integer of 1 or 2. General Formula [B] In the formula, ZIL represents a non-metallic atom necessary to form an S nitrogen oligomer ring, and the ring formed by Za may have a substituent. X represents a hydrogen atom or a substituent which can be separated by reaction with an oxidized product of Color Development 1 Mulberry. Further, RL represents a hydrogen atom or a substituent. Examples of the substituent represented by RcL include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, and a carbamoyl group. group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, peterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfone Amide group, imide group,
Examples include ureido group, sulfamoylamino group, alkoxycarbonylaminocarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group. Specific examples of mapinta couplers preferably used in the present invention are shown below, but the invention is not limited thereto. t t t t L t M-13 M-14 As a yellow dye-forming coupler used in the present invention (
J1 Compounds represented by the following general formula [Yl are preferred. -112 Formula [Yl In the formula, Rh is an alkyl group (e.g. methyl group, ethyl group,
Propyl group, butyl Nw) or aryl! represents S (e.g. phenyl group, p-methoxyphenyl, etc.), and R1
2 represents an aryl group, and Yl represents a hydrogen atom or a group that leaves during the color development reaction process. Further, particularly preferred yellow dye-forming couplers are compounds represented by the following general formula [Y']. General formula [Y'] In the formula, R13 represents a halogen atom, an alkoxy group, or an aryloxy group, and R+4, R15, and R+s are
hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, respectively.
It represents a carbonyl group, a sulfuryl group, a carboxylcarbamyl group, a sulfone group, a sulfamyl group, a sulfonamide group, an acylamido group, a ureido group, or an amino group, and Yl has the above-mentioned meaning. These include, for example, U.S. Pat. No. 2,778,658, U.S. Pat.
@, Same No. 3, 227, 155, Same No. 3, 227,
No. 550, No. 3,253,924, No. 3, 2
65, 506, 3,277, 155, 3,341, 331, 3,369,895,
3,384,657, 3,408,1
No. 94, No. 3,415, No. f352, No. 3,447
, No. 928, No. 3, 551, 155@, No. 3
, No. 582, 322, No. 3, 725, 072,
3,894,875, etc., German Patent Publication No. 1,547,868, German Patent Publication No. 2,057,941, German Patent Publication No. 2,162,899, German Patent Publication No. 2,163,812
No. 2,213,461, No. 2,219,91
No. 7, No. 2,261,361, No. 2.263.8
No. 75, Special Publication No. 49-13576, Japanese Patent Publication No. 48-29
No. 432, No. 48-66834, No. 49-10736
No. 49-122335, No. 50-28834,
and No. 50-132926. Typical specific examples of the yellow dye-forming coupler represented by the general formula [Y] are shown below, but the invention is not limited thereto. The following margin: Below the margin: between the emulsion layers of the silver halide photographic light-sensitive material of the present invention (same as -
(between color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity,
Color antifogging agents are used to prevent deterioration of sharpness and noticeable graininess. The eye color antifoggant may be used in the emulsion layer itself, or may be used in an intermediate layer provided between adjacent emulsion layers. An image stabilizer can be used in the silver halide photographic material of the present invention for the purpose of preventing deterioration of the dye image. The photosensitive material is used in hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic material of the present invention! It may contain an ultraviolet absorber to prevent fogging due to discharge caused by charging with II or the like and to prevent deterioration of the image due to UV light. The silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter base, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development. A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention to reduce the gloss of the light-sensitive material, increase the ease of writing, and prevent the sensitizers from sticking to each other. can be added. Slippage of the silver halide photographic material of the present invention 11! Lubricants can be added to reduce chafing. An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photographic material of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer. The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization). surfactants are used. The silver halide photographic light-sensitive material of the present invention includes a photographic emulsion layer, a flexible reflective support such as baryta paper or paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, cellulose nitrate, It can be applied to films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics. The silver halide photographic light-sensitive material of the present invention can be prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., as required, or directly or (adhesiveness, antistatic properties, etc. of the support surface).
Dimensional stability, abrasion resistance, hardness, antihalation properties, I
'j! It may be applied via one or more subbing layers (to improve cooling properties and/or other properties). When coating the silver halide photographic material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously. . The silver halide photographic light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. As a light source, natural light (sunlight)
Excited by , tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beam, X-ray, γ-ray, α-ray, etc. Any known light source can be used, such as light emitted from a phosphor. Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently. The silver halide photographic material of the present invention can form images by performing color phenomena known in the art. The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 g per 1 fL of color developing solution, preferably about 1 g to about 15 g per 1 fL of color developing solution.
Used at a concentration of
Oxytoluene, 2-amino-3-oxytoluene, 2
--oxy-3-amino-1,4-dimethylbenzene and the like. Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine salt m salt, N-methyl-p-phenylenediamine hydrochloride, N
, N'-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,
N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N. N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components that are normally added to the color developer, such as sodium hydroxide and sodium carbonate. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, etc. may be optionally contained. . The l)H value of this coloring phenomenon liquid is usually 7 or more, most commonly about 10.
〜about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a composition in which gold ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or R-containing acid such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These borine carboxylic acids or aminopolycarboxylic acids are alkali metal fi! , an ammonium salt or a water-soluble amine salt. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used in the sodium acetate salt contains a metal complex salt of an ionic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. In addition, substances known to be added to ordinary bleaching solutions, such as 111M salt, oxalate, acetate, carbonate, and phosphate buffers, alkylamines, and polyethylene oquinides, may be added as appropriate. can. Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite cum, ammonium bisulfite, potassium bisulfite, bisulfite III! Il! I sodium, meta m sub@
ammonium acid, potassium metabisulfite, metabisulfite Ij
Sulfites such as I'm sodium, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may contain one or more OHM buffers consisting of salts of. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank as desired, or an appropriate method may be used. Oxidizing agents such as hydrogen peroxide, bromates, persulfates, etc. may be added as appropriate. Margin below [Effects of the Invention] The silver halide photographic light-sensitive material of the present invention can significantly improve the dark fading resistance and light fastness of cyan dye images formed without adversely affecting other photographic properties. can. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these embodiments. <Example 1> A sample of a monochrome silver halide photographic material was prepared with the layer structure shown in the table below. Application: It! J/ 100c+j The cyan coupler dispersion used for the first layer is as follows (
A') to (C') were prepared. (a) Combine cyan couplers with the ratios shown in Table 1 to 3.
11,2.5-di(-octylhydroquinone0.
45g, compound 20 (] represented by the general formula [I[[])
and/or mixed with a mixed solution of the high boiling point organic solvent shown in Table 1 and ethyl acetate 1001N, and heated to 60°C to dissolve. (b) 40 g of photographic gelatin and 500 g of pure water are mixed at a different temperature and allowed to swell for 20 minutes. Then heat to 60'C,
5 of Alkanol B (manufactured by DuPont) after dissolving it.
Add 501Q% aqueous solution and stir evenly. (C) The solutions obtained in (a) and (b) were mixed and dispersed for 30 minutes using an ultrasonic disperser to obtain a cyan coupler dispersion. Samples 1 to 23 were prepared by changing the composition of the cyan coupler used in the first layer as shown in Table 1. These samples were exposed to red light using a photosensitive needle (Konishi Rokusha Page Industries Qll!J. KS-7 model) and then subjected to the following treatments. Standard processing steps (processing temperature and processing time) Color development 38℃ 3 minutes 30 seconds Bleach fixing
33℃ 1 minute 30 seconds water washing treatment 25-3
Dry at 0℃ for 3 minutes 75-80℃ for about 2 minutes Processing solution composition (color developer) Benzyl alcohol 151Q ethylene glycol 151g Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.29 potassium carbonate
30. OQ Hydroxylamine Sulfate
3.0g polyphosphoric acid (TPPS) 2.
5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.09 Hydroxylation Potassium 2.00 Add water to bring the total amount to 1ffi and adjust to pl-110,20. (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 Q Ethylenediaminetetraacetic acid M 30 Ammonium thiosulfate (70% solution) 1001Q Ammonium sulfite (40% solution) 27.5. f! Adjust the EIH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 12.
shall be. After processing, the lightfastness of the cyan dye image obtained and 11
1. A color selection test was conducted according to the method below, and the results are shown in Table 1. Light fastness test> It was shown as the residual rate of the initial concentration Do -1.0 when exposed to sunlight for 30 days using an underglass outdoor sunlight exposure table. (D-11 degrees after fading) Dark fading test> The fading of a pattern stored in the dark at 70° C. and 40% RH for 2 weeks was determined as a survival rate in the same manner as the light fastness. From the results in Table 1 below, in Samples 1 and 2, when the coupler represented by general formula [I] is used alone, when the high boiling point organic solvent is changed from (S-2) to (No. 15), Although an improvement in light fastness was certainly observed, the degree of improvement was insufficient. On the other hand, when the coupler represented by the general formula [I] is used alone, when the solvent is changed from (S-2) to (No. 15), dark fading occurs as seen in samples 4 and 6. Although some improvement was confirmed, it was completely insufficient, and on the contrary, the light fastness deteriorated significantly. However, when comparing samples 7 and 8, which combined both couplers, (No. 15
) sample 8 showed a unique effect in that both light fastness and dark fading resistance were improved to sufficient levels. The specific effects of these specific combinations could not be predicted at all from conventionally known techniques. Furthermore, as shown in Sample 9, the general formula [I[[]
Even if a known high boiling point organic solvent was used in addition to the compound represented by the formula, the effects of the present invention did not change at all, and no problems were caused. Furthermore, Samples 10 to 23 also exhibited excellent image storage properties as described above. Further, from the observation of the roughness of the coated samples, there was no precipitation in Samples 8 to 23. Example 2 A coating solution for each layer was prepared so as to have the structure shown in Tables 2 and 3, and the coating solution was applied sequentially from the support side to prepare a multilayer silver halide color photographic material. The same treatments and tests were carried out. The results are shown in Table 3. Below are blank spaces: Ultraviolet absorber uv-i Ultraviolet absorber V-2 Anti-stain agent S-1 0-CmHu(i) In the table, DBP represents dibutyl phthalate. From the results in Table 4, the multilayer silver halide color photographic material also shows the same effect as Example 1, and samples 4 to 10 according to the present invention have remarkable light fastness and dark fading resistance. It is clear that it has been improved.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the following general formula [I]. A silver halide photographic material characterized in that a cyan coupler, a cyan coupler represented by the following general formula [II], and a compound represented by the following general formula [III] are contained as oil droplets. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group. R_2 represents an alkyl group or an aryl group. R_3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Z_1
represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] General formula [II] ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R_4 represents an alkyl group or an aryl group. R_5 represents an alkyl group. R_6 represents a hydrogen atom, a halogen atom, or an alkyl group. Z_2 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Q is the compound necessary to form a 3- to 6-membered ring together with ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents a simple bond or a group of atoms. R_7, R_8, R_9 and R_1_0
are hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxycarbonyl group, respectively.
It represents an alkylcarbamoyl group, an arylcarbamoyl group, an acyl group or a cyano group. Any two selected from R_7, R_8, R_9 and R_1_0 may be combined to form a ring, and R_7
, R_8, R_9 and R_1_0 may be combined with the atomic group represented by Q to form a ring. ]