JPS59166955A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To prevent yellow staining due to light as well as improve resistance to light, humidity, and heat, and to obtain superior image quality retentivity by incorproating a specified cyan coupler in a silver halide emulsion layer and sensitizing silver halide with a specified compd. CONSTITUTION:A silver halide emulsion layer formed on a support contains one selected from silane couplers represented by formula I in which R1 is alkyl or aryl; R2 is alkyl, cycloalkyl, or the like; R3 is H, halogen, alkyl, or the like; and Z1 is H or a group releasable by the reaction with the oxidized product of an aromatic primary amine developing agent. The emulsion layer also contains one of compds. represented by formulae II and III to spectrally sensitizing the silver halide. Such a photosensitive material can form a dye image extremely reduced in yellow staining, and enhanced in the general image quality retentivity including heat and humidity resistance, color darkening and fading resistance, etc., and also good in processing stability, such as color recovery property, in bleach fixing, etc.

Description

Detailed Description of the Invention (1) Background Technical Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material suitable for printing.

Prior art and its problems In silver halide color photographic light-sensitive materials, dye images are
Usually, an aromatic primary amine color developing agent reduces silver halide grains and oxidizes itself, and this oxidized product reacts with a coupler pre-contained in the silver halide color photographic light-sensitive material to form a dye. Obtained by forming. usually,
As couplers, three dye-forming couplers, yellow, magenta and cyan, are used for color reproduction by subtractive color method.

Among these three dye-forming couplers, the basic properties required for cyan colorants are that the resulting cyan dye image has fastness to light, heat, moisture, etc. It is mentioned that the storage stability of dye images containing the dyes is significantly improved, and in particular, the fading resistance such as heat resistance and moisture resistance is improved.

Cyan couplers that meet these requirements include 2, in which the 2- and 5-positions of the phenol are substituted with acylamino groups;
Examples include 5-diacyl aminophenol cyankafree, such as those described in U.S. Pat. No. 2,895,826;
It is described in JP-A-5O-ti2o3s, JP-A-53-109630, and JP-A-55-163537.

These 2,5-diacylaminophenol-based cyan couplers have excellent image preservation properties, especially resistance to fading, of cyan dye images formed, and have excellent processing stability.
In particular, the color recovery property in bleach-fixing treatment is good. In particular, one or both of the 2- and 5-position acylamino groups have a sulfonamide group represented by the formula -NR14So 2R13 (R13 represents an alkyl group, aryl group, diluted or amino group, and R14 represents a hydrogen atom or an alkyl group). In addition to the above-mentioned properties, the 2,5-diacylaminophenol-based cyan coupler in which It also has excellent properties.

However, a silver halide photographic emulsion coating solution (hereinafter referred to as coating solution J) was prepared using the above-mentioned 2,5-diacylaminophenol cyan coupler having these excellent properties and having an L'honamido group. The sensitivity of silver halide changes significantly when coating on the support immediately after preparing the coating solution, and when coating on the support after the coating solution stagnates, resulting in defects after the coating solution stagnates. When mass-producing photosensitive materials, there is a serious drawback in that it is difficult to mass-produce photosensitive materials of consistent quality.

Therefore, in order to improve the stagnation property of the emulsion coating solution, there is a method of adding a sensitizing dye to the coating solution, but this method can be said to be sufficient to improve the stagnation property of the coating solution. As the amount of sensitizing dye added increases, residual color staining due to the sensitizing dye occurs frequently.

In addition to the methods described above, methods for improving coating liquid stagnation include adding azoles and azaindene compounds known as stabilizers to the coating liquid, such as adding reducing agents such as hydroquinones and sulfinic acids. method, or the method of using a certain copolymer and a fluorescent brightener in combination as described in JP-A-49-10629, but these methods reduce the stagnation of the coating solution. Not only do they not provide sufficient improvement, but some also have the drawback of deteriorating important photographic characteristics such as gradation and sensitivity.

■ Purpose of the Invention The purpose of the present invention is to prevent light color contamination, improve the light fastness, heat resistance, and moisture resistance of the formed dye image in a well-balanced manner, and provide a dye image with excellent overall image storage stability. A silver halide photographic sensitizer that can form images, has excellent image processing stability, especially color recovery in bleach-fixing processing, and has good stability over time of the emulsion coating solution during manufacturing, and can be stably mass-produced. The purpose is to provide materials.

The above object of the present invention is to provide a silver halide photographic material in which at least one silver halide emulsion layer is provided on a support, in which the silver halide emulsion layer has the following general formula [1].
], and the silver halide in the silver halide emulsion layer is contained in the silver halide emulsion layer as described below.

General formula [I] H zl [wherein R] represents an alkyl group or an aryl group. R2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also R3
may be combined with R1 to form a ring. zl represents a hydrogen atom or a group which can be separated by reaction with the arsenic acid of the primary amine color developing main mulberry for aromatic compounds. ] General formula (Ill [In the formula, Ll, B2 and B3 each represent a methine group. Yl and Y2 each represent an oxygen atom, a sulfur atom or a selenium atom. R4 Doyo and R5 each represent an alkyl group.However, R4 and R5
O Al, A2, at least one of which has a sulfo group;
B1%B2, Cl, C2, Dlg represent a koxycarbonyl group. Also A, and B1, B1 and C1, C1 and Dl
, A2 and B2, B2 and C2, and C2 and B2 may be condensed to form a benzene ring. M represents a cation. m represents 0 or 0] General formula 日日-,--22--1 In the formula, z2 is a group of nonmetallic atoms necessary to form a quinoline ring together with the bonded crab atom and carbon atom. represents. z3 is an atomic group necessary to constitute a thiazole ring, benzothiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole ring or naphthoselenazole ring together with the bonded hydrogen atom 3 and carbon atom. represent. R6, R7 and R8 each represent an alkyl group. Xθ represents an acid a=one group. l and n each represent an integer of 0 or l. [Detailed description of the invention] In the present invention ζ, the alkyl group represented by R1 in general formula (1) is a straight chain or branched one, such as a methyl group, an ethyl group, a 1so-propyl group, a butyl group. , pentyl group, octyl group, nonyl group, tridecyl group, etc., and the aryl group is, for example, phenyl group, naphthyl group, etc. These groups represented by R may have a single substituent or multiple substituents. For example, a typical 7% substituent introduced into a phenyl group is a no-rogen atom (
(e.g., fluorine, chlorine, bromine, etc.), alkyl groups (e.g., methyl, ethyl, propyl, butyl, dodecyl, etc.), hydroxyl, cyano, nitro, alkoxy (e.g., methoxy, ethoxy, etc.) Alkylsulfonamide groups (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide groups (
For example, phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (for example, butylsulfamoyl group, etc.), arylsulfamoyl group (for example, phenylsulfamoyl group, etc.), alkyloxycarbonyl group ( (e.g. methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, etc.), L7 minosulfonamide group (e.g. N, N-
dimethylaminosulfonamide group, etc.), acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group, sulfo group, aryl-furoxy group, alkoxy group, carboxyl group, alkylcarbonyl group, arylcarbonyl group, etc. can. Two or more of these substituents may be introduced into the phenyl group.

The halogen atom represented by R3 is, for example, fluorine, chlorine, bromine, etc., the alkyl group is, for example, methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc., and the alkoxy group is, for example, methoxy group. , ethoxy group,
These include propyloxy group, butoxy group, etc. R3 may combine with R1 to form a ring.

In the present invention ζ, the alkyl group represented by R2 in the general formula [1] is, for example, a methyl group, an ethyl group, a butyl group, a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, a fluorine-substituted so-called These include polyfluoroalkyl groups.

The aryl group represented by R2 is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. Examples of the heterocyclic group represented by R2 include a pyridyl group and a furan group. The cycloalkyl group represented by R2 is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by R2 may have a single substituent or multiple substituents. For example, a typical substituent introduced into a phenyl group is a halogen atom (for example, fluorine, chlorine, bromine, etc.). ), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyan group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (
For example, methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (for example, phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (for example, butylsulfamoyl group, etc.), arylsulfamoyl group groups (e.g. evaphenylsul7amoyl group etc.), alkyloxycarbonyl groups (e.g. methyloxycarbonyl group etc.), aryloxycarbonyl groups (e.g. phenyloxycarbonyl group etc.),
Examples include an aminosulfonamide group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfoxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group, and an arylcarbonyl group. Two or more of these substituents may be introduced into the phenyl group. Preferred groups represented by R2 include polyfluoroalkyl groups, phenyl groups or halogen atoms, alkyl groups, alkoxy groups, alkylsulfonamide groups, arylsulfonamide groups, alkylsulfamoyl groups, arylsulfamoyl groups, and alkylsulfonyl groups. , an arylsulfonyl group, an alkylcarbonyl group, a 71J −/I/carbonyl group, or a cyano group as a substituent.

Among the cyan couplers represented by the general formula [1] in the present invention, preferred are compounds represented by the following general formula (IV).

General formula [IV] H 4 In general formula [IV], R9 represents an alkyl group or a phenyl group. This alkyl group or phenyl group may have a single or multiple substituents, and typical examples of the substituents introduced include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group) group, octylsulfonamide group, etc.), arylsulfonamide i (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), Examples of these substitutions Two or more of the groups may be substituted with phenyl groups. Preferred groups represented by R9 include polyfluoroalkyl groups, phenyl groups, or).
rogen atoms (e.g. fluorine, chlorine, bromine), alkylsulfonamide groups (e.g. 0-methylsulfonamide group,
p-octylsulfonamide group, 0-dodecylsulfonamide group j, arylsulfonamide group (e.g. phenylsulfonamide group), alkylsulfamoyl group (e.g. butylsulfamoyl group), arylsulfamoyl group (e.g. phenyl sulfamoyl group), alkyl group (e.g. methyl group, trifluoromethyl group), alkoxy group (e.g. methoxy group, ethoxy group), alkyloxycarbonyl group, aryloxycarbonyl group, acylamino group, carbamoyl group, sulfonyl group, carbonyl group The radical is a phenyl group having one or more cyan groups as substituents.

1 (1o is an alkyl group or an aryl group. The alkyl group or aryl group may have a single substituent or more than one substituent, and C is a typical substituent). atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxyl group, carboxyl group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyan group, nitro group , alkoxy groups (e.g. methoxy group, ethoxy group, pairyloxy group, alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.),
Arylsulfonamide groups (e.g., phenylsulfonamide groups, naphthylsulfonamide groups, etc.), alkylsulfamoyl groups (e.g., butylsulfamoyl groups, etc.),
Arylsulfamoyl, alkyloxycarbonyl group (for example, methyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, etc.), aminosulfonamide group (for example, N.N-dimethylaminosulfonamide group, etc.), Alkylsulfonyl groups, arylsulfonyl groups, alkylcarbonyl groups, arylcarbonyl groups, ureido groups, carbamoyl groups, sulfinyl groups, etc. can be removed. Two or more types of these substituents may be introduced.

Preferred groups represented by RIO are an alkyl group when J=Q and an aryl group when zi or more.

A more preferable group represented by R10 is l! When it is 20, it is an alkyl group having L to 22 carbon atoms (for example, methyl group, ethyl group, proyl group, butyl group, octyl group,
dodecyl group), and an enyl group of 121 or more,
or an alkyl group (e.g. t-butyl group, t-amyl group, octyl group), an alkylsulfonamide group (e.g. butylsulfonamide group, octylsulfonamide group, dodecylsulfonamide group), an arylsulfonamide group (e.g. phenylsulfonamide group). phenyl having one or more substituents with aminosulfonamide group (e.g., N, N-dimethylaminosulfonamide group), or alkyloxycarbonyl group (e.g., methyloxycarbonyl group, butyloxycarbonyl group) It is the basis.

R11 represents an alkylene group, preferably a linear or branched group having 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms.
Two alkylene groups are preferred, and a branched alkylene group is particularly preferred.

A circle represents a hydrogen atom or a halogen atom (fluorine, chlorine, bromine, or iodine). Hydrogen atoms are preferred.

l is 0 or a positive integer, preferably O or l.

or -〇-1-CO-1-COO-1-OCO-1-C
ONRx'-1NR'xCO-1-8O2NR'x-5
-NR14SO2R13-1-S-1-so- or-
8T represents the divalent group of O2- group. Here, R'xSR"x
represents an alkyl group. X is preferably -0-1-S
-1-SO-1SO2- group.

z4 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.

In general formulas [1] O and [IV ], Zl ′j6
The groups which can be separated by reaction with the oxidized product of the aromatic primary amine color developing agent, represented by Therefore, in the coating layer or other layer ζ containing a coupler in a silver halide color photographic light-sensitive material, it has an advantageous effect by performing functions such as development inhibition, bleaching inhibition, and color correction. Typical examples include halogen atoms, alkoxy groups, aryloxy groups, arylazo groups, thioether groups, carbamoyloxy groups, acyloxy groups, imido groups, sulfonamide groups, thiocyano groups, and heterocyclic groups (e.g., oxacylyl, diazolyl, triazolyl, tetrazolyl, etc.). Particularly preferably zl or z4 is a hydrogen atom or a chlorine atom.

A more preferable cyan coupler of the present invention has the general formula (1■)
has a sulfonamide group (-NR14SO2R13, where R13 represents an a7.kyl group, an aryl group, or an amine group, and R14 represents a hydrogen atom or an alkyl group) in one or both of R9 and RIO.

Typical specific examples of the cyan coupler represented by formula [1] are shown below, but the invention is not limited thereto.

The following details are as follows: (1-11 (1-21 (1-31 11-41 1 1-5 ++-13J f-141 1-151 +1-161 (1-171 (1-181 (1-191 MJ) (1-201 (1-211 0H) (1-221 +1-231 +1-241 H [1-251 ( 1-261 H (1-271 +1-291 ++-30) +1-311 H ++-321 H 1-331 l-341 fl-35] (1-361 [f-371 +1-381 +1-391 +1-401 H +1-411 H l-421 H i, l-431 [+-441 H +1-451 ?) l-461 0■ Z +1-471 +1-481 In the present invention ζ, Ll of general formula [1] , R2 and R
When the methine group (-CH2) represented by 3 has 2 substituents, that is, when it is represented by the formula -CR20-, one substituent represented by this R20 is
~8 linear or branched alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, carboxylmethyl group, benzyl group), alkoxy groups (e.g. methoxy group, ethoxy group), and aryl Examples include groups (eg, phenyl group, tolyl group), γ, and the like.

The alkyl groups represented by R43 and R5 in general formula (n) are linear or branched, such as methyl group, ethyl group, n-propyl group, etc. -propyl group, n-butyl group, etc., and when the alkyl group represented by R4 and R5 has a substituent, the hyalkyl group is, for example, a hydroxylalkyl group (e.g. hydroxymethyl group, hydroxyethyl group, hydroxyethyl group). ), sulfoalkyl group (e.g. sulfoethyl group, sulfopropyl group, sulfobutyl group, 2-hydroxyl-3-sulfopropyl group)
, carboxyalkyl group (e.g. carboxymethyl group,
carboxyethyl group), acetoxyalkyl group (e.g. acetoxyethyl group), aralkyl group (e.g. benzyl group, phenethyl group), alkenyl group (e.g. allyl group,
impropenyl group), etc. However, at least one of R4 and R5 is an alkyl group having a sulfo group.

A1, A2, B1, B2, ClSC2 of general formula [11]
,D.

The alkyl group represented by and B2 has 1 to 1 carbon atoms.
About 5 linear or branched lower alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, trifluoromethyl group), and the alkoxy group has 1 to 5 carbon atoms.
a straight-chain or branched alkyloxy group (e.g. methoxy group, ethoxy group), the halogen atom is fluorine, dam, bromine or iodine, and the phenyl group is e.g. phenyl group without substituents, hydroxyphenyl group. A group, a carboxyphenyl group, an alkoxy group, a sulfonyl group, such as a methoxycarbonyl group, an ethoxycarbonyl group.

For example, hydrogen ions, sodium ions, potassium ions,
triethylammonium ion, pyridinium ion,
N,N-diethyl-N-inpropylammonium ion and the like.

When the compound represented by the general formula [n] forms an inner salt, m is O.

Specific examples of the compound represented by the general formula (n) are shown below, but the invention is not limited thereto.

il-11 (n-21 1-11(n-21(II-31(11 +11-61 +1l-71 0-8) (It-91 tll-101 +ll-111 +ll-12) ffl-131 +lt-141 [1l-151 fil-161'- mouth-17) eye-181 fil-191 (It-20) low 21) fil-221 (It-23) III-241 (II-251 (n-261 il+-271 C2H5 (II-281 (II-291 (II-301 (II-311 [1m-321 (If-331 (II-341) 2115 In the present invention, the quinoline ring of general formula When the substituent has, for example, a halogen atom, an alkyl group, an alkoxy group,
Hydroxyl group, cyan group, carboxyl group, alkoxycarbonyl group, alkylamino group, acylamino group,
Examples include acyl group, phenyl group, and cyclohexyl group. Specific examples of the quinoline ring having z2 as a constituent include 2-quinoline, 6-chloro-2-quinoline, 6-metal-2-quinoline, 6-medoxy-2-quinoline, 7
-Methyl-2-quinoline, 8-methyl-2-quinoline,
6-hydroxy-2-quinoline, 4-quinoline, 6-methyl-4-quinoline, 6-ethyl-4-quinoline, 6-
Medoxy 4-quinoline, 6-nitoki/-4-quinoline, 6-chloro-4-quinoline, 6-hydroxy-4-quinoline, 6-phenyl-4-quinoline, 7-methyl-4
-quinoline, 8-methyl-4-quinoline, and the like.

A thiazole ring containing z3 of the general formula [110] as a constituent component.

When the benzothiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole ring or naphthoselenazole ring has a substituent, examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, Examples include hydroxyl group, cyanogen group, carboxyl group, alkoxycarbonyl group, alkylamino group, acylamino group, acyl group, phenyl group, cycloalkyl group, and the like.

Specifics of the thiazole ring containing Z3 as a constituent? ll is, for example, thiazole, 4-phenylthiazole, 4゜5-diphenylthiazole, 4-methylthiazole, 5-methylthiazole, 4-chlorothiazole, 4-methoxythiazole, etc.; -chlorobenzothiazole, 5-phenylbenzothiazole.

5-methylbenzothiazole, 5-methoxybenzothiazole, etc., and the naphthothiazole ring is α-naphthothiazole, β-naphthothiazole, 5-methoxy-β-naphthothiazole, 5-methoxy-β-nandothiazole,
8-methoxy-α-naphthothiazole, 8-chloro-α
- naphthothiazole, etc.

The benzoxazole ring containing Z3 as a constituent is benzoxazole, 5-chlorobenzoxazole, 5-7
enylbenzoxazole, 5-phenylbenzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, etc., and naphthoxazole ring ha, α-naphthoxazole, β-naphthoxazole,
5-Methoxy-β-naphthoxazole, 5-methyl-
β-naphthoxazole, 5-methyl-β-naphthoxazole, 8-methoxy-α-naphthoxazole,
8-chloro-α-naphthoxazole and the like.

Benzoselenazole term C containing Z3 as a constituent component, benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, 5-phenylbenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole etc., and the naphthoselenazole ring is α-naphthoselenazole, β-naphthoselenazole,
5-Methoxy-β-naphthoselenazole, 5-methyl-
β-naphthoselenazole, 5-methyl-β-naphthoselenazole, 8-methoxy-α-naphthoselenazole, 8
-chloro-α-naphthoselenazole and the like.

The alkyl groups represented by R6, R7, and R8 in the general formula C■ are linear or branched, and examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-
butyl group, etc., and when the alkyl group represented by R4 and R5 has a substituent, the alkyl group is, for example, a hydroxylalkyl group (for example, a hydroxymethyl group,
hydroxyethyl group, hydroxyethyl group), sulfoalkyl group (e.g. sulfoethyl group, sulfopropyl group,
sulfobutyl group, 2-hydrokine-3-sulfopropyl group), sulfate alkyl group (e.g. sulfate propyl group, sulfate butyl group), carboxyalkyl group (e.g. carboxymethyl group, carboxyethyl group), acetoxyalkyl group (e.g. acetoxyethyl group) ), aralkyl groups (eg, benzyl group, phenethyl group), alkenyl groups (eg, allyl group, impropenyl group), and the like.

The acid anions represented by Xe in the general formula [■] are, for example, chlorine ion, bromide ion, iodine ion, perchlorate ion, fluoroborate ion, p-)luenesulfonate ion, ethersulfonate ion, methylsulfonate These include acid ions and nitrate ions.

When the compound represented by the general formula Cu1l) forms an inner salt, n is 0.

Specific examples of the compound represented by the general formula [■] are shown below, but the invention is not limited thereto.

(III-11 [:　ol(3(ySO3°) (III-21 (I[[-31 (I[l-4) The following plan e (n[-6) (111-7) 02HI!　　　　　　02H6 re (II[-81 (l[-111 0H200H.

The following is all white (III-14) (ill-15) C2H50H3 (OH3-C)-803e) The following is gold white (I[[-171 (III-18) (III-B) (32H5 (32H6, wa, bottom 7) Chishiro (III-21) (III-221 02H502H5 (J2kL4 (J(JH302H5) There are no particular restrictions on the number or order of the silver halide emulsion layer and the non-photosensitive layer. Typical examples include color positive or negative film, photographic paper, color slide, Alternatively, special photosensitive materials such as those for printing, X-rays, or high-resolution blades may be mentioned, but they are particularly suitable for color photographic paper.Usually, most of the silver halide emulsion layer and non-photosensitive layer are used. is a hydrophilic colloid layer containing a hydrophilic binder. Gelatin or a gelatin derivative is used as the hydrophilic binder.

The cyan coupler according to the present invention represented by formula [1] (hereinafter referred to as the cyan coupler according to the present invention) can be prepared by the same method used for ordinary cyan dye-forming couplers. The containing silver halide emulsion layer is coated onto a support to form a photographic element. The photographic element may be a single color element or a multicolor element.

In the case of multicolor elements, the cyan coupler according to the invention is usually contained in a red-sensitive silver halide emulsion layer, but it may also be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red. You can let me. Each structural unit forming a dye image in the present invention is a single emulsion layer or a multilayer emulsion layer sensitive to a certain region of the spectrum.

In order to incorporate the cyan coupler according to the present invention into an emulsion,
A conventionally known method may be followed. For example, phthalate esters (diptyl phthalate, etc.), phosphate esters (II
Cresyl phosphate, etc.) or N,N-dialkyl-substituted amides (N,N-diethyllaurinamide, etc.), and low-boiling organic solvents such as butyl acetate or butyl propionate, respectively. Or, if necessary, the cyan coupler according to the present invention is dissolved in a mixture of these solvents individually or in a mixture, and then mixed with an aqueous gelatin solution containing a surfactant,
After emulsification and dispersion using a high-speed rotary mixer, colloid mill, or ultrasonic dispersion machine, the silver halide emulsion used in the present invention can be prepared by adding silver halide.

When the cyan coupler according to the present invention is added to a silver halide emulsion, the cyan coupler is usually about 0.05 to 100% per mole of silver halide.
It is added in an amount of 2 mol, preferably in the range of 0.1 to 1 mol.

Furthermore, at least one compound of the compound group represented by general formula (4) and general formula (III) (hereinafter referred to as the sensitizing dye according to the present invention) is a halogenated compound containing a cyan coupler according to the present invention. It is necessary to add the sensitizing dye according to the present invention to the emulsion containing the cyan coupler according to the present invention by following a conventionally known method. Often, the sensitizing dye is dissolved in a suitable solvent such as methanol, ethanol, N,N-dimethylformamide, ethyl acetate, etc., or a mixed solution thereof, and used as a stabilizer and fog suppressor during or after the chemical ripening of the emulsion. This is done by adding the increasing dye solution either before or after adding the agent.

When the sensitizing dye according to the present invention is added to the 710 silver germide emulsion, the amount added is not particularly limited, but is usually about 1 x 10 to 1 xio = mol, preferably 5 x 10' to 1 xio = mol per mol of silver halide. Added in the range of 5X10' moles.

The sensitizing dyes according to the present invention can be used alone or in combination. Furthermore, a substance exhibiting a supersensitizing action, a so-called supersensitizer, may be used together with the sensitizing dye, if necessary.

A specific example of the method for producing the silver halide photographic material of the present invention is shown below. First, silver halide grains are produced by a known method, and after suitable physical ripening, soluble salts are removed, and then, after suitable chemical formation, the sensitizing dye solution and stabilizer solution of the present invention are added and chemically processed. A sensitized silver halide emulsion is obtained. On the other hand, the cyan coupler according to the present invention is dissolved in an appropriate high-boiling point solvent and low-boiling point solvent, added to a gelatin aqueous solution containing a surfactant, and then dispersed to form pores to obtain a cyan coupler dispersion g.

Next, a cyan coupler dispersion liquid is added to the chemically sensitized silver halide emulsion, and a spreading agent, a hardening agent, etc. are added to prepare a photographic emulsion coating liquid, which is coated on a support and dried. Obtain the sensitive material.

When the silver halide color photographic material of the present invention is a multicolor element, the necessary layers of the photographic element, including the layers of the image-forming units described above, may be added in various orders as known in the art. Can be arranged.

In this case, there are layers other than the image-forming structural unit layer, such as a filter layer, an intermediate layer, a protective layer, a protection layer, a non-photosensitive layer such as an undercoat layer, and the like.

Examples of the support according to the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper; transparent support with a reflective layer or a reflective material; glass plate; cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc. Examples include polyester film; polyamide film; polycarbonate film; polystyrene film. These supports are appropriately selected depending on the purpose of use of the silver halide photographic material of the present invention.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating are used for coating the silver halide emulsion layer and non-photosensitive layer used in the present invention.

The silver halide used in the silver halide emulsion of the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Includes anything that 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 (], OO] planes to [111] planes can be used.Furthermore, these silver halide grains The crystal structure of the grain may be uniform from the inside to the outside, or it may have a layered structure with different inside and outside parts.In addition, these silver halides form a latent image mainly on the surface. It may be of a type in which the particles are formed, or it may be of a type in which it is formed inside one particle.

Furthermore, these silver halides may be produced by any of the neutral method, ammonia method, acid method, and simultaneous mixing method, forward mixing method, back mixing method, conversion method, etc. Silver halide grains manufactured by either method can be used.

The silver halide emulsion according to the present invention contains, in addition to the sensitizing dye according to the present invention, a sulfur sensitizer such as arylthiocarbamide, thiourea, cystine, etc., an active or inactive selenium sensitizer, and Reduction sensitizers, such as stannous salts, polyamines, etc., ih metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-ourosulfobenzthiazole metherchloride, etc. or chemically sensitize using water-soluble salt sensitizers such as ruthenium and iridium, specifically ammonium chlorovaladate, potassium chlorozoratenate, and sodium chloropunguide, alone or in combination as appropriate. be able to.

Furthermore, the silver halide emulsion Q according to the present invention can be further modified by using a known additive for addition.

For example, photographic additives such as those described in Research Disclosure J December 1978, 417643.

The silver halide emulsion layer and non-photosensitive layer of the silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, antifoggants, color stain inhibitors, fluorescent brighteners, antistatic agents, hardeners, etc. described in Research Disclosure No. 17643,
Plasticizers, wetting agents, antioxidants, ultraviolet absorbers, and the like can be used as appropriate.

(2) Specific Use of the Invention The silver halide photographic material of the present invention thus constructed can be subjected to various photographic processing methods for color development after exposure. A preferable color developing solution used in the present invention is one containing an aromatic primary amine color developer as a main component. Specific examples of this color developing agent include p-
Typical examples include phenylenediamine-based compounds, such as diethyl-p-phenylenediamine hydrochloride and monomethyl-p-phenylenediamine hydrochloride.
p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-
dotecylamino)-toluene, 2-amino-5-(N-
Ethyl-N-β-methanesulfonamidoethyl)amine toluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4 (N
-x-y-ru N-β-hydroxyethylamine/)aniline, 2-amino-5-(N-ethel-β-methoxyetheraminotoluene, etc.) These color developing agents may be used alone or in combination. It is used in combination with the above, and if necessary, in combination with a black and white developing agent such as hydroquinone.Furthermore, the color developing solution is generally an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc. It may further contain various additives such as alkali metal halides such as potassium bromide, or development regulators such as human didicic acid.

The silver halide photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can produce a color developing herbal drug under alkaline conditions, and includes a perilla-7 based precursor with an aromatic altehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a phosphoric acid derivative precursor. Examples include amide derivative precursors, sugar amine reactant precursors, and urethane type precursors. Precursors for these aromatic primary amine color-forming agents are, for example, U.S. Pat. No. 3,342,
No. 599, No. 2,507,114, No. 2.695
, No. 234, No. 3,719,492, British Patent No. 8
No. 03.783, all books, JP-A-53-135, 62
No. 8, Publications No. 54-79,035, Research Disclosure Magazine No. 159, No. 12,146,
It is described in No. 14924.

These aromatic tertiary amine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. This amount varies considerably depending on the type of photosensitive material, etc., or is approximately 1 photosensitive silver halide.
The mole M fi is used between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol. These color-producing crude drugs or their precursors can be used alone or in combination. In order to incorporate the above compound into a 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 tricresyl phosphate, or it can be added by impregnating a latex remer as described in Research Dinuclosure No. 14850.

The silver halide photographic light-sensitive material of the present invention usually has color development 1.
Temporary bleaching and fixing, or bleaching and fixing, and washing are performed. Many compounds are used as bleaching agents, among them iron (1 [[), cobalt (IID), tin (
If) polyvalent whole compounds such as, in particular, complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid, Metal complex salts or ferricyanates such as tartaric acid, malic acid, diglycolic acid, dithioglycolic acid,
Dichromate and the like are used alone or in appropriate combinations.

■Specific Effects of the Invention According to the silver halide photographic light-sensitive material of the present invention, a dye image with extremely little light yellowing is formed, and comprehensive image preservation including heat resistance, moisture resistance, and fading resistance is achieved. It not only has excellent properties, but also has good processing stability such as recoloring property in bleach-fixing processing, and also has good stability of the emulsion coating solution during manufacturing, and can be stably mass-produced. Specific effects will be achieved.

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

Example-1 Said exemplary couplers t 1-8 , l-14, I-4
3) Or the following comparative coupler (1) was dissolved in dibnal phthalate and ethyl acetate, respectively, and alkanoyl
C (alkylnaphthalene sulfonic acid, manufactured by Typon) was added to a gelatin water bath solution and dispersed in a homogenizer to remove the cyan coupler dispersion.

Next, the exemplified compound (11-15, n -22, 1li
-3.

The sensitizing dyes shown in ll-11 and ll-271 or the following comparative sensitizing dyes (A, ml, C, i) and E+ were each added in an amount of 2.0 x 10' mol per mol of silver halide.Chemical ripening was completed. The above-mentioned cyan coupler dispersion was added to each 100μ of the finished silver chlorobromide emulsion so that it contained 90.4 moles per mole of silver halide to prepare 40 kinds of photographic coating solutions.

The coating solution prepared as described above was coated on polyethylene Co) M immediately after preparation, after being left at 40°C for 3 hours, and after being left at 40°C for 6 hours, and dried to obtain a silver halide photographic material. Ta.

Comparison Sensitizing dye 02H502H5 e re
Sensitometry was carried out using Model -60 (manufactured by Konishiroku Photo Industry KK), and the relative sensitivity of each coating solution after being left standing was determined by setting the sensitivity of the immediately applied dry sample as 100. The results are shown in Table 1. Note that all the phenomena were performed under the same conditions as follows.

Processing process (32.8℃) Processing time Color development
Bleach-fix for 3 minutes and 30 seconds Wash with water for 1 minute and 30 seconds Dry for 3 minutes and 30 seconds Color developer composition Bleach-fix composition 1;, 1. -"Fzu4, Self-Table -1 Table 1 (Continued) As shown in Table 1 above, the sensitizing dye according to the present invention is used when producing a silver halide photographic material containing the cyan coupler according to the present invention. In this case, the photographic coating solution of the present invention exhibits very little decrease in sensitivity even after a long period of time, and remains stable. Photographic coating liquids other than those of the present invention using f:f have a significant decrease in sensitivity and are unstable.

That is, it can be seen that the silver halide photographic material of the present invention always has a constant quality.

Example-2 The cyan coloring dye If! was prepared using the same method as in Example-1 for the samples of N[11 to 40 prepared in Example-1. ! J
A dark fading test was carried out by forming a 100% polygon and leaving it at a constant temperature of 77° C. for 500 hours in a dark place. And the dye residual rate (D/
Do X100) f Sakura Color giiPDA-60
Measured using a red filter. Table the results.
2vc shown.

Table 2 Table 2 (Continued) As shown in Item 2 above, as a result of conducting a fading test of cyan dye images on the above materials with N(L 1 to m40), it was found that the photosensitive material containing the cyan coupler according to the present invention was , it can be seen that the fading resistance of the cyan dye image is extremely superior compared to the comparative photosensitive material containing cyan coupler.Furthermore, Table 1
Together with the above results, it can be seen that the silver halide photographic material of the present invention has excellent fading resistance of cyan coloring dye images and always has constant quality.

Example-3 Example-1 with different cyan coupler and sensitizing dye
, -2 was conducted. That is, the exemplary couplers of Example-1 are Cl-4, 1-17, and 1-30.

l-36, l-46) and comparative couplers as shown below (
In place of Y), a sensitizing dye was added to the exemplified compound (I-8
゜1 [-14, n-29) and the following comparative sensitizing dye F
, G was replaced with 30 kinds of coating liquids for the upper summer in the same manner as in Example-1, and after the preparation, after being left at 40°C for 3 hours, and at 40°C.
After being left at 0° C. for 6 hours, it was coated on polyethylene coated paper and dried to obtain a silver halide photographic material.

Furthermore, tests similar to those in Example-1 and Example-2 were conducted, and the results are shown in Table-3.

Comparative coupler JL Comparative sensitizing dye 1e 1 (OH213803e(OH213803H-N(c2
H51s Table-3 Table-3 (Continued j J',:,-,','From the results of All-mounted Table-3, silver halide photographic sensitizers containing the cyan coupler according to the present invention as in Example-1 When producing the material, the photographic coating solution of the present invention using the sensitizing dye according to the present invention is stable with very little decrease in sensitivity even after being aged for a long time.
Similarly to Example 2, it can be seen that the silver halide photographic material containing the cyan coupler of the present invention has extremely excellent fading resistance on the cyan dye surface.

That is, it can be seen that the silver halide photographic material of the present invention has excellent cyan dye image fading resistance and always has constant quality.

Example 4 Coating solutions for each layer were prepared on a support made of polyethylene coated paper so as to follow the structure shown in Table 4, and the layers were sequentially applied from the support side to form a multilayer silver halide color photosensitive material Nu.
A sample of 71-Nα86 was prepared.

Here, each coating solution for the first layer, third layer, and fifth layer was prepared by VC as follows.

The first layer yellow coupler Y-1 and stain inhibitor AS-1 are dissolved in dinonyl phthalate and ethyl acetate, mixed with an aqueous gelatin solution containing sodium alkylnaphthalene sulfonate, and emulsified and dispersed using an ultrasonic hogenizer. The resulting yellow coupler dispersion is added to a silver chlorobromide emulsion spectrally sensitized with sensitizing dye H to prepare a coating solution.

Third layer Magenta coupler M-1, anti-stain agent As-1, and anti-fading agents AO-1 and AO-2 are dissolved in dioctyl phthalate and acid acetic acid ether, and mixed in an aqueous gelatin solution containing sodium alkylnaphthalene sulfonate. A magenta coupler dispersion obtained by dispersing the emulsion using an ultrasonic homogenizer is added to a silver chlorobromide emulsion spectrally sensitized with sensitizing dye I to prepare a coating solution.

Fifth layer cyan coupler 1-4 and stain inhibitor As-1 are dissolved in dioctyl phthalate and ethyl acetate, mixed with an aqueous gelatin solution containing sodium alkylnaphthalene sulfonate, and emulsified and dispersed using an ultrasonic homogenizer. The cyan coupler dispersion obtained above was added to a silver chlorobromide emulsion spectrally sensitized with sensitizing dye 1-15 to prepare a coating solution No. 71.

Similarly, a coating solution of N (172 to Nα86) was prepared under the composition conditions of the five layers shown in Table 5 (cyan coupler, sensitizing dye).

In order to examine the effect of the present invention, the valley coating g prepared as described above was coated on polyethylene-coated paper immediately after conditioning, after being left at 4 and 4 ocvc for 3 hours, and after being left at 40'CVc for 6 hours. As shown in Tables 4 and 5, the layers from layer to 7 are coated sequentially from the support side and dried. All tests similar to those in Example-1 and Example-2 were conducted, and the results are shown in Table-5.

Table-4 Table-4 (continued) The numbers in parentheses indicate the amount of coating or addition.

Yellow coupler y-i L'NI Macenta coupler M-1 0 is UV absorber UV-1 0, Hll (t) Ultraviolet absorber UV-2 H 04H9 (t) Anti-fading agent AO-1 Anti-fading agent J~ 0-2 Llti3 Lih3 Sensitizing dye H Sensitizing dye [Stain inhibitor As-1 H From the results shown in Kinpaku Table-5 below, the cyan coupler according to the present invention and the sensitizing dye according to the present invention were used. The silver halide photographic light-sensitive material of the present invention shows very little decrease in sensitivity even if the photographic coating solution is aged for a long time during the production of the silver halide photographic light-sensitive material, and the sensitivity balance of the three layers is well-balanced. It can be seen that it always has a constant quality. Furthermore, the silver halide photographic light-sensitive material of the present invention has extremely excellent dark fading resistance of cyan dye images.
It can be seen that the layers are well balanced.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer provided on a support, wherein the silver halide emulsion layer has a cyan power represented by the following general formula [1]. The silver halide in the silver halide emulsion layer contains at least one of the following general formulas [■
] and a silver halide photographic light-sensitive material, which is spectrally sensitized with at least one compound from the group of compounds represented by the general formula (1). In the general formula El) H 1 L, R1 represents an alkyl group or an aryl group. R2 represents an alkyl group, a cycloalkyl group, an aryl group, or a (J heterocyclic group. R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.
It may be combined with Gi R1 to form a ring. Zz Lt
It represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a 6J aromatic primary amine color developing crude drug. ] General formula [11] [In the formula, "1", R2 and B3 each represent a methine group. 6 and Y26;
6Jz each represents an alkyl group. However, at least one of R4 and R5 has a sulfo group. iAl
, A2, B1, B2, C1, C2, Dl and B2
&t, respectively hydrogen atom, halogen atom, alkyl group,
Represents an alkoxy group, phenyl group, cyan group, nitro group, or alkoxycarbonyl group. Also, A1 and Bl, Bl and C1, C1 and Dl, A2 and B2, B2
and C2, and the combination of C2 and B2, both of which are 1
They may be condensed to form a benzene ring. Me represents a cation, and m represents O or l. ] General formula [table] 7-・-22-1 In the c formula, 22 represents a nonmetallic atom group that is essential for constituting a quinoline ring together with the nitrogen atom and carbon atom connected to the bond T. Zs (tt A group of atoms necessary to constitute a thiazole ring, benzothiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole ring or nandoselenazole ring together with the bonded yaro atom and carbon atom) "6, R7 and R8
have 8 alkyl groups each. XC) represents an anion. l and nLJ each represent an integer of 0 or 1. ]