JP2535569B2 - Silver halide color photographic light-sensitive material containing a novel photographic cyan coupler - Google Patents

Description

The present invention relates to a novel pyrazoloazole-based uncoupler used in a color photographic light-sensitive material, and in particular, a pyrazolo compound capable of obtaining a cyan image excellent in sharpness and durability. The present invention relates to an azole type cyan coupler.

BACKGROUND OF THE INVENTION After exposing a silver halide photographic light-sensitive material to color development processing, an oxidized aromatic primary amine color developing agent reacts with a dye-forming coupler to form a dye. A color image is formed.

Generally, in this photographic method, a color reproduction method by a subtractive color method is used to form yellow, magenta and cyan color images.

Heretofore, phenols or naphthols have been widely used as cyan image forming couplers.

However, the cyan image obtained from the conventionally used phenols and naphthols has a serious problem in color reproduction. That is, sharpness on the short wave side of absorption is poor, and unnecessary absorption, that is, irregular absorption, is also present in the green region.
As a result, in the negative, the irregular absorption must be corrected by masking or the like, and in the case of the paper, there is no correction means, and the color reproducibility is considerably deteriorated.

Further, dye images obtained from conventionally used phenols and naphthols have some problems in storage stability. For example, U.S. Pat.
The dye images obtained from the 2-acylaminophenol cyan couplers described in 7,531 and 2,423,730 are generally inferior in heat fastness and are described in U.S. Pat.Nos. 2,369,929 and 2,772,162, 2,5- The dye image obtained from the diacylaminophenol cyan coupler is generally inferior in light fastness, and the dye image obtained from the 1-hydroxy-2-naphthamide cyan coupler is generally insufficient in terms of both light and heat fastness.

Also, U.S. Pat.No. 4,122,369 and Japanese Patent Laid-Open No. 15553/1982.
No. 8, 2,5-diacylaminophenol cyan couplers described in the specification such as JP-A-57-157246 and the ballast moiety having a hydroxy group described in U.S. Pat.No. 3,880,661 2, The 5-diacylaminophenol cyan coupler has not yet been sufficiently satisfactory in terms of fastness to light and heat and generation of yellow stain for long-term storage of the dye image.

Therefore, the present inventors have searched for a coupler that gives a cyan dye that is durable against color reproduction and heat and humidity, and found that the pyrazoloazole-based compound satisfies both of them, The present invention has been made based on this finding.

[Object of the Invention] Therefore, a first object of the present invention is to provide a novel cyan coupler used in a color photographic light-sensitive material.

A second object of the present invention is to provide a cyan coupler which provides a sharp cyan image with sharp absorption and little absorption in the green region and excellent spectral absorption characteristics.

A third object of the present invention is to provide a cyan coupler capable of forming a cyan image that does not change its hue with respect to heat and humidity.

[Construction of the Invention] The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one red light-sensitive silver halide emulsion layer on a support, and at least one of the red light-sensitive silver halide emulsion layers. It is achieved by a silver halide color photographic light-sensitive material characterized in that the layer contains at least one cyan coupler represented by the following general formula [I].

General formula [I] [Wherein R ₁ and one or two R ₂ are substituents having a substituent constant σp defined by Hammett of +0.20 or more, and other R ₂ are substituents. n represents 1 or 2, and when n = 2, R _{2 s} may be the same or different.

Z represents a nonmetallic atomic group necessary for forming a nitrogen-containing heterocycle. X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent. The present invention will be specifically described below.

The coupler represented by the general formula [I] according to the present invention is characterized in that the pyrazoloazole nucleus has an electron withdrawing group, and as the electron withdrawing group represented by at least two selected from R ₁ and R ₂ , Preferably, the substituent constant δ _p defined by Hammett is a substituent of +0.20 or more, specifically, sulfonyl, sulfonyloxy, sulfinyl, sulfamoyl, phosphoryl, halogen, alkyl halide, alkoxy halide. , Halogenated aryloxy, nitro, pyrrolyl, tetrazolyl, cyano, carbamoyl, acyl, acyloxy, carboxyl, oxycarbonyl and the like.

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

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

Examples of the sulfinyl group include groups such as alkylsulfinyl such as methylsulfinyl, octylsulfinyl and 3-phenoxybutylsulfinyl, and arylsulfinyl such as m-pentadecylphenylsulfinyl.

As the sulfamoyl group, N-propylsulfamoyl, N, N-diethylsulfamoyl, N-ethyl-N
Examples thereof include groups such as alkylsulfamoyl such as -dodecylsulfamoyl and arylsulfamoyl such as N-phenylsulfamoyl.

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

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

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

The halogenated aryloxy group is preferably tetra or pentafluoroaryloxy.

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

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

The carbamoyl group may be substituted with an alkyl group such as ethyl, butyl or dodecyl, an aryl group or the like.

Examples of the acyl group include groups such as alkylcarbonyl and arylcarbonyl.

As the acyloxy group, alkylcarbonyloxy and the like are preferable.

As the oxycarbonyl group, alkoxycarbonyl,
Examples include groups such as aryloxycarbonyl.

As the halogenated alkyl group, an alkyl group having a halogenated α-position such as a trifluoromethyl group is preferably used.

As the halogenated aryl group, a tetra- or pentafluoroaryl group is preferable.

Further, an arylsulfonylmethyl group and an alkylsulfonylmethyl group are also preferably used.

The above groups may 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 present invention, the electron-withdrawing group preferably used includes at least one group such as alkyl halide, alkylsulfonyl, arylsulfonyl, alkylsulfonyl halide, alkylsulfinyl, arylsulfinyl, and alkylsulfinyl halide, and more preferably. Is an alkyl halide, alkylsulfonyl, arylsulfonyl, alkylsulfinyl,
Groups such as arylsulfinyl are used.

Of the electron withdrawing groups used in the present invention, particularly preferably R ₁ is a group such as alkyl halide, alkylsulfonyl, arylsulfonyl, alkylsulfonyl halide, alkylsulfinyl, arylsulfinyl, and alkylsulfinyl halide, Preferred is a case where R ₁ and R ₂ are both groups such as alkyl halide, alkylsulfonyl, arylsulfonyl, alkylsulfonyl halide, alkylsulfinyl, arylsulfinyl, and alkylsulfinyl halide.

In the general formula [I], when n = 2, when R ₁ or R ₂ is a substituent other than an electron-withdrawing group, the substituent is preferably a hydrogen atom or any substituent.

As the substituent, typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio,
Examples thereof include arylthio, alkenyl, and cycloalkyl groups. In addition to these, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, carbamoyloxy, amino, alkylamino, imide, ureido, and sulfur. Famoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro compound residues,
Examples include bridged hydrocarbon compound residues.

The alkyl group represented by R ₁ or R ₂ other than the electron-withdrawing group preferably has _{1 to} 32 carbon atoms, and may be linear or branched. A phenyl group is preferred as the aryl group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the above alkyl groups and aryl groups.

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

The cycloalkenyl group has 3 to 12 carbon atoms, especially 5 carbon atoms.
The thing of -7 is preferable.

Examples of carbamoyloxy group include alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .: Ureido group such as alkylureido group, arylureido group, etc .: Sulfamoylamino group such as alkylsulfamoylamino group, arylsulfamoylamino group, etc. The heterocyclic group is preferably a 5- to 7-membered one, and specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc .; Having a heterocycle of is preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; Heterocyclic thio groups are preferred, for example 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-to Azole-6-thio group and the like; siloxy group, such as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; Examples of the group capable of splitting off upon reaction with the oxidation product of the color developing agent represented by X include halogen atom ( Chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ₁ ′ has the same meaning as R ₁ above, Z ′ has the same meaning as Z above, and Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group.) And the like. Is preferably a halogen atom, particularly a chlorine atom.

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

What is represented by the general formula [I] is more specifically represented by, for example, the following general formulas [II] to [VI].

General formula [II] General formula [III] General formula [IV] General formula [V] General formula [VI] In the above general formula [II] ~ [VI], R 1 and R ₁ of the general formula [I], R ₃ ~R ₉ and X are as defined above R ₂ and X.

Typical representative examples of the compound according to the present invention are shown below,
This is an example, and the present invention is not limited to this.

These cyan couplers of the present invention are journal of
The Chemical Society Perkin I (J.Chem.So
c., Perkin I) (1977), 2047-2052, Journal of Heterocyclic Chemistry (J. Heterocycl.C)
hem.,) 11 .423 (1974 ), Berihite (Ber.) 32, 797 ( 189
9), Hemische Berichte (Chem.Ber.) 95 .2861,2881
(1962), U.S. Pat. Nos. 3,705,896, 3,725,067, JP-A-58-42045, 59-99437, 59-162548, 59.
-171956, 60-33552, 60-43659, 60-17
2982, 60-190779, 60-197688, 61-6524
No. 7, Japanese Patent Publication No. 46-43947, Japanese Patent Application No. 61-120054 and the same
It can be easily synthesized with reference to No. 61-122450.

 Hereinafter, typical synthesis examples will be shown.

Synthesis Example 1 (Step 1) 0.012 mol of O-ethyl-S-methyldiethiomalonate and 0.01 mol of S-methylisothiocarbohydrazide hydrogen iodide salt are heated in 25 ml of amyl alcohol for 30 minutes.

After cooling, the precipitate was collected and washed with ether to give crude crystals.
1 0.006 mol was obtained.

(Step 2) 0.006 mol of 1 was dissolved in 15 ml of acetic acid, 5 ml of 35% hydrogen peroxide solution was slowly added dropwise, and the mixture was stirred at 60 ° C. for 2 hours. After that, 50 ml of water is added thereto, the mixture is slowly neutralized with an aqueous sodium hydroxide solution, the reaction solution having a pH of 6.5 is extracted with ethyl acetate, and the solvent is distilled off. The obtained precipitate was washed with acetonitrile to obtain 0.005 mol of white needle crystals II-1.

Synthesis Example 2 (Synthesis of II-2) Step 1 O-ethyl-S-phenyldiethiomalonate 0.012
And 0.01 mol of S- (p-nitrophenyl) isothiocarbohydrazide hydrogen iodide to 25 mol of amyl alcohol.
After heating in ml for 1 hour and cooling, the precipitate was collected, washed with ether and dried to give 0.0059 mol of 2 .

Step 2: 0.0059 mol of 2 was dissolved in 50 ml of THF and hydrogenated using pd / c. After separating pd / c, the reaction solution was distilled off. 10 deposits
It was dissolved in 0 ml of acetonitrile, 0.01 mol of tetradecanesulfonyl chloride was added, and 0.012 mol of triethylamine was added dropwise. After stirring at room temperature for 2 hours, the precipitated crystals were separated and recrystallized from ethyl acetate to give compound 3
Was obtained in an amount of 0.0055 mol.

Step 3 3 was oxidized in the same manner as in Step 2 in Synthesis Example 1 to obtain 0.0039 mol of white needle crystals II-2.

Synthesis Example 3 (Synthesis of II-3) Step 1 4 was obtained according to the method described in Japanese Patent Application No. 61-120054.

4. Dissolve 0.02 mol in 100 ml of acetonitrile and add 0.03
After adding 0 mol of urea, the mixture was stirred for 2 hours and the precipitate was collected. This 50ml acetic acid, 20 ml sulfuric acid, 1.0 ml water mixed solvent was heated to reflux for 1 hour, and neutralized with sodium hydroxide solution, by solvent distillation and extracted with ethyl acetate, 5
0.0128 mol was obtained.

Step 2 5 Dissolve 0.0062 mol in 60 ml of acetonitrile and add 0.0
070 mol of tetradecane carbonyl chloride was added dropwise,
After adding a small amount of pyridine, the mixture was stirred at room temperature. The reaction solution was poured into water and the precipitate was taken to obtain 6 . Further, 0.0035 mol of II-3 was obtained in the same manner as in Step 2 of Synthesis Example 1.

Synthesis Example 4 (II-4) The compound 5 in Synthesis Example 3 was used.

5. Dissolve 0.006 mol in 60 ml of acetonitrile and add 0.00
65 mol of m-nitrophenylsulfonyl chloride was added dropwise, and after adding a small amount of pyridine, the mixture was stirred at room temperature. The reaction solution was drained and the precipitate was collected. Further, this was reacted with tetradecanecarbonyl chloride after hydrogenation reduction in the same manner as in Synthesis example 2 and step 2, and further oxidized in the same manner as in Synthesis example 1 and step 2 to obtain 0.0028 mol of II-4.

Synthesis Example 5 (Synthesis of II-6) J. Heterocycl. Chem. Vol. 11.423 (1974) and Japanese Patent Application No.
7 was synthesized according to the method described in 61-120054 or the like.

7 0.01 mol and 0.015 mol of m-nitrophenylsulfonylbenzoyl chloride were added to 50 ml of ethyl acetate to obtain 1.0
Triethylamine (g) was added dropwise, the mixture was stirred for 2 hours, the precipitated crystals were washed with water, and the crystals and 0.01 mol of phosphorus oxychloride were heated and refluxed in 30 ml of toluene for 2 hours. The solvent was distilled off, 10 g of pyridine and 30 ml of acetonitrile were added, the mixture was heated under reflux for 2 hours, and the precipitate was recrystallized from acetonitrile to obtain 8 0.0050 mol. Subsequently, the reaction is carried out in the same manner as in Step 2 of Synthesis Example 2 and the desired product II
-6 0.0031 mol was obtained.

Synthesis Example 6 (Synthesis of III-1) Step 1 The following aminopyrazole was synthesized according to a conventional method,
We got 9 , 10 , and 11 .

Further, the following 12 and 13 were synthesized from the corresponding nitrile compounds according to the method described in JP-A-61-65247.

Step 2 9 0.01 mol and 12 0.011 mol in 20 ml of toluene, 20
After heating under reflux for an hour, toluene is distilled off and the residue is methanol.
The solution was dissolved in 20 ml, a methanol solution of hydroxylamine was added at 0 ° C., and the mixture was stirred at room temperature for 1 hour. This was poured into 200 ml of water and the precipitate was collected.

This is dissolved in 50 cc of THF, 0.004 mol of triethylamine is added, and while stirring, a THF solution of 0.7 g of p-toluenesulfonic acid chloride is added. After further stirring, the insoluble matter is separated, and the liquid is placed in nitrogen. The mixture was heated under reflux for 7 hours. After that, THF was distilled off, the residue was dissolved in a small amount of methanol, and water was added.
When applied in 0 ml, 14 0.004 mol was obtained.

Hydrogenation reduction of 14 0.004 mol was carried out in the same manner as in Synthesis example 2, step 2, followed by reaction with acid chloride, and further oxidation was carried out in the same manner as in synthesis example 2, step 3 to obtain 0.0026 mol III-1.

Synthesis Example 7 (Synthesis of III-2, 6, 7) Using Synthesis Example 6, 9 and 13 synthesized in Step 1, III-2
III- 10 using 10 and 12 and III-7 using 11 and 13
According to the method of Synthesis Example 6, Step 2, respectively.
%, 47%, 30%.

Synthesis Example 8 (Synthesis of IV-1) J.Heterocyclic.Chem. 10 .411 (1973) and JP 59
15 and 16 were synthesized according to −162548.

15 0.01 mol and 16 0.012 mol in anhydrous ethanol, 10
The mixture was heated under reflux for an hour, the solvent was removed, and the residue was distilled under reduced pressure to obtain 17 0.0072 mol.

17 0.0072 mole of this is 300 ml of ethanol, 80 ml of 20% sulfuric acid
The mixture was heated under reflux for 3 hours, and after cooling, excess solid sodium carbonate was added, the solvent was removed, and the resulting residue was recrystallized from acetonitrile to obtain 0.0040 mol of IV-1.

Synthesis Example 9 (Synthesis of IV-5) 18 and 19 were synthesized in the same manner as in Synthesis Example 8.

In the same manner as in Synthesis Example 8, 0.05 mol of 18 and 0.06 mol of
Reaction with 19 gave 20 0.031 mol.

After hydrogenating and reducing 20 in the same manner as in Synthesis Example 2, Step 2, crude crystals obtained by the reaction with 1.2-fold molar acid chloride in ethyl acetate in the presence of pyridine are recrystallized from acetonitrile. This gave 0.025 mol of IV-5.

Synthesis Example 10 (Synthesis of IV-2) 20 0.01 mol, methanol 0.03 mol, dichloroethane
0.05 ml of sulfuric acid is added to the mixture of 20 ml, and the mixture is refluxed for 8 hours. After cooling, add 50 ml of water and extract with ethyl acetate. The ethyl acetate solution is washed with an aqueous sodium hydrogen carbonate solution, the solvent is distilled off, and the residue is recrystallized from acetonitrile. Further, hydrogenation reduction was carried out in the same manner as in the step 2 of Synthesis Example 2, and then 0.0065 mol of IV-2 was obtained by the reaction with acid chloride.

The coupler of the present invention usually contains 1 mol per mol of silver halide.
× 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10
It can be used in the range of ^-1 mol.

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

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

A further preferred embodiment is the above-mentioned red light-sensitive silver halide emulsion layer containing a coupler represented by the general formula [I], further comprising the following general formulas [A], [B], [C],
It contains at least one sensitizing dye selected from the sensitizing dyes represented by [D], [E] and [F]. In this case, the sensitivity is good and the stability of the coating solution over time is expected. The effect of being superior to the above is obtained.

In the formula, Z _{1 to} Z ₉ represent a pyridine ring, an imidazole ring, a thiazole ring, a selenazole ring, an oxazole ring, or an atom group necessary for forming a benzene ring or a naphthalene ring fused to a tetrazole ring, and Z ₁₀ represents Represents a group of atoms necessary for forming a benzothiazole ring, benzoselenazole, β-naphthothiazole ring, β-naphthelenazole ring, benzimidazole ring or 2-quinoline ring, and Q ₁ and Q ₂ jointly represent 4 -Thiazolidinone, 5-thiazolidinone or a group of non-metal atoms necessary for completing a 4-imidazolidinone nucleus, R ₁ and R ₁₅ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₇ , R ₈ and R ₇ 'and R _8' represents an alkyl group, respectively R ₉ and R ₁₁ are an alkyl group, an aryl group or a heterocyclic group, R _2, R _3,
R ₄ , R ₅ , R ₆ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₆ each represent an alkyl group or an aryl group.

l represents 1 or 2, Y represents a sulfur or selenium atom, L _{1 to} L ₆ each represent a substituted or unsubstituted methine group, K
Is an acid anion.

General formulas [A], [B], which are preferably used in the present invention,
The sensitizing dyes represented by [C], [D], [E], and [F] are known ones. For example, F. M. Harmer, The Chemistry of Heterocyclic.
Compounds (The Chemistry of Heterocyclic Compou
nds) Volume 18, The Cyanine Drys and Rel
ated Compounds) (A.Weisshergered.Inter science
It can be easily synthesized by the method described in “New York, 1964”, published by the company.

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

A method well known in the art can be used to add the sensitizing dye to the emulsion. For example, these sensitizing dyes can be dispersed directly in the emulsion, or dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone or a mixture thereof, or diluted with water. Or dissolved in water and added to the emulsion in the form of these solutions.
Ultrasonic vibration can also be used during the dissolution process. Further, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. As described in JP-B-46-24185, a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to an emulsion can also be used. Further, the dye can be added to the emulsion in the form of a dispersion prepared by an acid dissolution dispersion method. To add to other emulsions,
U.S. Pat.Nos. 2,912,345, 3,342,605, 2,99
The methods described in each specification such as 6,287 and 3,425,835 can also be used.

The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion production process, but is preferably during or after chemical ripening. Further, it may be added in plural times during the chemical aging and after the chemical aging.

The sensitizing dyes represented by the general formulas [A] to [F] are
It 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 solvent, and these solutions may be mixed or added separately prior to addition to the emulsion. If added separately, the order,
The time interval can be arbitrarily determined depending on the purpose.

The amount of the sensitizing dye for use in the present invention is a silver halide per mole of 1.20x10 ^-4 ~0.15x10 ^-4 mol, preferably 1.0x10 ^-4 ~0.3x10 ^-4 mol, more preferably 0.8 × 10 ^-4
~ 0.4x10 ^-4 mol.

The cyan coupler of the present invention is often used mainly as a material for a color light-sensitive material, and examples thereof include color negative and positive films, and color photographic paper.

The light-sensitive material using the cyan coupler of the present invention, such as this color photographic paper, may be of single color or multicolor. In the multicolor light-sensitive material, the cyan coupler of the present invention may be added to any layer, but it is preferably contained in the red-sensitive silver halide emulsion layer.

The multicolor light-sensitive material has a dye image-forming constituent unit having photosensitivity in each of the three primary color regions of the spectrum. Each building block can consist of a single layer or multiple emulsion layers sensitive to certain regions of the spectrum.

The constituent layers of the photosensitive material, including the layers of the image forming constituent units,
It can be arranged in various orders as is known in the art. A typical multicolor light-sensitive material is a cyan dye image-forming structural unit (at least one of the cyan couplers is a cyan coupler of the present invention) comprising at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler. A), a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, and at least one blue-sensitive silver halide containing at least one yellow coupler. It comprises a yellow dye image-forming structural unit consisting of an emulsion layer supported on a support.

The light-sensitive material can have additional layers such as filter layers, intermediate layers, protective layers, subbing layers and the like.

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

The silver halide composition preferably used in the light-sensitive material using the cyan coupler of the present invention is silver chloride, silver chlorobromide or silver chloroiodobromide. Further, it may be a combination mixture such as a mixture of silver chloride and silver bromide. That is, when the silver halide emulsion is used for color photographic paper,
Since particularly fast developability is required, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and silver chloride, silver chlorobromide or silver chloroiodobromide containing at least 1% of silver chloride. Particularly preferred.

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

Silver halide emulsions are known as anti-fogging agents or stabilizers in the photographic industry for the purpose of preventing fog during the manufacturing process of light-sensitive materials, storage or photographic processing, and / or keeping photographic performance stable. A compound can be added.

In the color light-sensitive material using the cyan coupler of the present invention, it is possible to use a color fog-preventing agent, a dye image stabilizer, an anti-UV agent, an antistatic agent, a matting agent, a surfactant and the like which are usually used in light-sensitive materials. it can.

Regarding these, for example, Research Disclosure Volume 176, pages 22 to 31 (1978
(December) can be referred to.

The color light-sensitive material using the cyan coupler of the present invention is
An image can be formed by performing color development processing known in the art.

The color light-sensitive material using the cyan coupler according to the present invention can contain a color developing agent as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and can be processed with an alkaline activating bath.

The color light-sensitive material using the cyan coupler of the present invention is
After color development, bleaching treatment and fixing treatment are performed. The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, a stabilizing 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 described with reference to Examples.
The present invention is not limited to these.

Example 1 A red light-sensitive color light-sensitive 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. Unless otherwise specified, the addition amount of the compound is per 1 m ² (silver halide is equivalent to silver).

First layer: emulsion layer 1.2 g of gelatin, red-sensitive silver chlorobromide emulsion (silver chloride 96 mol%
Content) and a red-sensitive emulsion layer consisting of 0.45 g of the comparative cyan coupler a dissolved in 1.50 g of trioctyl phosphate.

Second layer: protective layer A protective layer containing 0.50 g of gelatin. As a hardening agent, 2,4-
Dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

Next, Samples 2 to 20 were prepared in exactly the same manner as Sample 1 except that the comparative coupler a was replaced with the coupler of the present invention shown in Table 1 (the addition amount was the same mole as that of Sample 1).

The samples 1 to 20 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

(Development processing step) Color development 38 ° C 3 minutes 30 seconds Bleach fixing 38 ° C 1 minute 30 seconds Stabilization treatment / or water washing treatment 25 ° C-30 ° C 3 minutes Drying 75 ° C-80 ° C 2 minutes Treatment used in each processing step The liquid composition is as follows.

(Color developer) Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino -N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0
g Calium hydroxide 2.0 g Add water to adjust the total volume to 1 and adjust to pH 10.20.

(Bleach fixer) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml To pH 7.1 with potassium carbonate or glacial acetic acid Adjust and add water to bring the total to 1.

(Stabilizing liquid) 5-chloro-2-methyl-4-isocyazolin-3-one 1.0 g Ethylene glycol 10 g Water is added to make 1.

420 of the maximum absorption wavelength (λ _max ) of each sample treated above and the reflection density at λ _max of 1.0
Half-width of reflection density and spectral absorption at nm (λ1 / 2; λ
the wavelength of the reflection density 0.5 in the longer wavelength side than the _max, lambda _max
The difference from the wavelength at which the reflection density is 0.5 on the shorter wave side is measured.

The smaller the value of Dλ _420, the less irregular absorption in the blue region, and the smaller the full width at half maximum, the sharper the absorption and the better the color reproducibility.

 The absorption spectra of Samples 1, 2, and 13 are shown in FIG.

In addition, the above-mentioned processed samples are subjected to high temperature and high humidity (60 ℃, 80% RH).
The dye image was allowed to stand for 14 days in the atmosphere, and the moist heat resistance of the dye image was examined. The obtained results are also shown in Table 1. However, the moist heat resistance of the dye image is represented by the percentage of the dye remaining after the moist heat resistance test with respect to the initial density of 1.0.

A KD-7 type densitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used for various measurements.

 Table 1 summarizes the above results.

As is clear from the results shown in Table-1, the sample using the coupler of the present invention, compared to the sample using the comparative coupler,
It can be seen that the full width at half maximum (W1 / 2) is small, the irregular absorption detected by Dλ ₄₂₀ is small, and the color reproducibility is very good. The sample of the present invention has a λ
_{Although the max} is small, the spectral waveform is good, so that a cyan image with excellent color reproducibility is provided.

Further, it can be seen that the sample using the coupler of the present invention has a higher residual ratio of dye and is excellent in wet heat resistance as compared with the comparative sample.

Incidentally, FIG. 1 shows that the coupler of the present invention has less unfavorable asymmetric absorption in the green region (550 nm) and sharper absorption near λ _max than the conventional phenolic couplers. ing.

Example 2 Red-sensitive color reversal photographic light-sensitive materials 21 to 29 were prepared by sequentially coating the following layers on the triacetyl cellulose film support from the support side. Unless otherwise specified, the addition amount of the compound is per 1 m ² (silver halide is equivalent to silver).

First layer: emulsion layer Gelatin 1.4 g, red-sensitive silver chlorobromide emulsion (silver chloride 96 mol%
0.5g and dioctylphenyl phosphate 1.65
A red-sensitive emulsion layer comprising a coupler (9.1 × 10 ⁻⁴ mol) shown in Table 2 dissolved in g.

Second layer: Protective layer Protective layer containing 0.5 g of gelatin, 2,4− as hardener
Dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 g per 1 g 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 1st development 6 minutes 38 ℃ Wash with water 2 minutes 38 ℃ Reversal 2 minutes 38 ℃ Color development 6 minutes 38 ℃ Adjustment 2 minutes 38 ℃ Bleach 6 minutes 38 ℃ Fixing 4 minutes 38 ℃ Wash 4 minutes 38 ℃ Stable 1 minute Drying at room temperature Use the following composition of the treatment liquid.

[First developer] Water 700 ml Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Add water to 1000 ml (pH 10.1) [Inversion solution] Water 700 ml Nitrilo-N, N, N, -Trimethylenephosphonic acid-6-Na salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 5 g Glacial acetic acid 15 ml Water was added to 1000 ml [Color developer C] Water 700 ml Sodium tetrapolyphosphate 2 g Sodium sulfite 7 g Sodium triphosphate (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazic acid 1.5 g N- Ethyl-N -(Β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g Ethylenediamine 3 g Water was added to 1000 ml [Preparation liquid] Water 700 ml Sodium sulfite 12 g Ethylenediamine, sodium tetraacetate (2 Water salt) 8
g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water added 1000 ml [Bleach] Water 500 ml Ethylenediaminetetraacetic acid sodium (dihydrate) 2.0 g Ethylenediaminetetraacetate Iron (III) ammonium (dihydrate) 120.0 g Bromide Potassium 100.0 g Water added 1000 ml [Fixer] Water 800 ml Ammonium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water added 1000 ml [Stabilizer] Water 800 ml Formalin (37% by weight) 5.0 ml Spectral absorption maximum wavelength (λ _max ) of the sample treated with 1000 ml above by adding water
And the half-value width (W1 / 2) were measured by the same measurement method as in Example 1. The results are shown in Table-2.

The transmission density was measured by using a KD-7R type thermometer for the various measurements in Example 2.

As is clear from Table-2, the samples using the coupler of the present invention have a smaller full width at half maximum, less irregular absorption, and are very excellent in color reproducibility as compared with the sample using the comparative coupler. .

Further, it can be seen that the sample using the coupler of the present invention has a higher residual ratio of dye and is excellent in wet heat resistance as compared with the comparative sample.

Example 3 In Example 1, 1.50 g of trioctyl phosphate
Sample 30 of a red color photosensitive material in the same manner as in Example 1 except that 0.20 g of dioctyl phthalate was replaced with
Was produced. Next, in Sample 30, Samples 31 to 33 of the present invention were produced in exactly the same manner except that the comparative coupler a was replaced with the coupler of the present invention shown in Table 3.

Each of Samples 30 to 33 obtained above was subjected to wedge exposure according to a conventional method, and then subjected to the development processing step described in Example 1.

The spectral absorption maximum wavelength (λ
550 nm when the reflection density at _max ) and λ _max is 1.0
And reflection density at 700 nm (Dλ550 and Dλ70
0) was measured. A smaller value of Dλ550 means less improper absorption in the green region, and a smaller value of Dλ700 means sharper absorption and better color reproducibility.

The absorption spectra of Samples 30, 31 and 33 are shown in FIG.

In addition, the above processing agent samples were subjected to high temperature and high humidity (60 ℃, 80% RH)
It was left in the atmosphere for 14 days, and the heat resistance and humidity resistance of the dye image were examined. The obtained results are also shown in Table-3. However, the heat 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.

A KD-7R densitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used for various measurements.

From Table 3 samples 31 to 33 using the couplers of the invention
It can be seen that in both cases, Dλ550 and Dλ700 are small and the color reproducibility is good. Among them, the couplers (II-33), (II-43) and (II-24) are excellent in terms of λ _max . Also, the residual ratio of the dye image was significantly improved as compared with the comparative sample, and it was found that fading did not easily occur even when placed in high temperature and high humidity.

Example 4 [Preparation of red light-sensitive silver halide emulsion] 1 × 10 ^-5 per mol of silver chlorobromide emulsion containing 96 mol% of silver chloride
Mole of sodium thiosulfate was added, chemical ripening was carried out, and 5 minutes before the completion of chemical ripening, the following sensitizing dye a for the red light-sensitive emulsion layer was added to 5.0 x 10 ^-5 mol 0.1% per mol of silver halide.
It was added as a solution. After 5 minutes, 4-hydroxy-6-methyl-1,3,3a, 7- was added as a stabilizer at the end of the chemical ripening.
Tetrazaindene was added as a 0.5% aqueous solution. Thereafter, a 10% gelatin aqueous solution was added, and the mixture was stirred and cooled to prepare a red-sensitive silver halide emulsion.

[Preparation of Photosensitive Material] A red photosensitive color photosensitive material sample 34 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side. Unless otherwise specified, the addition amount of the compound is per 1 m ² (silver halide is equivalent to silver).

First layer: emulsion layer Comparative cyan coupler a dissolved in 1.2 g gelatin, 0.30 g red-sensitive silver chlorobromide emulsion and 0.24 g dioctyl phthalate.
A red-sensitive emulsion layer consisting of 0.45 g (9.1 x 10 ^-4 mol).

Second layer: protective layer A protective layer containing 0.50 g of gelatin. As a hardening agent, 2,4-
Dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

Next, in Sample 34, the comparative coupler a was replaced by the coupler of the present invention shown in Table 4 and the sensitizing dye a was replaced by the sensitizing dye shown in Table 4 (the amount of each of the coupler and the sensitizing dye added was Sample 34). Samples 35 to 50 of the present invention were prepared in exactly the same manner except that they were equimolar to. In addition, in the samples 34 to 50,
In order to examine the stability of the coating solution over time, two kinds of samples were prepared by coating the first layer emulsion layer coating solution on each of the samples, and after coating for 1 hour and 5 hours. Each of Samples 34 to 50 obtained above was subjected to wedge exposure according to a conventional method and then subjected to the development processing step described in Example 1.

The reflection densities at the spectral absorption maximum wavelengths (λ _max ) and λ _max of the samples treated as described above after 1 hour aging were 1.0 at 420 nm, 550 nm and 700 nm (Dλ ₄₂₀ , Dλ ₅₅₀ and Dλ). ₇₀₀₎ and to measure the difference) between the wavelength of the reflection density of 0.5 in the short side of the wavelength and the lambda _max of reflection density 0.5 in the longer wavelength side from the half-value width (lambda _max of the spectral absorption. The smaller the half-value width, the sharper the absorption and the better the color reproducibility.

Further, when λ _max is the same, the smaller the value of Dλ ₄₂₀ , the less irregular absorption in the blue region, and the smaller the value of Dλ ₅₅₀ ,
The less irregular absorption in the green region and the smaller the value of Dλ ₇₀₀ , the sharper the absorption and the better the color reproducibility.

The absorption spectra of Sample Nos. 35, 38 and 49 are shown in FIG.

In addition, the above-mentioned processed samples are subjected to high temperature and high humidity (60 ℃, 80% RH).
It was left in the atmosphere for 14 days, and the heat resistance and humidity resistance of the dye image were examined. The obtained results are also shown in Table 4. However, the heat 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.

Further, the reflection density of each sample of the coating liquid after 1 hour and 5 hours was measured using a densitometer to measure the sensitivity and fog. The optical density reference point that determines the sensitivity is fog +0.20
And the point.

The sensitivity ratio is 10% for the sample No. 22 using the comparative coupler a and the sensitizing dye a when the coating solution is stagnant for 1 hour.
It was set to 0.

A KD-7 type densitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used for various measurements.

 The above results are summarized in Table-4.

As is clear from the results shown in Table 4, the samples using the coupler of the present invention each have a smaller half-value width as compared with the sample using the comparative coupler, and have Dλ ₄₂₀ , Dλ ₅₅₀ and Dλ _700.
It can be seen that the respective irregular absorptions are small, the dye residual ratio is high, and the color reproducibility is good. Further, it can be seen that, in the case of the sensitivity decrease with time of the coating solution, the combination of the sensitizing dye preferably used in the present invention causes a small decrease in the sensitivity and is a preferable embodiment.

Incidentally, FIG. 3 shows that the coupler of the present invention has less unfavorable asymmetric absorption in the green region (550 nm) and a sharp absorption near λ _max as compared with the conventional phenolic coupler. .

Example 5 In preparation of a red light-sensitive silver halide emulsion, a red light-sensitive halogen was prepared in the same manner as in Example 4 except that the coupler and the sensitizing dye of the present invention shown in Table 5 were used. A silver halide emulsion was prepared.

The following layers were sequentially coated on the triacetyl cellulose film support from the support side to prepare samples 51 to 55 of red-sensitive reversal photographic light-sensitive material.

Unless otherwise specified, the addition amount of the compound is per 1 m ² (silver halide is equivalent to silver).

First layer: emulsion layer A red-sensitive emulsion layer comprising couplers shown in Table 5 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 A protective layer containing 0.50 g of gelatin. As a hardening agent, 2,4-
Dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

The samples 51 to 55 obtained above were each subjected to wedge exposure according to a conventional method, and then subjected to the reversal development processing step described in Example 2.

With respect to the coating solution for the first emulsion layer prepared so as to have the above composition, the sample sensitivity ratios of the coating solution for 1 hour and 5 hours were determined in the same manner as in Example 4, and the spectral absorption maximum of the sample treated above was determined. The wavelength (λ _max ) and the full width at half maximum (W1 / 2) were measured by the same measurement method as in Example 4.

The sensitivity ratio is 10% for the sample No. 51 using the comparative coupler a and the sensitizing dye b when the coating solution is stagnant for 1 hour.
It was set to 0.

In addition, the transmission density was measured using a KD-7 type densitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.) for various measurements in Example 5.

 The results are shown in Table-5.

As is clear from the results in Table 5, the sample using the coupler of the present invention has a smaller full width at half maximum as compared with the sample using the comparative coupler, and the color reproducibility is good. Further, the residual ratio of the dye image is also significantly improved as compared with the comparative sample.

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

[Effect of the Invention] As in the present invention, a color photographic light-sensitive material containing a pyrazoloazole-based cyan coupler in a red light-sensitive silver halide emulsion layer can form a clear cyan image excellent in spectral absorption characteristics. In addition, the cyan image is stable to heat and humidity and very stable to light.

Further, in the present invention, by using the sensitizing dye as described above in combination, the sensitivity is further promoted and the stability of the coating solution with time is excellent.

[Brief description of drawings]

FIG. 1 shows absorption spectrum curves of the developed samples Nos. 1, 2 and 13. Specimen 1 ... Comparative coupler a Specimen 2 ... Inventive coupler II-2 Specimen 13 ... Inventive coupler III-10 FIG. 2 shows absorption spectrum curves of developed samples Nos. 30, 31 and 33. Sample 30 …… Comparative coupler a Sample 31 …… Coupler of the present invention (II-33) Sample 33 …… Coupler of the present invention (II-24) FIG. 3 is an absorption spectrum curve of developed sample Nos. 35, 38 and 49. . Sample 35 …… Comparative coupler a Sample 38 …… Inventive coupler (II-28) Sample 49 …… Inventive coupler (II-38)

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Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one red light-sensitive silver halide emulsion layer on a support, wherein at least one of the red light-sensitive silver halide emulsion layers has the following general formula: [I] A silver halide color photographic light-sensitive material containing at least one cyan coupler. General formula [I] [Wherein R ₁ and one or two R ₂ are substituents having a substituent constant σp defined by Hammett of +0.20 or more, and other R ₂ are substituents. n represents 1 or 2, and when n = 2, R _{2 s} may be the same or different. Z represents a nonmetallic atomic group necessary for forming a nitrogen-containing heterocycle. X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent. ]