JPS6172245A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material which has a good spectral absorption characteristic and provides a cyan dye image of relatively long wavelength by incorporating a specific photographic cyan coupler into a photosensitive emulsion layer. CONSTITUTION:The photographic cyan coupler expressed by the formula is incorporated into the photosensitive emulsion layer. In the formula, R<1> denotes an alkyl group or aryl group, the alkyl group is an alkyl group of 1-20C and may have a substituent and a phenyl group is preferably the aryl group, and Z denotes a hydrogen atom or the group which can be desorbed in the stage of coupling reaction with the resulted product of oxidation of a color developing agent. These groups can control the reactivity of the coupler and can exert an advantageous influence on the own layer or the other layer by providing functions such as development restraining, bleach restraining, bleach acceleration and color correction after detaching from the coupler. The representative examples of these groups are a halogen atom, (chlorine atom, fluorine atom, etc.), etc.

Description

Detailed Description of the Invention ■1 Background of the Invention Technical Field The present invention relates to a silver halide color photographic light-sensitive material that exhibits particularly good spectral absorption characteristics and that can be used in a bleach bath or a bleach-fix bath that has been fatigued by running. The present invention also relates to a silver halide color photographic material that provides a cyan dye image without dye loss.

<Prior art and its problems> Usually, in a silver halide color photographic light-sensitive material, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the color developing agent produced at this time is A dye image can be obtained by coupling the oxidized form of the main drug with couplers that form yellow, magenta, and cyan dyes.

The couplers widely used to form the cyan dye are phenol-based and naphthol-based cyan couplers.

In recent years, in the photographic industry, with the rapid development of color photography, the amount of color negative film to be processed has become enormous, and a phenomenon has arisen in which the bleach bath or bleach-fix bath becomes fatigued during running.

Naphthol compounds, which have been widely used as cyan couplers for color negative films, have the disadvantage that when processed in a tired bleach bath or bleach-fix bath, the dye that has been formed returns to the leuco form, causing dye loss. discovered.

In order to improve these drawbacks, Japanese Patent Application Laid-Open No. 47-2113
Publication No. 9, Publication No. 56-65134, Publication No. 57-204
No. 543, No. 57-204544, No. 57-
No. 204545, No. 58-98731, No. 5
As described in Publication No. 8-187928, cyan couplers having a phenylureido group at the 2-position of phenol were developed, which dramatically improved dye loss. In terms of spectral absorption characteristics, since the maximum absorption wavelength is relatively short compared to naphthol couplers, absorption in the green light region on the short wavelength side is large, which is disadvantageous in terms of color reproduction. In particular, green light is the most sensitive part of the human visual system, and even a small reduction in unnecessary absorption will bring about a significant visual improvement, so further improvements have been desired.

(1) Object of the Invention The first object of the invention is to provide a silver halide color photographic light-sensitive material which has good spectral absorption characteristics and provides a cyan dye image with a relatively long wavelength.

A second object of the present invention is to provide a silver halide color photographic material that provides a cyan image without dye loss even when using a bleach bath or a bleach-fix bath that is fatigued by running.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material having a cyan image with high sensitivity and high color density.

A fourth object of the present invention is to provide a silver halide color photographic material having a cyan image that can be manufactured at relatively low cost.

A fifth object of the present invention is to provide a silver halide color photographic material that provides a cyan image with excellent dispersion stability.

The above object of the present invention was achieved by containing a photographic cyan coupler represented by the following general formula [I] in a photosensitive emulsion layer.

General formula [I]: (However, in this general formula, R1 is a group sufficient to impart diffusion resistance to the coupler, R2 and R3 are a hydrogen atom or a halogen atom, and Z is a hydrogen atom, or Represents a group that can be eliminated during a camping reaction with an oxidation product of a color developing agent, and R
2 and R3 (both are halogen atoms) ■1 Detailed description of the invention In the present invention, R1 in general formula (1) represents an alkyl group or an aryl group; is an alkyl group having 1 to 20 carbon atoms, which may have a substituent, and is preferably a group represented by the following general formula (n).

General formula [■]: [However, in this general formula, Y is 10-1-5-1-SO□-, R4 is an alkylene group having 1 to 20 carbon atoms (methylene, 1
, 1-ethylene, 1,1-propylene, 1°3-propylene, 2-methyl-1,1-propylene, 1,1. -benthylene, 1.1-hebutylene, 1.1-nonylene, 1
．． 1-undecylene, 1゜1-tridecylene, -1,1
-pentadecyl group, etc.), R5 is a halogen atom (chloro atom, fluorine atom, etc.), a hydroxy group, an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a tert-butyl group, a tert-pentyl group, cyclopentyl group,
tert-octyl group, pentadecyl group, etc.), alkoxy group (methoxy group, ethoxy group, isopropoxy group,
butoxy group, hexyloxy group, dodecyloxy group, etc.)
, alkylsulfonamide group (methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group,
octylsulfonamide group, hexadecylsulfonamide group, etc.), arylsulfonamide group (henzenesulfonamide group, m-chlorobenzenesulfonamide group, toluenesulfonamide group, p-methoxybenzenesulfonamide group, p-dodecyloxybenzenesulfone amide group, etc.), alkylsulfamoyl group (butylsulfamoyl group, tert-butylsulfamoyl group, dodecylsulfamoyl group, etc.), arylsulfamoyl group (benzenesulfamoyl group, toluenesulfamoyl group, etc.), group, dodecyloxybenzenesulfamoyl group, etc.), alkylsulfonyl group (methanesulfonyl group, butanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, p-benzyloxyphenylsulfonyl group, p-benzyloxyphenylsulfonyl group,
-hydroxyphenylsulfonyl group, etc.), and alkoxycarbonyl groups (ethoxycarbonyl group, butoxycarbonyl group, hexadecyloxycarbonyl group, etc.). ! represents an integer of 1 to 4, preferably 1 or 2. When l is 2 or more, Rs may be the same or different. ] In the present invention, when R1 in general formula (1) is an aryl group, it is preferably a phenyl group, and the phenyl group may be substituted with R5 shown in the above general formula (I[).

In the present invention, Z in the general formula (1) represents a hydrogen atom or a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent, but such a group can be easily understood by those skilled in the art. Are known. These groups can also control the reactivity of the coupler and, after leaving the coupler, perform functions such as development inhibition, bleach inhibition, bleach acceleration, color correction, etc., thereby improving the white layer or other properties. layers can be advantageously influenced.

Typical examples of these groups include halogen atoms (chloro atom, fluorine atom, etc.), alkoxy groups (methoxyethylaminocarbonylmethoxy group, methanesulfonylethoxy group, etc.), and aryoloxy groups (p-ethoxycarbonylphenoxy group, p-ethoxycarbonylphenoxy group, -Methoxyphenoxy group, p-butanesulfonamidophenoxy group, p-β-carboxypropanamidephenoxy group, etc.), arylthio group (0-butoxyphenylthio group, p-tertbutylphenylthio group, m-butanesulfonamidophenyl thio group, etc.). Such groups that are eliminated during coupling are described, for example, in U.S. Pat. No. 2.455.169; 3,22
No. 7,551: No. 3,432.521; 3,476
．． No. 563; No. 3.617, 291; No. 3,880.6
No. 61; No. 4,052,212 and No. 4,134,7
No. 66 and British Patent and Patent Application Publication No. 1,466.728; No. 1,531,927:1.
No. 533,039; No. 2,006,755 and 2,
No. 017.704.

In the present invention, R2 and R3 in general formula (1) are
It represents a hydrogen atom or a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and a chlorine atom is preferred.

The cyan coupler used in the present invention is preferably represented by the following general formula (nl).

General formula [■]: <Z' [In this general formula, Rz' and R'' are hydrogen atoms or chlorine atoms, R'' is alkylene having 1 to 2 o carbon atoms, R5
is a hydroxy group or an alkyl group having 1 to 2 carbon atoms, Z
'represents a hydrogen atom, a halogen atom, or an aryloxy group, at least one of , / and R3' is a chloro atom, l is an integer of 1 or 2, and when l is 2, R'' may be the same. Even if the number of carbon atoms is different, it is preferable that the number of carbon atoms is 8 to 25.] Representative specific examples of the cyan coupler of the present invention are described below, but the present invention is not limited thereto.

The cyan coupler of the present invention can be easily synthesized by conventionally known methods. General synthesis examples are shown below.

Cold shyness (''-μ ahead A Meng two fever'' 1st day illusion-(A) 2-(4
-Synthesis of chloro-3-cyano)phenylureido-5-ditrophenol 15.4 g of 2-amino-5-ditrophenol, 27.3 g of 4-chloro-3-cyanophenyl carbamate, and 0.7 g of imidazole were added in 300 ml of toluene. Inside was washed with oil. 20.1 g of yellow crystals were obtained (yield 60.4%).

(B) Synthesis of coupler 6 ○2N CN CN0H 2-(410rho3-cyano)phenylureido-5-
16.6 g of nitrophenol in 3 g of tetrahydrofuran
00m1! After dispersing the mixture, hydrogenation was performed under normal pressure using a Raney-Kell catalyst. After consuming the theoretical amount of hydrogen, the Raney nickel catalyst was filtered off, and 4.7 g of pyridine, α
20.2 g of -(2,4-di-tert-amyl)phenoxyhexanoyl chloride was added, and the mixture was stirred at room temperature for 1 hour. Tetrahydrofuran was distilled off from the reaction solution under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. After washing the oil layer with water and separating it, ethyl acetate was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography. It was crystallized from acetonitrile to obtain 24.1 g of white powder.

The structure was measured using NMR and MASS, and it was found to be the desired product.

Synthesis Example-2 (Synthesis of coupler number 7) (^”) Synthesis of 2-(4-chloro-3-cyanophenyl)ureido-4-chloro-5-nitrophenol H J1 2-amino-4-chloro-5 -nitrophenol18.
9 g of 4-chloro-3-cyanophenyl phenyl-1-27.3 g and 0.9 g of imidazole were added to 300 ml of toluene, and the mixture was boiled and refluxed for 5 hours. After the reaction solution was allowed to cool to room temperature, the precipitated crystals were filtered off and washed with methanol. 23.5 g of yellow crystals were obtained (yield: 64
．． 0%).

(B) Synthesis of coupler Kan7 2-(4-chloro-3-cyanophenyl)ureido-4
After dispersing 18.4 g of -chloro-5-ditrophenol in 300 ml of tetrahydrofuran, hydrogenation was performed at normal pressure using a Raney nickel catalyst.

After consuming the theoretical amount of hydrogen, the Raney nickel catalyst is filtered off,
4.7 g of pyridine and α-(2,4-tert) were added to the filtrate.
-amyl) phenoxyhexanoyl chloride 20.2
g was added thereto, and the mixture was stirred at room temperature for 1 hour. Tetrahydrofuran was distilled off from the reaction solution under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. After washing the oil layer with water and separating it, ethyl acetate was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography.

It was crystallized from acetonitrile to obtain 22.0 g of white powder. The structure was measured using NMR and MASS, and it was found to be the desired product.

A silver halide color photographic light-sensitive material prepared using the coupler according to the present invention (hereinafter referred to as the coupler of the present invention) may contain a conventionally used dye-forming coupler.

The cyan dye-forming couplers used in this invention can be used in conventional methods and purposes for using cyan dye-forming couplers in photographic technology.

Typically, the cyan coupler of the present invention is contained in a silver halide emulsion layer and/or a non-photosensitive layer adjacent thereto. A silver halide color photographic light-sensitive material containing the silver halide emulsion layer can be obtained by blending it into an emulsion and coating this emulsion on a support. This silver halide color photographic light-sensitive material may be monochromatic or multicolored. In the case of multicolor, the diazicoupler of the present invention is usually contained in a red-sensitive emulsion, 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.

Each structural unit forming a dye image in the present invention is
It consists of a single-hole emulsion layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

The layers necessary for silver halide color photographic materials, including the layers of image-forming units described above, can be arranged in various orders as known in the art.

A typical multicolor silver halide color photographic light-sensitive material consists of a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler. one is a cyan coupler of the invention), at least one has at least one magenta dye-forming coupler.
A magenta dye image-forming unit consisting of two green-sensitive silver halide emulsion layers and a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler are carried on a support. consists of things.

The photographic material may have additional layers, such as a filter layer, an interlayer, a subbing layer, etc.

In order to prepare a silver halide color photographic light-sensitive material using the coupler of the present invention, each light-sensitive layer containing a yellow dye-forming coupler and a magenta dye-forming coupler is also required.

As the yellow dye-forming coupler that can be used, conventionally known ones can be mentioned. For example, it is represented by the following general formula (IV).

General formula (IV) RhCOCHCONHR' represents a group that can be separated by campling with an oxidation product of a drug. ] In the general formula (IV), Z can be represented by the following general formula [V
], (VI) are preferred.

General formula [■] Knee N! ' [However, in this general formula, F represents a group of nonmetallic atoms capable of forming a 5- or 6-membered ring. ] General formula [■] K-OR" [However, in this general formula, R8 represents an aryl group, preferably a substituted phenyl group.] As magenta dye-forming couplers that can be used, conventionally known ones can be mentioned. For example, , the following general formula [■], [■
], (IX).

General formula [■]: [However, in this general formula, R9 is an alkylcarbonyl group, arylcarbonyl group, or aryl group, RIG is a monovalent group, and Z is a hydrogen atom or an oxidation product of a color developing agent. Represents a group that can be removed by coupling. ] General formula [■]: [However, in Mele's general formula, R" is an alkyl group or an aryl group, RI2 is an alkyl group, aryl group, or alkylthio group, and 2 is a coupling with an oxidation product of a color developing agent. General formula [■]: [In this general formula, Rl3 represents a monovalent group, R- represents an alkyl group, aryl group, acylamino group, alkoxy group, Z represents a hydrogen atom or a group that can be eliminated by coupling with an oxidation product of a color developing agent.] Furthermore, the cyan dye-forming coupler of the present invention may be combined with other cyan dye-forming couplers. can.

Cyan dye-forming couplers that can be used include conventionally known ones. For example, the following general formula % Formula % General formula [X]: [However, in this general formula, RIM is an alkyl group or an alkyl group, and Z is a hydrogen atom or a cup with an oxidation product of a color developing agent. The ring represents a group that can be removed. ] General formula (IV), [■], [■], (IX), (X
Specific examples of the yellow, magenta, and cyan couplers represented by ) include the following compounds, but are not limited to these. Further, each of these couplers may be arbitrarily selected as required, and two or more types may be used in combination.

(Y-1) (Y-2) (Y-3) (Y-4) (Y-5) (Y-6) (Y-7) (Y'-3) (Y-9) (Y-10 ) 1'M (Y-11) (M-1) CM-2) N (M-3) (J (M-4) (M-5> (M-61 l (M-7) l (M- 8) C+oHi+ (M-9) (C-1) H C6Hu(t) (C-2) H OCHtCONHCH2CH20CHs (to 3) H (C-41 CsH++ω ((, -51 H ■ rzHts (C-6) This invention In order to incorporate the cyan coupler and each coupler according to the present invention into a silver halide photographic material, conventionally known methods may be followed.For example, known high boiling point solvents and low boiling point solvents such as butyl acetate and butyl propionate may be used. After dissolving the cyan coupler of the present invention or each coupler according to the present invention in a mixed solution of can be added to silver halide to prepare the silver halide emulsion used in the present invention.

As the high boiling point solvent that can be used, conventionally known ones can be mentioned. For example, the following general formulas (XI), (XII), [
Such as XI[r), [XIV), and (XV).

Among these, formulas (XI) and CX2] are preferred, and phthalic acid diesters are particularly preferred.

General formula (XI): CB)p [However, in this general formula, B is a halogen atom, having 1 to 2 carbon atoms
0 alkoxy group or -COOR16, Rlh is an alkyl group having 1 to 20 carbon atoms or phenyl group, p is 0 to 3
represents an integer. When p is 2 or more, B may be the same or different. ] General formula (XII): 0 = P (ORlh)3 [However, in this general formula, RIth has the same meaning as R1'' shown in the above general formula (XI).] General formula (XII [): [However, In this general formula, R" and R" represent an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R'9 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or a phenyl group.
I8 and RI'' may form a 5-membered or 6R ring using a nonmetallic atomic group.] General formula (XIV): R"Co○R" [However, in this general formula, R2 (1 is RI6 is an alkyl group having 1 to 20 carbon atoms, and R1 is represented by the general formula (XI).
It is synonymous with 1+. [However, in this general formula, RZI represents an alkyl group having 1 to 20 carbon atoms, m represents an integer of 1 to 3, and when m is 2 or more, R'' may be the same or different. Good.] The general formula (XN, (X[I], (Xlll), (XIVI, (X
Specific examples of the high boiling point solvent represented by V) include the following compounds, but are not limited thereto. Further, these high boiling point solvents may be arbitrarily selected and two or more kinds may be used in combination.

(HBS-1) (HBS-2) (
HBS-3) (HBS-4)
(HBS-5) (HBS-
6) C, Hs (HBS-7) (HBS-
8) (HBS-9) (H
BS-10) C, H.

(+1135-1'll (Ht3
S-1ri (HBS-131 (HBS-14) Hs (HBS-15) (HBS
-10 (HBs-17) (
HBS-1 second (HBS-19)
(HBS-20) (HBS-21)
(HBS-22)〇H3 (HBS-25) (H
BS-24) (HBS-23)
(HBS-26) (HBS-D
(HBS-28) (II
t3S 29) (HHS
-301ocaH9 (HB S-311 (HB S - Katana (HBS-33) (HB
S-34) (HBS-351 (HBS-Sword (HBS-37) (HBS
-38) (HBS-39)
(HBS-40) (HBS-41)
(HBS-42) (HBS-43)
(HBS-44) (HBS-4
3) (HBS-46)
(HB S-47) (HB
S-43) (HB S-31) CH* COOCHz CHt OCHz CHz O
Ca Hq (HBS-32) (HBS-53) (HBS-
Death 2M5 (HBS-55) (HB
S-56) (HBS-57)
(HBS-58) (HBS-59)
(HBS-60) The silver halide color photographic light-sensitive material prepared according to the present invention may contain a colored coupler for color correction or a so-called DI.
R coupler, colorless coupler for improving the hue of sensitive materials;
Alternatively, various commonly used additives such as ultraviolet absorbers and stabilizers for photographic performance may be included.

Colored couplers that can be used include colored magenta couplers and colored cyan couplers, and are represented by the following general formulas (XVI) and (XV If).

General formula (XVI): M-N=N-Ar [However, in this general formula, M represents a residue obtained by removing one hydrogen atom from the active site of the magenta coupler, and A' represents an aryl group.] General Formula (XVIII: C-fJ +TN = N-Ar [However, in this general formula, C is a residue obtained by removing hydrogen from the active site of a phenolic or naphthol-based cyan coupler,
J represents a divalent bonding group, Ar represents an aryl group, and q represents O or I. ] M in the general formula (XVI) is the general formula (V
Magenta couplers represented by n ) are preferred (R9 is a substituted phenyl group). Moreover, the general formula CXV [I
) is preferably a cyan coupler represented by the above-mentioned general formula [x], and q is preferably l. - Colored magenta couplers and colored cyan couplers represented by general formulas (XVI) and (XV II) include, but are not limited to, the following compounds, and two or more of each may be used in combination. good.

(CM-1) l l (CM-3) (,L i (CM-4) I2 (CM-5) (CM-6) (CM-7) (CG-1) (CC-2) (CC-4) (CC-5) COOCH.

(CC-6) DIR couplers that can be used include the following general formula (XV
Im).

General formula (XVI[[): Cp-+Jh-■ [However, in this general formula, Cp has a site capable of campling with the oxidation product of the color developing agent, and one hydrogen atom is removed from that site. J' is a divalent group that can be released from Cp by reaction with the oxidation product of the color developing agent and can release ■ by intramolecular nucleophilic substitution reaction, electron transfer, hydrolysis, etc. represents a development-inhibiting group, and q represents 0 or 1. ] Preferred DIR couplers are illustrated below, but are not limited to these. Each DIR coupler is variously selected depending on the purpose and use, and if necessary, 2
More than one species may be used in combination.

(D-1) N N CzHs (D-3) CD-4) (D-5) (D-6) (D-8) (D-9) (D-10) (D-11) (D- 12) (D-13) As the ultraviolet absorber that can be used, the following general formula (XIX
) and general formula (XX).

- Tomin CXEX3: [However, in this general formula, R22 represents an alkyl group having 1 to 20 carbon atoms, RZ3 represents a halogen atom, r represents an integer of 1 or 2, and β represents an integer of O or 1, respectively.

When r is 2, Rtz may be the same or different. ] General formula (XX): [However, in this general formula, R14 represents an aryl group or a vinyl group, and R25 and R2& represent a cyano group, an alkoxycarbonyl group, or an arylsulfonyl group. ] Specific examples of ultraviolet absorbers are listed below, but they are not limited to these, and two or more types may be used in combination if necessary.

(U-1) c4Hq(t) (II 2) C=Hq(di℃) (Ll-3) C[1°(IJ-4) caHJt) (U-5) l-1 CsH++(t) (U -6) CaHq(t) (U-7) CtH Police (U-8) (U-9) Cz Hs (U-10) (U-11) (U-12) (U-13) COOCuMtj ([J -14) (U-15) C Stabilizers that can be used include antifoggants and image dye stabilizers, but those of the following general formula [XXI], (XX
If ), (XX I[).

General formula [XXI): R27 R2a [However, in this general formula, RZ7 and R211 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R29 represents an alkyl group having 1 to 20 carbon atoms.
20 alkyl groups or sulfoxy groups, and t represents an integer of 1 or 2. When t is 2, R29 may be the same or different, and Roll and R'' may form a 5- or 6-membered ring using a nonmetallic atomic group.] General formula ( XXn): [However, in this general formula, Rzt, R'' and RZ9 represent the above general formula (XXI).
It is synonymous with Z9. t' represents an integer of 1 or 2,
When t' is 2, R29 may be the same or different, and R29 may form a 5- or 6-membered ring at the ortho position. ] General formula (XXIII): l-1 [However, in this general formula, Rio is an alkyl group having 1 to 20 carbon atoms, phenoxycarbonyl group, Hensensulfonamide group, or alkylsulfonamide group, and a is 1 to 3 represents an integer of , and when a is 2 or more, R3° may be the same or different. ] Below, general formula [XXI], [X
X II ], (XXII+], but the stabilizers are not limited to these, and if necessary, two or more of them may be used in combination H (A2) H 1,5ec) +zhzs' H (A- 3) H H (A-4) (A-5) H H (A~6) CsH+1(t) (A-7) OCa H17 (A-8) (A-9) (A-10) C+zHzsCHCCOCzHs (A -11) (A-13) When the cyan coupler of the present invention and each coupler according to the present invention are added to a silver halide emulsion, it is usually about 0.005 to 2 moles per mole of silver halide, preferably 0.005 to 2 moles, preferably 0.005 to 2 moles per mole of silver halide. 01
It is added in a range of 0.5 mol.

As the silver halide used in the silver halide emulsion used in the present invention, common /S halides such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Includes anything used in emulsions.

The silver halide emulsion constituting the silver halide emulsion layer according to the present invention can be produced by various manufacturing methods including the usual manufacturing method.
For example, a method such as that described in Japanese Patent Publication No. 7772/1984 is used, that is, an emulsion of silver salt grains consisting of at least a portion of silver salt whose solubility is higher than that of silver bromide is formed, and then,
A method for producing a so-called co-op emulsion in which a small amount of these grains (some of them are converted to silver bromide or silver iodobromide), or a method for producing a co-op emulsion with a small number of grains, or 0.
It can be formed by any manufacturing method, such as the method for manufacturing J-Tubman emulsions made of fine-grained silver halide having an average grain size of 1 μm or less. Furthermore, the silver halide emulsion of the present invention is
Sulfur sensitizers, such as arylthiocarbamide, thiourea, cystine, etc., also active or inactive selenium sensitizers, and reduction enhancers, such as stannous salts, polyamines, etc., and noble metal enhancers, such as gold sensitizers. , specifically potassium aurithiocyanate, potassium chloroaurate, 2
- Aurosulfobenzthiazole methyl chloride, etc., or sensitizers of water-soluble salts such as ruthenium, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chlorooleate and sodium chlorovaladite, etc. alone or Chemical sensitization can be achieved by using appropriate combinations.

Further, the silver halide emulsion used in the present invention can contain various known photographic additives. For example, "Research Disclosure" December 1978,
Photographic additives such as those described in Na 17643.

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

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat. No. 2,269,234;
No. 270.378, No. 2.442.710, No. 2
．． Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Patent Nos. 454,620, 2.776, and 280.

The support according to the present invention may be appropriately selected from conventionally known supports such as plastic film, plastic laminated paper, baryta paper, synthetic paper, etc. depending on the intended use of the photographic material. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer.

The thus constructed silver halide color photographic light-sensitive material of the present invention can be subjected to various photographic processing methods for color development treatment after exposure. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component.

A typical example of this color developing agent is a p-phinyl diamine type, such as diethyl-p-
Phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-3-(N-ethyl-N-β-hydroxyl ethylamino)-toluene, 2-amino-3-(N
-ethyl-N-β-methanesulfonamidoethyl)amine toluene sulfate, 2-amino-3-(N-ethyl-N
-β-methanesulfonamidoethylamino)toluene,
4-(N-ethyl-N-β-hydroxyethylamino)
Examples include aniline, 2-amino-3-(N-ethyl-β-methoxyethyl)aminotoluene, and the like. Among these, 2-amino-3-(N-
It is selected from ethyl-N-β-hydroxyethylamino)-toluene and 2-amino-3-(N-ethyl-N-β-methanesulfonamidoethylamino)-toluene. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, color developing solutions generally contain alkaline agents such as sodium hydroxide,
It contains ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and may further contain various additives such as alkali metal halides such as potassium bromide, or development regulators such as citradinic acid.

The silver halide color 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. A color developing herbal drug precursor is a compound that can produce a color developing agent under alkaline conditions,
Examples include Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, phthalic acid imide derivative precursors, phosphoric acid amide derivative precursors, sugar amine reactant precursors, and urethane type precursors. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
No. 42,599, No. 2,507.114, No. 2.
No. 695.234, No. 3.719.492, British Patent No. 803.783, Japanese Patent Application Publication No. 135628/1983,
No. 54-79035, Research Disclosure No. 15.159, No. 12,146, No. 13,924
No. is stated in each specification.

These aromatic primary amine color developing agents or their precursors need to be added in an amount that will provide sufficient color development during development. This amount varies considerably depending on the type of photosensitive material, etc., but is generally between 0.1 and 5 moles, preferably 0.1 to 5 moles, per 1 mole of photosensitive silver halide.
It is used in a range of 5 mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the compound into a photographic light-sensitive material, it can be added after being dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc.
They can also be added as emulsified dispersions using high-boiling organic solvents such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., or by impregnating latex polymers as described in Research Disclosure No. 14850. You can also do that.

The silver halide color photographic light-sensitive material of the present invention is usually subjected to bleaching and fixing, bleach-fixing, and water washing after color development.

Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron (■), cobalt (■), and tin (n), and especially complex salts of these polyvalent metal cations and organic acids, such as: Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylenediaminediacetic acid, metal complex salts or ferricyanates such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, dichromic acid Salts and the like may be used alone or in appropriate combinations.

(2) Specific Examples of the Invention The present invention will be specifically described below with reference to Examples, but the manner in which the present invention may be carried out is not limited thereto.

As shown in Table 1, each of the cyan couplers of the present invention was weighed in an amount of 0.1 mol per 1 mol of silver, and dibutyl phthalate (as a high-boiling solvent) of the same weight as the coupler was weighed. Each was added to 3 times the amount of ethyl acetate and heated to 60°C to completely dissolve. For comparison, 0.1 mol of each conventionally known comparative coupler was weighed per 1 mol of silver, added to phthalic acid dibutyl ester of the same weight as the coupler weight and 3 times the amount of ethyl acetate, and heated to 60°C. It was completely dissolved by heating. This solution was mixed with 120ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate: manufactured by DuPont).
Mix with 1200 ml of 5% aqueous gelatin solution containing N,
The mixture was dispersed using an ultrasonic dispersion machine to obtain an emulsion.

Thereafter, this dispersion was added to 4 kg of red-sensitive silver iodobromide emulsion (containing 7 mol% miodine), and 1,
2% solution of 2-bis(vinylsulfonyl)ethane (water:
Methanol = l: 1) 120 ml was added and coated on a subbed transparent polyester base and dried to obtain a sample with a stable coating film (coating weight 15μ/1).
00 cJ).

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment.

The results are shown in Table 1.

Note that the sensitivity and maximum color density were measured using a PDA-65 type densitometer manufactured by Konishiroku Photo Industry Co., Ltd.

[Processing process] (38°C) Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 1 minute and 30 seconds
Fix for 3 minutes 15 seconds Wash with water for 6 minutes 30 seconds 3 minutes 15 seconds
Second stabilization bath The composition of the treatment liquid used in the 1 minute 30 second treatment step was as follows.

[Color developer composition]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 9 salt 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxyamine A sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make up to 1 liter, and use potassium hydroxide to adjust the pH to 1o, o
Adjust to.

[Bleach solution composition]

Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g
Ethylenedi7minetetraacetic acid diammonium salt 10.0 g
Ammonium bromide 150.0 g
Glacial acetic acid 10.0ml
Add water to bring the mixture to 1N, and adjust the pH to 6.0 using aqueous ammonia.

[Fixer composition]

Ammonium thiosulfate (50% aqueous solution) 162
ml anhydrous sodium sulfite 12.4
g Add water to make 11, and use acetic acid to adjust pH to 6.5.

[Stabilizing liquid composition]

Formalin (37% aqueous solution) 5. Om
1 Konidafukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5
Add ml water to make IIt.

(Leaving space below) In Table 1, the relative sensitivity is shown with the sensitivity obtained for sample patient 1 as 100, the maximum absorption wavelength (λwax) is the wavelength of the part where the concentration is 1.0, and the wavelength λS is the wavelength of the part where the concentration is 1.0. The absorption wavelength on the short wave side that gives 20% of the spectral absorption characteristics obtained at a concentration of 1.0 is λw
The value subtracted from ax is shown.

Comparative coupler (A): (compound described in JP-A-56-65134) Comparative coupler (B): (compound described in JP-A-57-204544) Comparative coupler (C); (JP-A-57-204544) Compound described in JP-A No. 204544) Comparative coupler CD): (Compound described in JP-A-57-204544) Comparison coupler (E): Equivalent to the comparison coupler (Compound described in JP-A-57-204544) The sensitivity and maximum color density are as follows. The maximum absorption wavelength and AλS are compared with comparative couplers (A) to (E). In particular, this numerical difference was a significant difference considering that it extended to the green light region, and brought about a significant improvement in color reproduction.

Example-2 After performing wedge exposure on the sample obtained in Example-1,
The development process of Example-1 was performed. On the other hand, the composition of the bleach-fix solution was changed as shown below to examine the discoloration of the cyan dye caused by the fatigued bleach-fix solution.

[Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 50 g Ammonium sulfite (40% solution) 50m7!
Ammonium thiosulfate (70% solution) 140m
1 Ammonia water (28% solution) 20m
1 Ethylenediaminetetraacetic acid 4g Hydrosulfide 5g Add water to make 11.

The maximum color density of the obtained sample was measured. The results are shown in Table 2. Incidentally, the dye residual rate at the maximum density was determined as follows.

(Margins below) Table 2 From Table 2, it is understood that the sample using the naphthol coupler (C-1) shows less fading of the cyan dye, similar to the sample using the cyan dye in the fatigue bleach-fix solution treatment. It will be.

Each sample having the configuration shown in Table 3 was prepared.

1st layer (antihalation layer): ' A gelatin aqueous solution containing black colloidal silver was added at 0.5 g/r of silver.
The coating was applied at a ratio of d to give a dry film thickness of 3.0 μm.

Second layer (intermediate layer): An aqueous gelatin solution was coated to a dry film thickness of 1.0 μm.

Third layer (red-sensitive, low-sensitivity silver halide emulsion layer) Silver iodobromide emulsion (average grain size 0.6μ, silver iodobromide emulsion containing 4 mol% silver iodide, average grain size 0.3μ, A silver iodobromide emulsion containing 4 mol% of silver iodide was mixed in a ratio of 2:1) was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3 was added as a red-sensitive sensitizing dye. ,3'-di(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide: anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3- sulfobutyl)
Thiacarbocyanine hydroxide: and anhydrous 2-(
2-1(5-chloro-3-ethyl-2(5-benzothiazolindene)methyl-1-butenyl-5-chloro-
After adding 5-(4-sulfobutyl)]benzoxacilium, 4-hydroxy-6-methyl-1,3,3a
, 7-chitrazyten 1.0g, 1-phenyl-5
- 20.0 µm of mercaptotetrazole was added to obtain a red-sensitive and low-sensitivity emulsion.

The cyan coupler, DIR compound, colored cyan coupler, antifoggant and high boiling solvent were then added to 150 mj of ethyl acetate! 550 mj of a 7.5% aqueous gelatin solution containing 5 g of sodium triisopropylnaphthalene sulfonate! and emulsified and dispersed using a colloid mill. After heating the dispersion and removing ethyl acetate, the above red-sensitive low-sensitivity emulsion was added to the dispersion to give a dry film thickness of 4.0.
It was coated so that it was μ (1 mole per mole of silver halide).
Contains 00g of gelatin. ).

4th layer (red-sensitive high-sensitivity silver halide emulsion layer) Silver diiobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide) is chemically sensitized with gold puyo and sulfur sensitizers. death,
Furthermore, as a red-sensitive sensitizing dye, anhydrous 9-ethyl-3,3'-
Di(3-sulfopropyl)-4,5°4',5-dibenzothiacarbocyanine hydroxide; anhydrous 3,3'-
dichloro-9-ethyl-3,3'-di(3sulfobutyl)thiacarbocyanine hydroxide; and anhydrous z-
[z-is-chloro-3-ethyl-2(5H)-benzothiazolidene)methicari-1-butenyl-5-chloro-3
-(4-sulfobutyl)'J benzoxacillium and then 4-hydroxy-6-methyl-1,3,3a
.

1.0 g of 7-chitrazyten and 1-phenyl-5
-Mercaptotetrazole 10°0 was added to obtain a red-sensitive emulsion.

Furthermore, cyan coupler, DIR compound, antifoggant and high boiling point solvent were added to 5Qml of ethyl acetate, dissolved by heating, and 1 ml of sodium triisopropylnaphthalene sulfonate was added.
．． The above red-sensitive high-sensitivity emulsion was added to a dispersion that was added to 30 ml of a 7.5% gelatin aqueous solution containing 5 g and emulsified and dispersed in a colloid mill, and the dry film thickness was 2. It was coated so that θμ (contains 100 g of gelatin per mole of halogenated l!).

Fifth layer (middle layer): Same as second layer.

6th layer (green-sensitive, low-sensitivity silver halide emulsion layer): silver iodobromide emulsion with an average grain size of 0.6μ, containing 4 mol% of silver iodide, and an average grain size of 0.3μ, iodide! I! A silver iodobromide emulsion containing 7 mol % was chemically sensitized with gold and sulfur enhancers, respectively, and anhydrous 5,5'-dichloro- as a green-sensitive sensitizing dye.
9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide; anhydrous 3,3'-diphenyl-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide; and anhydrous 9-
Add ethyl-3,31-di(3-sulfopropyl)-5°6,5',6'-dibendioxacarbocyanine hydroxide, then 4-hydroxy-6-methyl-1,3,3a,7 - 1.0 g of chitrazaindene and 20.0 g of l-phenyl-5-mercaptotetrazole
+ng was added and adjusted in the usual manner. The two types of silver halide emulsions thus obtained were mixed at a ratio of 1:1 to obtain one green-sensitive and low-sensitivity halide emulsion.

Furthermore, magenta coupler, DIR coupler, colored magenta coupler, antifoggant, and high boiling point solvent were added to 240 ml of ethyl acetate, dissolved by heating, added to a 7.5% gelatin aqueous solution containing triisopropylnaphthalene sulfonic acid sorta, and milled in a colloid mill. The above green-sensitive low-sensitivity emulsion was added to the dispersion emulsified and dispersed in the process, and the coating was applied to a dry film thickness of 4.0 μm (10 μm per mole of halogenated
Contains 0 g gelatin. ).

7th layer (green-glare high-strength silver halide emulsion layer): Chemically sensitized silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide) with gold and sulfur sensitizers. In addition, as a green-sensitive sensitizing dye, anhydrous 5,5'-dichloro-9-ethyl-3,
3'-di(3-sulfobutyl)oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide; and anhydrous 9-ethyl- 3,3'-
Di(3-sulfopropyl) -5,6,5', 6
Add '-dibenzoxacarbocyanine hydroxide followed by 4-hydroxy-6-methyl-1,3,3a.

1.0 g of 7-chitrazaindene and 1-phenyl-
By adding 5-mercaptotetrazoles io and o, a green-sensitive and highly sensitive silver halide emulsion was obtained.

Furthermore, magenta coupler, DIR coupler, colored magenta coupler, antifoggant, and high boiling point solvent were added to 200 ml of ethyl acetate, dissolved by heating, and added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate to form a colloid. The above-mentioned green-sensitive high-sensitivity emulsion was added to the dispersion emulsified and dispersed in a mill to obtain a dry film thickness of 2.0 μm.
(1 mole of halogenated S)
00 g gelatin).

8th layer (middle layer): Same as second layer.

9th layer (yellow filter layer): 2. In an aqueous gelatin solution in which yellow colloidal silver is dispersed.
3 g of 3-di-t-octylhydroquinone and 1.5 g of di-2-ethylhexyphthalate in 10 ml of ethyl acetate.
A dispersion prepared by dissolving the gelatin in an aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate was added, and this was added to a gelatin solution of 0.9 g/rd, 2.5-
Di-t-octylhydroquinone 0.10g/r+? It was applied to a dry film thickness of 1.2μ at a ratio of .

10th layer (blue-sensitive, low-sensitivity silver halide emulsion layer): A silver iodobromide emulsion (average grain size 0.6μ, containing 6 mol% silver iodide) is chemically sensitized with gold and sulfur sensitizers, Furthermore, as a sensitizing dye, anhydrous 5,5'-dimethoxy-3,3'-di(3-
sulfopropyl) thiacyanine hydroxide, then 4-hydroxy-6-methyl-1,3,3a,7-
1.0 g of citrazaindene and 20.0 g of 1-phenyl-5-mercaptotetrazole were added and adjusted in a conventional manner to prepare a blue-sensitive, low-sensitivity silver halide emulsion.

Furthermore, yellow coupler and high boiling point solvent were added to 30% ethyl acetate.
The above blue-sensitive low-sensitivity emulsion was added to the dispersion, which was added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate and emulsified in a colloid mill, and then dried into a film. It was coated to a thickness of 4.0 μm (containing 240 g of gelatin per mole of silver halide).

11th layer (blue-sensitive high-sensitivity silver halide emulsion layer): A silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide) is chemically sensitized with gold and sulfur enhancers, and Anhydrous 5,5'-dimethoxy-3,3'-di(3
-sulfopropyl) thiacyanine hydroxide,
Then 4-hydroxy-6-methyl-1,3,3a,?
-tetrazaindene 1.0 g and l-phenyl-5
-Mercaptotetrazole 1030 cm was added and adjusted in a conventional manner to prepare a blue-sensitive and highly sensitive silver halide emulsion.

Furthermore, yellow coupler and high boiling point solvent were added to ethyl acetate 24
The above blue-sensitive high-sensitivity emulsion was added to the dispersion, which was added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate and emulsified and dispersed in a colloid mill, and then a dry film was formed. It was coated to a thickness of 2.0 μm (containing 160 g of gelatin per mole of halogenated S).

12th layer (intermediate layer): A high boiling point solvent and an ultraviolet absorber were added to 2 ml of ethyl acetate, added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed using a colloid mill. This was applied at a rate of 1.0 g/n of gelatin to give a dry film thickness of 1.0 μm.

13th layer (protective layer): An aqueous gelatin solution containing 4 g of gelatin and 0.2 g of 1.2-bisvinylsulfonylethane per 100 ml was applied at a rate of 1.3 g/m of gelatin to give a dry film thickness of 1.2 μm. .

Table 3 In Table 3, the amount added is the amount added per mole of silver halide, couplers, DIR couplers, and colored couplers are expressed in mol%, and high boiling point solvents and antifoggants are expressed in weight based on the amount of coupler. %, the weight of the ultraviolet absorber was used per unit d, and the same weight (g) (per rrr) of the high boiling point solvent used in the 12th layer as the ultraviolet absorber was used. In addition, the antifoggant used in the fifth layer is expressed in weight (g) per d,
The high boiling point solvent was used in the same weight as the antifoggant.

Examples of each sample obtained with the configuration shown in Table 3 above
As a result of processing according to the processing steps shown in 1, it was found that the silver halide color photographic material had stable color balance.

Large blood charcoal 2↓ Sample Nll obtained in Example-1, C obtained in 2.8
The spectral absorption characteristics of each dye of -1, comparative coupler (A), and (6) are shown in the drawing.

From this figure, it is understood that the dye formed by the coupler (6) of the present invention has a maximum absorption wavelength at a long wavelength and has good sharpness on the short wavelength side, and is a preferable dye in terms of color reproduction.

[Brief explanation of drawings]

The drawing is a graph showing the spectral absorption characteristics of dyes formed by various couplers. Agent: Patent Attorney Hiroshi Aisaka (Voluntary) Proceedings: July 2, 1985 1, Indication of the case, 1988 Patent Application No. 195233 2, Name of the invention: Silver halide color photographic light-sensitive material 3 Amendment Relationship with the case of a person who does
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Number of inventions to be increased by amendment (1), ``The second line of page 10 of the specification is corrected. (2), page 14 of the specification, 9 Correct "-chloro-3-cyanophenylcarbamate" in line 1 to "-chloro-3-cyanophenyl phenylcarbamate." (3), page 30, line 2 is corrected. (4), page 46, line 4 is corrected. (5), page 49, line 17 i\r OH0C14H21 N! I'll correct it to NJ. (6), page 50, line 2, “○F(OH N: N
” I am corrected. (7), page 54, line 5 from the bottom (8), page 60, line 9, one or more - Patent Application No. 195233 2, Name of the invention: Silver halide color photographic light-sensitive material 3, Relationship with the case of a person who makes a mistake Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name:
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent Address: 2-4-1 Shibasaki-cho, Tachikawa-shi, Tokyo FINE Building 6, Number of inventions increased by amendment 7, Detailed explanation of the invention in the specification subject to amendment Column G, 6) 8・Correction 0 S 60 z
2(1), the following statement is added next to line 7 on page 13 of the statement. ” - Above 1

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material, which contains a photographic cyan coupler represented by the following general formula [I] in a light-sensitive emulsion layer. General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in this general formula, R^1 is a group sufficient to provide diffusion resistance to the coupler, and R^2 and R^3 are a hydrogen atom or a halogen atom, Z represents a hydrogen atom or a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent, and at least one of R^2 and R^3 is a halogen atom; be.)