JPH01557A - Silver halide color photographic material containing a new cyan coupler - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan coupler, and more specifically, to a silver halide color photographic material containing a cyan coupler having excellent spectral absorption characteristics. Regarding photographic materials.

[Background of the Invention] After a silver halide photographic material is exposed to light and subjected to color development processing, an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye. A color image is formed.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images.

Phenols or naphthols have been widely used as cyan image forming couplers.

However, cyan images obtained from conventionally used phenols and naphthols have serious problems in color reproduction. The reason is that the absorption is not sharp on the short wavelength side and has unnecessary absorption, that is, asymmetric absorption, even in the green region. As a result, in the case of negatives, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of paper, there is no means for correction, and the current situation is that the color reproducibility is considerably deteriorated.

Furthermore, dye images obtained from conventionally used phenols and naphthols have some problems in their storage stability. For example, U.S. Patent Nos. 2 and 3
The dye images obtained with the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 67.531 and U.S. Pat. Dye images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 772,162 generally have poor light fastness, while dye images obtained from the 1-hydroxy-2-natutamido cyan coupler are Generally poor in both light and heat fastness.

Also, U.S. Patent No. 4,122,369 and Japanese Patent Application Publication No. 5
2,5-diacylaminophenol cyan couplers described in specifications such as No. 7-155538 and JP-A-57-157246, and U.S. Patent No. 3,880,661.
The 2,5-diacylaminophenol cyan coupler that has a hydroxyl group in the ballast part described in the specification of the patent is also required in terms of fastness to light and heat and generation of yellow stain in order to preserve the dye image for a long time. However, a fully satisfactory level has not yet been achieved.

[Object of the Invention] The first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel cyan coupler.

The second object of the present invention is to improve the drawbacks of the conventionally used cyan dye-forming couplers, that is, to provide a clear cyan colorant with sharp absorption, little absorption in the green region, and excellent spectral absorption characteristics. An object of the present invention is to provide a silver halide color photographic material that provides images.

A third object of the present invention is to provide a silver halide color photographic material that forms cyan images that do not change hue due to heat or humidity.

A fourth object of the present invention is to provide, in combination with a sensitizing dye,
The object of the present invention is to provide a silver halide photographic material having good stability of a coating solution over time under good sensitivity.

[Structure of the Invention] The above object of the present invention was achieved by using a coupler in which the pyrazoloazole nucleus has an electron-withdrawing group at a position adjacent to its active site. That is, the present invention provides a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer contains a coupler represented by the general formula [I]. This is a silver halide color photographic light-sensitive material characterized by:

- Formula [11 [wherein, at least R is sulfonyl, sulfinyl,
represents a group selected from sulfonyloxy, sulfonylmethyl, sulfamoyl, phosphoryl, tetrazolyl, pyrrolyl, halogenated alkoxy, halogenated aryloxy, acyl, halogen, nitro, and carboxyl;
represents a hydrogen atom or a group that is released by reaction with an oxidized product of a developing agent. Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle. R2 represents a hydrogen atom or a substituent, and is bonded to a carbon atom in the nitrogen-containing heterocycle. n is 1 or 2, and when n is 2, R2 may be the same or different. ] Hereinafter, the present invention will be explained in more detail.

- In the coupler represented by formula [11, at least R1 is a sulfonyl group, a sulfinyl group, a sulfonyloxy group, a sulfonylmethyl group, a sulfamoyl group, a phosphoryl group, a halogenated alkoxy group, a halogenated aryloxy group, an acyl group, or a halogen atom. , nitro group, tetrazolyl group, pyrrolyl group, carboxyl group, etc.

Examples of the sulfonyl group include groups such as alkylsulfonyl such as methylsulfonyl, arylsulfonyl such as benzenesulfonyl and p-toluenesulfonyl, halogenated alkylsulfonyl such as trifluoromethylsulfonyl, and halogenated arylsulfonyl.

Examples of the sulfinyl group include groups such as methylsulfinyl, octylsulfonyl, 3-phenoxybutylsulfinyl, alkylsulfinyl, arylsulfinyl such as di-bentadecylphenylsulfinyl, and halogenated alkylsulfinyl and halogenated arylsulfinyl. .

Examples of the sulfonyloxy group include groups such as alkylsulfonyloxy such as methylsulfonyloxy and trifluoromethylsulfonyloxy, and arylsulfonyloxy such as benzenesulfonyloxy.

Examples of the sulfasoyl group include N,N-dipropylsulfamoyl, N-phenyl-N-methylsulfamoyl,
An alkyl group, aryl group, etc. forming N,N-diethylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, etc. may be substituted.

Examples of the phosphoryl group include groups such as alkoxyphosphoryl such as ethoxyphosphoryl and butoxyphosphoryl, aryloxyphosphoryl such as alkylphosphoryl, arylphosphoryl, and phenoxyphosphoryl.

As the halogenated alkoxy group, a 1-halogenated alkoxy group such as a trifluoromethoxy group is preferable.

Preferred examples of the halogenated aryloxy group include a tetrafluoroaryloxy group and a pentafluoroaryloxy group.

Examples of the halogen atom include fluorine, bromine, and chlorine.

Examples of the tetrazolyl group include groups such as 1-tetrazolyl and 5-chloro-1-tetrazolyl.

Examples of the pyrrolyl group include groups such as 1-pyrrolyl.

Examples of the acyl group include alkylcarbonyl groups such as acetyl and dodecanoyl, and arylcarbonyl groups such as benzoyl and p-chlorobenzoyl.

Examples of the sulfonylmethyl group include groups such as alkylsulfonylmethyl and arylsulfonylmethyl.

Among the above substituents, particularly preferred are sulfonyl, sulfonylmethyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, tetrazolyl, pyrrolyl, halogenated alkoxy, halogenated aryloxy, and acyl.

- In formula [11], those having at least these substituents as R1 give very favorable spectral absorption characteristics. Further, among these substituents, more preferable ones are sulfonyl, sulfinyl, sulfonyloxy,
Sulfamoyl, acyl, most preferred are
Sulfonyl, sulfinyl, etc., and those having these substituents provide more preferable spectral absorption characteristics.

The above group may further have a diffusion-resistant group such as a long-chain hydrocarbon group or a polymer residue, or a substituent such as an electron-withdrawing group.

In the general formula [11], R2 may include the above substituent and any other substituent or hydrogen atom.

The substituent represented by R2 typically includes polygroups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl; in addition, cycloalkenyl, alkynyl, and heterocyclic , alkoxy, aryloxy,
Also included are heterocyclic oxy, siloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, carbonylamino, heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, etc. .

The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R2 is preferably a phenyl group.

Examples of the acylamino group represented by R2 include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R2 include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R2 include the alkyl group and aryl group represented by R2 above.

The alkenyl group represented by R2 has 2 to 32 carbon atoms.
The cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be straight or branched.

The cycloalkenyl group represented by R2 has 3 carbon atoms.
-12, especially 5-7 are preferred.

Carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; sulfamoylamino groups include alkylsulfamoylamino groups, arylsulfamoylamino groups, etc. ; As the heterocyclic group, a 5- to 7-membered one is preferable; specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc.; as a heterocyclic oxy group, a 5- to 7-membered one is preferable. Preferably, those having a heterocycle of 3,
4,5.6-tetrahydropyranyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-diphenoxy-1 , 3,5-triazole-6 monothio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group. group, glutarimide group, etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2,2,1
] heptan-1-yl, tricyclo[3,3,1,1”
]]Decan-1-yl7,7-dimethyl-bicyclo[2
,2,1]butan-1-yl and the like.

Examples of the carbonylamino group include groups such as alkoxycarbonylamino and aryloxycarbonylamino.

The above group may further have a diffusion-resistant group such as a long-chain hydrocarbon group or a polymer residue, or a substituent such as an electron-withdrawing group.

Among the substituents represented by R2, particularly preferred are those in which an aryl group, preferably a phenyl group, is directly bonded to the pyrazoloazole core.

Examples of the group that is released by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
carboxyl, (R8' is the same as the above R or R2, 2' is the same as the above Z, and Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group), etc. Among these groups, a halogen atom, particularly a chlorine atom is preferable.

Examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, and a triazole ring.

More specifically, the coupler represented by the general formula [11]
For example, it is represented by the formulas [11] to [V1].

General formula [! ■] General formula [Ill] General formula [■] General formula [V] General formula [VT] N-N! Nil In the above formulas [n] to [VI], R1 is the general formula [
R of 11, R3-R9 and X are the above-mentioned R2 and X
is synonymous with

Typical specific examples of the compounds according to the present invention are shown below.

(Margin below) These cyan couplers of the present invention are manufactured by J. Chem.

Soc, Perkin I [977), 2047
~2052, J, ) Iter-cycle, Che
m,, 11.423 (1974), Her, 32.
797 (1899), Chem, Ber, 95.2
861.2881 (1962), U.S. Special Liver No. 3, 70
5. B'16, No. 3,725,067, JP-A-59
-99437, 59-162548, 59-1
No. 71956, No. 60-43659, No. 60-172
No. 982, No. 60-197688, No. 61-6524
No. 7, Special Publication No. 48-43947 and Patent Application No. 1988-1
Those skilled in the art can easily synthesize it by referring to No. 20054 and the like.

Typical synthesis examples are shown below.

(Left below) Synthesis Example 1 (Synthesis of II-1) H25rt- was synthesized according to the method described in Japanese Patent Application No. 120054/1982.

[A-mutual] 0.01 mol of a was dissolved in 50a+J of acetonitrile, 0.12 mol of m-nitropenzoyl chloride was added to Q, and 0.1 mol of triethylamine was added dropwise. After stirring at room temperature for 3 hours, the precipitated crystals were filtered off.

0.0072 mol of each was obtained.

[Mutual] 0.0072 mol of b and 0.0095 mol of phosphorus oxychloride were added to 7hj of toluene, and the mixture was heated under reflux for 3.5 hours. After distilling off toluene, 0.1 mol of pyridine and 50 m
J! of acetonitrile was added, and the mixture was further heated under reflux for 2.5 hours. It was collected by filtration while hot to obtain 0.0041 mol.

[Dan-Dan] c O, 0041 mol to acetic acid 2S + ail, sulfuric acid 7 m
1 and water (0.8 mj), and the mixture was heated under reflux for 1.5 hours.

Neutralize with aqueous sodium hydroxide solution, extract with ethyl acetate,
After concentration, water was added and 0.030 moles of dO, which did not precipitate, was collected by filtration.

[i-Dan-JLI d O, 0030 mol dissolved in T HF 50 mJ,
Hydrogenation was performed using Pd/c. After Pd/c was filtered off and the solvent was distilled off, the precipitate was dissolved in 100 mj of acetonitrile, 0.0052 mol of E was added, and 0.004 mol of triethylamine was added dropwise. After stirring at room temperature for 2 hours, the precipitated crystals were collected by filtration and recrystallized from ethyl acetate to obtain 24 mol of JLO, OO.

[L→ll-1] Dissolve 0.0024 mol of 5 in 15IIIj of acetic acid,
Slowly add 5 ml of 35% hydrogen peroxide solution and heat to 55°C.
The mixture was stirred for 2.5 hours. After that, water 501 was added and the mixture was slowly neutralized with an aqueous sodium hydroxide solution, extracted with ethyl acetate and distilled off, and the resulting precipitate was recrystallized with acetonitrile to produce white needle-like crystals. II-10,
0019 mol was obtained.

Synthesis Example 2 (Synthesis of II-18) Using 3-carboxy-4-chloro-5-aminopyrazole as a raw material, it was converted into a hydrazine form and reacted with an acid chloride according to a conventional method, and then Synthesized.

[Looking at each other] a O, 01 mol and 2N sodium hydroxide aqueous solution 5mR
in 20+aJ of acetonitrile while cooling with water and stirring,
After slowly dropping 0.01 mol of benzyloxycarbonyl chloride and 3 ml of 4N aqueous sodium hydroxide solution,
Stir for a minute. After neutralization with hydrochloric acid, it was cooled, and the precipitate was collected by filtration and washed with cold water to obtain bo, ooa moles.

[Alternatively] 2 hR of benzene solution to which o and ooa moles were added is IN
of methyllithium in diethyl ether with stirring, and stirred for 20 hours. Add 100+ ai' of cooled sewage water, extract with ethyl acetate, evaporate the solvent, recrystallize the precipitate with acetonitrile,
! 0.0040 moles in a barrel.

[Dan → 11-18] Dissolve 0,0040 mol of cO in 60mj of THF,
It was reduced using Pd/c.

After removing Pd/c and distilling off the solvent, the residue was recrystallized from ethyl acetate to obtain 0.0030 mol of pale yellow needle crystals of 11-18.

Synthesis Example 3 (Synthesis of 1■-1) With reference to Japanese Patent Application No. 61-120054, compound a was synthesized according to a conventional method.

° [0.01 mole of beans and 0.011 mole of toluene
After heating under reflux for 20 hours in 0 mβ, toluene was distilled off and the residue was mixed with methanol 20+nJ! A methanol solution of hydroxylamine was added at 0°C, and 1.
Stirred for 5 hours. This is 200mj! The precipitate was collected by filtration. Dissolve this in 60mR THF and
．． 004 mol of triethylamine was added and while stirring, 0.7 g of p-toluenesulfonic acid chloride was added.
After adding an HF solution and further stirring, insoluble matter was filtered off, and the filtrate was heated and refluxed in nitrogen for 7 hours, and THF was distilled off. When the residue is poured into a small amount of methanol 50mj+, c O,00
45 mol were obtained.

[JL-11-1] in the same manner as in Synthesis Method 1.
Oxidation of 0,045 moles of 1 gave 0,0039 moles of 1.

0.0039 mol of 1 of
-JL ], the crude crystals are reduced to zero by hydrogenation reduction, and further reaction with the corresponding acid chloride.
．． 0031 mol was obtained.

[Dan→+u −11 0,0031 moles of 2 is 50 m1! of chloroform and added 0.0050 mol of N-chlorosuccinimide. After stirring at room temperature for 30 minutes, the solvent was distilled off, and recrystallization was performed using a mixed solvent of ethyl acetate and n-hexane to obtain 0.0022 mol of white powder crystals of III-1.

Synthesis Example 4 (Synthesis of II!-16) Lil'ts 0.01 mol of a and 0.022 mol of sodium diethylaminosulfinate at 50 mA! of methanol and heated under reflux for 3 hours. The solvent was distilled off, acetic acid was added to the residue, insoluble materials were filtered off, and the filtrate was concentrated to a concentration of 0.006
1 mol was obtained.

[Alternatively] 0.0061 mol of b was added to 100 mA+ of ethanol, and o, ooao mol of 100% hydrazine hydrate was added dropwise.

After heating under reflux for 7 hours, the solvent was distilled off, and the residue was recrystallized from ethanol to obtain 0.0031 mol of tan.

[Dan-! ] 0.0031 mol of Dan was reacted with Sho in the same manner as described in [Synthesis of Dan] in Synthesis Method 3, followed by ring closure to obtain 0,0014 mol of eO.

[Nill-16] 0.0014 mol of 2 in Synthesis Method 1 [Sho→! →
jL], hydrogenation reduction and reaction with acid chloride were performed. The obtained crude crystals of lll-16 were recrystallized using acetonitrile to obtain lll-16 of 0.
0010 moles were obtained.

Synthesis Example 5 (Synthesis of ■-1) ＼ C2H5 Dan [Synthesis of Dan] 0.010 mol of a and 0.010 mol of b at 50 mJ
The mixture was heated under reflux in anhydrous ethanol for 17 hours, the solvent was distilled off, and the mixture was distilled under reduced pressure to obtain 0,060 mol of cO.

[Mutual synthesis] c Q, 60 mol of 0Q, 10 mn of ethanol and 25
% sulfuric acid under reflux for 6.5 hours, and after cooling 0.0
Add 5 moles of sodium carbonate and stir. Insoluble materials were filtered off, the solvent was distilled off, and the resulting residue was recrystallized from acetonitrile to obtain 0.0040 mol of d.

[and-i] 0.0040 mol of each other [and-! →
0.0032 mol of e was synthesized by hydrogenation reduction and further reaction with acid chloride according to the same method as [E. A mixed solvent of ethyl acetate and hexane was used as the recrystallization solvent.

[See→■-1] Using 10.0032 mol, [JL
→II-1], peracetic acid oxidation was performed, and after recrystallization with acetonitrile, 0.0070 mol■
-t white needle crystals were obtained.

The couplers of the invention typically have IX per mole of silver halide.
10-3 mol to 1 mol, preferably I x 10-2
It can be used in the range of -8 x 10-' moles.

The coupler of the present invention can also be used in combination with other types of cyan couplers.

The methods and techniques used for conventional cyan dye-forming couplers are similarly applicable to the cyan couplers of the present invention. Typically, the cyan coupler of the present invention is blended into a silver halide emulsion, and this emulsion is coated on a support to form the color light-sensitive material of the present invention.

In a further preferred embodiment, the red-sensitive silver halide emulsion layer containing a coupler represented by general formula [I]
Furthermore, the following formulas [A], [B], [C], [D],
It contains at least one kind of sensitizing dye selected from the sensitizing dyes represented by [E] and [F], and in this case, the sensitivity is good and the stability of the coating solution over time is better than expected. You can get the effect of being there.

[D] [E] [F] Old 2, (KO), 1 In the formula, 21 to Z9 are a benzene ring or a naphthalene ring fused to a pyridine ring, imidazole ring, thiazole ring, selenazole ring, oxazole ring, or tetrazole ring. represents the atomic group necessary to form zl. represents an atomic group necessary to form a benzothiazole ring, benzoselenazole, β-naphthothiazole ring, β-naphthoselenazole ring, benzimidazole ring or 2-quinoline ring, and Ql and Q2 jointly represent 4 -thiazolidinone, 5
- each represents a hydrogen atom, an alkyl group, or an aryl group, R17+ Rlap l 1' and Ra' represent an alkyl group, R19 and R21 each represent an alkyl group, an aryl group, or a heterocyclic group, and R02゜R
+3・R14+ RIS* R16・R20・
R, 2, R23/R24 and Rwe each represent an alkyl group or an aryl group.

bu represents 1 or 2, Y represents sulfur or selenium atom,
L1 to L each represent a substituted or unsubstituted methine group. K
is an acid anion.

General formulas [A], [B], [
The sensitizing dyes represented by [C], [D], [E], and [F] are known, for example, F.M.
Written by The Chemstry of Heterocyclic Compounders
teracycltc Compoundsl Volume 18, The Cyanine Drys
andRelated Compounds) (
^, Weissherged, Intersc
(Published by New York, 1964)
It can be easily synthesized by the method described in .

Typical specific examples of sensitizing dyes preferably used in the present invention are shown below.

(Left below) [S-S] [S-8] [S-11] [S-121 (C?hbS(JiliN('-2, 2M5h) Well known methods can be used. For example, these sensitizing dyes can be dispersed directly in the emulsion or dispersed in water such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone or mixtures thereof. It can be dissolved in a soluble solvent, diluted with water, or dissolved in water, and added to the emulsion in the form of a solution. Ultrasonic vibration can also be used in the dissolution process. As described in U.S. Pat. No. 3,469,987, etc., a method involves dissolving a dye in a volatile organic solvent, dispersing this solution in a hydrophilic colloid, and adding this dispersion to an emulsion. , Japanese Patent Publication No. 46-24185, etc., a method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion. It can be added to an emulsion in the form of a dispersion by an acid dissolution dispersion method.Other additions to an emulsion include U.S. Pat. No. 2,912,345;
．． No. 605, No. 2,996,287, and No. 3
, 425,835 and the like can also be used.

The timing of adding the sensitizing dye used in the present invention to the emulsion is as follows:
It may be carried out at any time during the emulsion manufacturing process, but preferably during or after chemical ripening.

Further, it may be added in multiple portions during and after chemical ripening.

Moreover, the sensitizing dyes represented by formulas [A] to [F] can also be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In this case, each sensitizing dye may be dissolved in the same or different solvents, and the solutions may be mixed or added separately prior to addition to the emulsion. When adding them separately, the order and time interval can be arbitrarily determined depending on the purpose.

The amount of sensitizing dye used in the present invention is 20xlO"' to 0.15xlO-' per mole of silver halide.
molar, preferably 0xlO-' to 0.3xL
O-'mol, more preferably 0.8xlO-' to 0.4
xlO-' mole.

The color photosensitive materials of the present invention include, for example, color negative and positive films, and color photographic paper.

The photosensitive materials of the present invention, including this color photographic paper,
It may be for a single color or for multiple colors. In a multicolor light-sensitive material, the cyan coupler of the present invention may be contained in any layer, but is preferably contained in a red-sensitive silver halide emulsion layer. Multicolor light-sensitive materials have dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum. Each building block can consist of a single or multiple emulsion layer sensitive to a certain region of the spectrum. The constituent layers of the photosensitive material, including the layers of image-forming units, can be arranged in various orders as is known in the art.

A typical multicolor light-sensitive material is a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler (at least one of the cyan couplers is a diazo coupler of the present invention). ), a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler. It consists of a yellow dye image-forming structural unit consisting of an emulsion layer supported on a support. The photosensitive material is
Additional layers may be present, such as filter layers, interlayers, protective layers, subbing layers, etc.

In order to incorporate the cyan coupler of the present invention into an emulsion, a conventionally known method may be followed. For example, the cyanogen of the present invention may be added to a high boiling point organic solvent having a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as butyl acetate or butyl propionate, or a mixture thereof as necessary. After the couplers are dissolved alone or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotary mixer or colloid mill, and then added to the silver halide to form the halogen used in the present invention. A silver oxide emulsion can be prepared.

Silver halide compositions preferably used in the present invention include silver chloride, silver chlorobromide, and silver chloroiodobromide. Furthermore, a combination mixture such as a mixture of silver chloride and silver bromide may be used. That is, when the silver halide emulsion according to the present invention is used in color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains chlorine atoms, and at least 1% of chlorine atoms are included. Particularly preferred are silver chloride, silver chlorobromide, or silver chloroiodobromide containing silver chloride.

The silver halide emulsion is chemically sensitized by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known as antifoggants or stabilizers in the photographic industry may be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

The color photosensitive material of the present invention includes a color antifoggant, a dye image stabilizer, an ultraviolet inhibitor, which are commonly used in photosensitive materials,
Antistatic agents, matting agents, surfactants, etc. can be used.

Regarding these, for example, Research Disclosure w
-(Research Disclosure) 17
[You can refer to the description in Volume i, pages 22-31 (December 1978).

An image can be formed on the color photosensitive material of the present invention by subjecting it to a color development process known in the art.

The color light-sensitive material according to the present invention may contain a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath.

After color development, the color photosensitive material of the present invention is subjected to a bleaching process and a fixing process. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[Examples] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 A red-sensitive color photosensitive material sample 1 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side. Incidentally, unless otherwise specified, the amount of the compound added is approximately III+2 (silver halide is a silver equivalent value).

1st layer: Emulsion layer 1.2 g of gelatin, 0.30 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 0 dioctyl phthalate.
．． Red-sensitive emulsion layer consisting of 45 g of comparative cyan coupler aO dissolved in 20 g.

Second layer: Protective layer Protective layer containing 0.50 g of gelatin. In addition, as a hardening agent, 2
．． 4-Dichloro-6-hydroxy-9-)-'J azine sodium salt was added at a concentration of 0.017 g per gram of gelatin.

Next, Samples 2 to 24 of the present invention were prepared in exactly the same manner as in Sample 1 except that comparative coupler a was replaced with the coupler shown in Table 1 (the amount added was the same molar amount as comparative coupler a).

Samples 1 to 24 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

(Development process) Color development 38℃ 3 minutes 30 seconds bleach fixing
Stabilization treatment at 38°C for 1 minute and 30 seconds/or washing treatment at 25°C to 30°C for 3 minutes Drying at 75°C to 80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) Benzyl alcohol 15 mR
Ethylene glycol 15m2 Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate
30.0 g Hydroxylamine sulfur fi tfi 3, 0 g Polyphosphoric acid (TPPS) 2.5 g Aniline sulfate 5.5 g Optical brightener (4
, 4'-diaminostilbendisulfonic acid derivative)
1.0g potassium hydroxide 2
,0g water was added to bring the total volume to 1℃, p) + 10.20
Adjust to.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100+uj! Ammonium sulfite (40% solution) 27.5mj! Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 1.
Set to 1.

(Stabilizing liquid) Add 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 g water and i
It shall be IL.

For samples 1 to 24 treated above, the spectral absorption maximum wavelength (λ+max) and the reflection density at λ□8 are as follows:
Reflection density at 420 nm at 1.0 (Dλ42o
) and the half-width (W%), which is the difference between one point on the longer wavelength side than λ,□ and one point on the shorter wavelength side than λ□, where the reflection density is 0.5, is measured. , spectral absorption characteristics and color reproducibility were investigated.

Dλ4□. The smaller the value of W%, the less asymmetric absorption in the green region, and the smaller the value of W%, the sharper the absorption and the better the color reproducibility.

Further, the absorption spectra of samples 1.2 and 12 are shown in FIG.

In addition, each of the above treated samples was heated at high temperature (60℃, 80%R).
H) The dye image was left in an atmosphere for 14 days, and the heat resistance and moisture resistance of the dye image were examined. The obtained results are also shown in Table-1. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining after the heat and humidity resistance test with respect to the initial density of 1.0. Incidentally, a D-78 type densitometer (manufactured by Konica Corporation) was used for various measurements.

Comparison coupler a! (Leaving space below) Table 1 As is clear from the results in Table 1, the samples using the coupler of the present invention had a much smaller half-width than the samples using the comparative coupler, and had asymmetric absorption. Its small size indicates that it has excellent spectral absorption characteristics. Furthermore, it can be seen that it has a high dye residual rate, excellent heat resistance and moisture resistance, and is robust.

Furthermore, FIG. 1 shows that the coupler of the present invention has less undesirable asymmetric absorption in the green region and sharper absorption in the vicinity of λ, l, compared to conventional phenolic couplers. There is.

Example 2 Red-sensitive color reversal photographic materials 25 to 32 were prepared by sequentially coating the following layers on a triacetyl cellulose film support from the support side. Incidentally, unless otherwise specified, the amount of the compound added is shown per 1 m2 (silver halide is a silver equivalent value).

1st layer: Emulsion layer 1.4 g of gelatin, 0.5 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 0.24 g of dibutyl phthalate.
The coupler shown in Table 2 (9,1XlO-4
mol), a red-sensitive emulsion layer consisting of

2nd layer: Protective layer A protective layer containing 0.5 g of gelatin, and 2.0 g as a hardening agent.
4-dichloro-6-hydroxy-5-triazine sodium salt was added in an amount of 0.017 g per gram of gelatin.

The samples obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

[Reversal process] Process Time Temperature - Development 6 minutes 38℃ Water washing 2 minutes 38℃ Incubation
Transfer 2 minutes 38℃ Color development 6 minutes 38℃ Adjustment 2 minutes 38℃ bleaching
White 6 minutes 38℃ fixation 4 minutes 38℃ water
Wash 4 minutes Stable at 38℃
Dry for 1 minute at room temperature. The composition of the processing solution used is as follows.

[First developer] Water
700mj! Sodium tetrapolyphosphate
2g sodium sulfite 2
0 g hydroquinone monosulfonate 30
g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 2g potassium bromide
2.5g potassium thiocyanate
1.2g potassium iodide (0.1% solution)
21° Add water at 1000 mA' (pH 10,1) [Turn over] Water
700+nj! Nitrilo N,N,N-)-rimethylenephosphonic acid 6Na salt 3g
Stannous chloride (dihydrate) Igp-aminophenol 0.18 Sodium hydroxide 5g Glacial acetic acid
Add 15 ml water
At 1000 m [color developer] water
700 mN sodium tetrapolyphosphate
2g Sodium sulfite 7g
Tertiary sodium phosphate (decahydrate) 36g Potassium bromide 1g Potassium iodide (0,
1% solution) 90 mB Sodium hydroxide 3g Citrazic acid
1.5g-4-aminoaniline sulfate
11 g ethylenediamine
Add 3g water for 1000
rnR [adjustment solution] water
700 mR sodium sulfite
12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid
Add 3 mj water
1000 1111 [Bleach solution] Water
500mj! Sodium ethylenediaminetetraacetate (dihydrate) 2.0gIron (Ill) ethylenediaminetetraacetate Ammonium (dihydrate) 120.0g Potassium bromide 100. ．． Add 0 g water and 1000 mR [Fixer water]
800 mal ammonium thiosulfate
80.0g sodium sulfite
5.0g Sodium bisulfite 5
．． Add 0g water 1000
ml [stabilizer] water
800 I! R formalin (37% by weight)
5.0mA + water added
1000 mA Samples 25-32 treated above
As in Example 1, the maximum spectral absorption wavelength (λ□×
) and half-width (Vll) ·Dλ420 were measured. The results are shown in Table-2.

Incidentally, in the various measurements in Example 2, a KD-7R plasticity meter was used to measure the transmission density.

Table 2 As is clear from Table 2, the sample using the coupler of the present invention has a smaller half-value width and smaller Dλ420 than the sample using the comparative coupler, so it has excellent spectral absorption characteristics and color reproducibility. It can be seen that the results are good.

It can also be seen that the sample using the coupler of the present invention has a markedly improved dye image retention rate and is robust.

Example 3 [Preparation of red-sensitive silver halide emulsion] 1xlO-5 mol of sodium thiosulfate was added per 1 mol of silver chlorobromide emulsion containing 96 mol% of silver chloride, and chemical ripening was performed. 5 minutes before applying the following sensitizing dye a for the red-sensitive emulsion layer.
5.0xlO-5 mol 0.1 per mol silver halide
*Added as a solution. After 5 minutes, at the end of the chemical ripening, 4-hydroxy-6-methyl-1,3,
3a,7-chitrazaindene was added as an aqueous O,596 solution. Thereafter, an aqueous gelatin solution of 1096 was added, stirred, and cooled to prepare a red-sensitive silver halide emulsion.

[Preparation of Photosensitive Material] Red-sensitive color photosensitive material sample 33 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side. Incidentally, the amount of the compound added is shown per 1 m' unless otherwise specified (silver halide is a silver equivalent value).

1st layer: Emulsion layer gelatin 1.2 g, red-sensitive silver chlorobromide emulsion 0.30 g
and dioctyl phthalate o, z 4 g (,: dissolved comparative cyan coupler a O, 45 g (9,1xlO-
A red-sensitive emulsion layer consisting of 'mol).

Second layer: Protective layer Protective layer containing 0.50 g of gelatin. In addition, as a hardening agent, 2
, 4-dichloro-6-hydroxy-5-t-riazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

Next, in Sample 33, comparative coupler a was replaced with the coupler of the present invention shown in Table 3, and sensitizing dye a was replaced with the sensitizing dye shown in Table 3. Samples 34 to 5L of the present invention were prepared in exactly the same manner except that the molar ratio was set to be equimolar. In addition, the above samples 33 to 51
In order to examine the stability of the coating solution over time, two types of samples were prepared for each sample, in which the coating solution for the first emulsion layer was prepared and then coated after 1 hour and 5 hours. Samples 33 to 51 obtained above were each subjected to wedge exposure according to a conventional method, and then developed using the processing steps described in Example 1.

421) r++++, S50nm when the spectral absorption maximum wavelength (λ, □) and reflection density at λmmN of each sample coated after 1 hour of treatment above are 1.0
and reflection density at 700 nm (Dλ42G, Dλ
ss.

and Dλ,. . ) and the half-width of spectral absorption (λ□8
The wavelength with a reflection density of 0.5 on the longer wavelength side and λ, S, ,
The difference between the wavelength and the reflection density of 0.5 on the shorter wavelength side than 1) was measured. The smaller the half-width, the sharper the absorption and the better the color reproducibility.

Furthermore, when λ111X is the same, the smaller the value of Dλ420, the less asymmetric absorption in the blue region, and the smaller the value of Dλ5. . The smaller the value of Dλtoo, the less asymmetric absorption in the green region, and the smaller the value of Dλtoo, the sharper the absorption and the better the color reproducibility.

The absorption spectra of samples No. 34.37 and 44 are shown in FIG.

In addition, each of the above-mentioned treated samples was heated at high temperature and high humidity (60℃, 80%R).
) I) The dye image was left in an atmosphere for 14 days and the heat resistance and moisture resistance of the dye image were examined. The obtained results are also shown in Table 3. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining after the heat and humidity resistance test with respect to the initial density of 1.0.

In addition, reflection density was measured using a densitometer for each sample of the coating solution after 1 hour and 5 hours, and sensitivity and fog were measured. The reference point for light and optical density that determined the sensitivity was fog + 0.
The score was 20.

In addition, the sensitivity ratio is the sample sensitivity of sample movement 33 using comparison coupler a and sensitizing dye a after 1 hour of stagnation of the coating solution.
It was set as 00.

In addition, KD-7 plasticity meter (manufactured by Konica Corporation) was used for various measurements.
was used.

The above results are summarized in Table 3.

Sensitizing dye a As is clear from the results in Table 3, the samples using the coupler of the present invention all have a smaller half-width than the samples using the comparative coupler, and Dλ4□. , Dλ550 and Dλ
It can be seen that the asymmetric absorption of each of 700 is small, and furthermore, the dye residual rate is high and the color reproducibility is good. Furthermore, regarding the decrease in sensitivity over time of the coating solution, it can be seen that in combination with the sensitizing dye preferably used in the present invention, the decrease in sensitivity is small and is a preferred embodiment.

FIG. 2 shows that the coupler of the present invention has less unfavorable asymmetric absorption in the green region (550 nm) than conventional phenolic couplers, and has a wavelength of λ1. ．． This shows that the absorption near aX is sharp.

Example 4 A red-sensitive silver halide emulsion was prepared in the same manner as in Example 3, except that the couplers and sensitizing dyes of the present invention shown in Table 4 were used. A silver oxide emulsion was prepared.

Samples 52 to 59 of red-sensitive reversal photographic materials were prepared by sequentially coating the following layers on a triacetyl cellulose film support from the support side.

Incidentally, the amount of the compound added is per 1 m2 unless otherwise specified (silver halide is a value in terms of silver).

1st layer: Emulsion layer A red-sensitive emulsion layer consisting of the couplers shown in Table 4 dissolved in 1.4 g of gelatin, 0.50 g of red-sensitive silver chlorobromide emulsion, and 0.24 g of dibutyl phthalate.

Second layer: Protective layer Protective layer containing gelatin o, sog. In addition, as a hardening agent, 2
．． 4-dichloro-6-hydroxy-8-triazine sodium salt was added at 0.017 g per gram of gelatin.

The samples obtained above were subjected to wedge exposure according to a conventional method, and then subjected to the reversal development process described in Example 2.

Regarding the coating solution for the first emulsion layer prepared to have the above composition, the sample sensitivity ratio of the coating solution after 1 hour and 5 hours was determined in the same manner as in Example 3, and the spectral absorption maximum of the sample treated above was determined. Wavelength (λ□X) and half-width (Wl/2)
was measured by the same measuring method as in Example 3.

The results are shown in Table 4.

For the sensitivity ratio, the sample sensitivity of sample No. 52 using comparative coupler a and sensitizing dye after 1 hour of stagnation of the coating solution was set as 100.

In addition, a KD-7 type thermometer (
The degree of permeability AtfA was measured using the following product (manufactured by Konica Corporation).

Sensitizing dye b CH, C0Nf (2) As is clear from the results in Table 4, the sample using the coupler of the present invention has a smaller half-value width and better color reproducibility than the sample using the comparative coupler. It can be seen that the residual rate of the dye image was also significantly improved compared to the comparative sample.

Further, the coupler of the present invention has good sensitivity and excellent stability over time of a coating solution when a sensitizing dye preferably used in the present invention is used at the same time.

[Effects of the Invention] The color photographic material containing the pyrazoloazole cyan coupler of the present invention can form a clear cyan image with excellent spectral absorption characteristics, and the cyan image is resistant to heat and humidity. It has a particularly remarkable effect of being very stable against.

Further, in the present invention, by using the above-mentioned sensitizing dyes in combination, it is possible to enhance the -layer sensitivity and to obtain a coating solution having better stability over time than expected.

[Brief explanation of drawings]

FIG. 1 shows absorption spectrum curves of developed samples No. 1.2 and 12. Sample 1... Comparison coupler a (sample Not) Sample 2...
・Invention coupler II-2 (sample movement 2) sample 12...
- Coupler III-4 of the present invention (sample No. 12) Figure 2 shows absorption spectrum curves of developed samples No. 34, 37 and 45. Sample 34: Comparison coupler a (sample No. 34) Sample 37: Invention coupler ll-50 (sample No. 37)
Sample 44--Coupler of the present invention +1l-25 (sample No.
44) Patent applicant: Konica Co., Ltd. Representative patent attorney: Miki Nakajima Yugai 1 liquid length (nm) Figure 2

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains a coupler represented by the general formula [I]. A silver halide color photographic light-sensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, at least R_1 is sulfonyl, sulfinyl, sulfonyloxy, sulfonylmethyl, sulfamoyl, phosphoryl, tetrazolyl, pyrrolyl, halogenated alkoxy, halogenated aryloxy, acyl , represents a group selected from halogen, nitro, carboxyl,
X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a developing agent. Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle. R_2 represents a hydrogen atom or a substituent, and is bonded to a carbon atom in the nitrogen-containing heterocycle. n is 1 or 2, and when n is 2, R_2
may be the same or different. ]