JPH01105251A - Silver halide color photographic sensitive material containing novel cyan coupler - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material capable of forming a clear cyan image with excellent spectral absorption characteristic by incorporating a coupler composed of a specified compd. in at least one layer of a silver halide emulsion layer. CONSTITUTION:The coupler shown by formula I is incorporated in at least one layer of the silver halide color photographic sensitive material comprising at least one layer of the silver halide emulsion layer mounted on a supporting body. In formula I, R1 is cyano, acyloxy, oxycarbonyl or carbamoyl group, R2 and Y groups are each hydrogen atom or a substituting group, X is hydrogen atom or a group capable of being released by allowing to react with the oxidant of a color developing main agent. Thus, the clear cyan image with the excellent spectral absorption characteristics can be formed, and the obtd. cyan image has the excellent stability against the heat and the humidity.

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 pyrazolotriazole cyan coupler.

[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.

In general, how do you like this photo? In aesthetics, subtractive color reproduction is used 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 . Generally poor in both light and heat fastness.

Also, U.S. Patent No. 4,122,369 and Japanese Unexamined Patent Publication No. 5
7-155538, JP-A-57-157246 and other specifications, and U.S. Patent No. 3,880,661.
The 2,5-diacylaminophenol cyan coupler having a hydroxyl group in the ballast portion described in the specification is still sufficiently satisfactory in terms of fastness to light and heat for long-term preservation of dye images. I haven't reached the level I can.

As a means to solve the above problems, the patent application No. 62-473
No. 23 has been reported, and by using the pyrazoloazole coupler described in that specification, a wide improvement effect was found. However, surprisingly,
When this compound is used, it has been found that the following new problems arise. In other words, the patent application No. 82-473
When the pyrazoloazole coupler described in No. 23 is dispersed and incorporated into a silver halide emulsion, it has a practical drawback that it tends to precipitate when the dispersion is stored in a refrigerator. They discovered that this was the case, and aimed to improve this.

As a result of various studies regarding the above-mentioned problems, the present inventors discovered that a pyrazolotriazole nucleus having a specific electron-withdrawing group gave preferable results, and completed the present invention. I ended up doing it.

[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 having an electron-withdrawing group.

A second object of the present invention is to use a new cyan coupler that improves the drawbacks of the conventionally used cyan dye-forming couplers, that is, it has sharp absorption and absorbs in the blue and green regions. It is an object of the present invention to provide a silver halide color photographic material that gives a clear cyan image with low so-called excellent spectral absorption characteristics.

A third object of the present invention is to provide a silver halide color photographic material containing a novel cyan coupler that does not change hue in response to heat and humidity and is capable of forming a cyan image.

A fourth object of the present invention is to provide a silver halide photographic material which exhibits good dispersion stability of cyan coupler especially during refrigerated storage and stability of coating solution over time.

[Structure 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 silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the formula - This was achieved by incorporating a coupler represented by [I].

[In the formula, R4 represents a cyano group, an acyloxy group, an oxycarbonyl group, or a carbamoyl group, R2 and Y represent a hydrogen atom or a substituent, and represents a group that ] Hereinafter, the present invention will be explained in more detail.

The cyan coupler represented by the general formula [I] according to the present invention is a pyrazolotriazole compound having an electron-withdrawing group, and the electron-withdrawing group is preferably Ham.
The substituent constant Op defined by Mett is + 0
．． 20 or more substituents.

Specifically, in the cyan coupler represented by the general formula [I], R1 is a cyano group, an acyloxy group, an oxycarbonyl group, or a carbamoyl group.

As the acyloxy group, alkylcarbonyloxy groups such as acetyloxy and 2-chloroacetyloxy are preferred.

Examples of the oxycarbonyl group include groups such as alkoxycarbonyl such as ethoxycarbonyl, and aryloxycarbonyl such as phenoxycarbonyl.

Examples of carbamoyl groups include alkyl groups and aryl groups (preferably phenyl groups) forming N,N-dibutylcarbamoyl, N-ethyl-N-dodecylcarbamoyl, etc.
etc. may be replaced.

Among these substituents, groups such as cyano, oxycarbonyl, and carbamoyl are particularly preferred in the present invention.

The substituent represented by R2 in general formula [I] is not particularly limited, but typically includes multiple groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. In addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, sulfamoyl, sulfonyloxy, alkoxy, aryloxy, heterocycleoxy,
Polygroups such as siloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro, sulfonic acid, and Also included are spiro compound residues, bridged hydrocarbon compound residues, and the like.

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

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

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

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

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
-7 is preferred.

Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyposbonyl groups, and arylphosphonyl groups. Ring; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl group ring; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; sulfamoylamino groups include alkylsulfamoylamino groups, Arylsulfamoylamino group, etc.; the heterocyclic group is preferably a 5- to 7-membered one, specifically 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group , 1-tetrazolyl group ring; The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3,4,5.6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5 −
Oxy group, etc.; As the heterocyclic thio group, a 5- to 5-membered heterocyclic thio group is preferable, 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, 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
]hebutan-1-yl, tricyclo[3,3,1,13
7] Decan-1-yl, 7,7-dimethyl-bicyclo[
2,2,1]heptane-1-yl and the like.

The substituent represented by R2 is particularly preferably one in which an aryl group, preferably a phenyl group, is directly bonded to the pyrazoloazole core.

The aforementioned substituents R1 and R2 may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

, X represents a group that leaves by reaction with an oxidized product of a color developing agent, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R0' has the same meaning as R8 above, Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group, and Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle. , the nitrogen-containing heterocycle may have a substituent, but preferably represents a triazole ring which is a partial structure of the general formula [1] of the present invention).
Preferably it is a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

In the general formula [II, Y represents a hydrogen atom or a substituent, and the preferred substituent represented by Y is, for example, one that is eliminated from the compound of the present invention after it reacts with the oxidized developing agent. However, for example, the substituent represented by Y may be a group that can be separated under alkaline conditions as described in JP-A No. 61-228444, etc.
Examples include substituents that are coupled off by reaction with an oxidized developing agent, as described in No. 133734 and the like. Preferably Y is a hydrogen atom.

Therefore, the compound represented by general formula CI] is more specifically represented by, for example, the following general formula [TI].

In the above general formula [II], R1, R2 and X have the same meanings as R1, R2 and X in the general formula [II], respectively.

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

The following margins indicate that these couplers of the present invention are J, Chem, -Soc
.

Perkin 1.2047-2052 (1977),
J, Hetercycle.

Chem, 11.423 (1974), Bar, 3
2,797 (1899), Chew.

Ber, 95.2861.2881 (1962), U.S. Patent No. 3,705°896, U.S. Pat. can.

Next, a typical synthesis example of the coupler of the present invention will be shown. still,
The coupler of the present invention can be synthesized according to these methods.

Synthesis example 1 tL; aMl.

Compound 1 [Synthesis] 3-carboxy-4-chloro-5-aminopyrazole 0
．． Add 25 mol to 1.5 fl of 6N hydrochloric acid, once completely dissolve, cool to below 5°C, and at 5 to 10°C, 19
60 ml of an aqueous sodium nitrite solution was added thereto, and the mixture was stirred at 0°C for 30 minutes.

Next, 120 g of stannous chloride dihydrate was added to 500 m
The mixture was dissolved in N concentrated hydrochloric acid and slowly added dropwise at below 0°C, and then stirred for 1 hour, and further stirred for 2.5 hours at room temperature.

Water was added to make up to 4 J:L, and hydrogen sulfide gas was introduced for 1 hour. The precipitated solid was separated by filtration, the filtrate was concentrated, 400 mL of ethanol was added, and the precipitated white crystals were collected by filtration. Dissolve this in water, neutralize it with an aqueous sodium bicarbonate solution,
10.15 mol was obtained.

[i-day] 0.15 mol of Mutual was dissolved in 750 mj of acetonitrile, 0.18 mol of Mutual was added, and 210 u+jl of triethylamine was added dropwise. After stirring at room temperature for 3 hours, the precipitated crystals were collected by filtration. These crystals and 0.15 mol of phosphorus oxychloride were added to 1 ft of toluene, and the mixture was heated under reflux for 4 hours.

Toluene was distilled off, and 750ml of acetonitrile was added.
Pyridine at 120 mA+ was added and the mixture was further heated under reflux for 3.5 hours. Filtration while hot gave 062 moles of cO.

[Dan-Sho] c O, 062 mol and 2N aqueous sodium hydroxide solution 3
1mR, 120mj! While cooling and stirring in acetonitrile with water, 0.062 mol of benzyloxycarbonyl chloride and 4NN aqueous sodium hydroxide solution 20j+ were slowly added dropwise, and the mixture was stirred for 30 minutes.

After neutralization with hydrochloric acid, the mixture was cooled, and the precipitate was collected by filtration and washed with cold water to obtain o, oso mol of 1.

[Sho-mi] 0.050 mol of d and 7 mR triethylamine in 10
Dissolve in 0mJ of dichloromethane, 24mJ of 6mR thionyl chloride dichloromethane solution! was added dropwise, and the mixture was stirred at room temperature for 1 hour. After adding ice water and stirring, the organic layer was separated and the solvent was distilled off, and the resulting residue was dissolved in 100 mA' acetonitrile. of pyridine and 0.06
A molar amount of diethylamine was added and stirred for 1 hour.

After further stirring at 55°C for 2 hours, the liquid was added to 300 mJ of water, the precipitate was collected by filtration, and this was recrystallized with ethyl acetate.
eO,022 mol was obtained.

[See - Compound U] 022 mol of eO was dissolved in 330mj+ of THF and reduced using pd/C. By removing pd/C,
After distilling off the solvent, the residue was recrystallized from ethyl acetate to obtain 0.014 mol of white needle-like crystals of Compound 21.

Synthesis Example 2 Compound 11 [The same compound as in Synthesis Example 1 was used as a raw material. 0.125 mJ of sulfuric acid was added to a mixture of 025 mol of dQ of Synthesis Example 1, 3.05 ml of methanol, and 50 ml of dichloroethane, and the mixture was refluxed for 7 hours. After cooling, add 100mR of water.
The extract was extracted with ethyl acetate, washed with an aqueous sodium bicarbonate solution, the solvent was distilled off, and the residue was recrystallized from acetonitrile to obtain 0.15 mol of aO.

[And - Compound] Dissolve 0.015 mol in methanol 200ml,
It was reduced using pd/C. After removing pd/C, the solvent was distilled off and recrystallized from ethyl acetate to obtain o and ooa moles of a white powder.

(Left below) The cyan coupler of the present invention usually has a content of 1X10-' mol to 1 mol, preferably IX10-', per 1 mol of silver halide.
It can be used in the range of 'mol-8X 1 (1-' mole).

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.

In the formula, 21 to Z9 represent an atomic group necessary to form a benzene ring or naphthalene ring fused to a pyridine ring, imidazole ring, thiazole ring, selenazole ring, oxazole ring, or tetrazole ring, and Z. represents an atomic group necessary to form a benzothiazole ring, benzoselenazole, β-naphthothiazole ring, β-naphthoselenazole ring, benzimidazole ring or 2-quinoline ring, and Q+ and Q2 jointly represent 4 -thiazolidinone, 5
-represents a group of nonmetallic atoms necessary to complete the thiazolidinone or 4-imidazolidinone nucleus; R11 and R2fi each represent a hydrogen atom, an alkyl group, or an aryl group;
R1? , R+a, R? ' and Ra ' represent an alkyl group, R11l and R21 each represent an alkyl group, an aryl group, or a heterocyclic group, and R12゜R
13+ R14+ RIS+ R18+ R20
+ R22, R23+R24 and R28 each represent an alkyl group or an aryl group.

°C represents 1 or 2, Y represents sulfur or selenium atom,
L1 to L6 each represent a substituted or unsubstituted methine group. K
is an acid anion.

General formula [A], CB], [preferably used in the present invention
The sensitizing dyes represented by C, [D], [E], and [F] are known, for example, F.M.
Author: The Chemistry of Heterocyclic Compounder
The Cyanine Drys Volume 18, The Cyanine Drys
andRelated [:pounds)
(A, Weissherged, Inters
It can be easily synthesized by the method described in J. Science, New York, 1964).

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

(Margin below) [S-1] [S-2] [5-33 [3-4] [S-5] [S-8] [5-10] [S-111 [S-121 (in I'' i2noco5υcoHN (C2Mco) Methods well known in the art can be used to add the above sensitizing dyes to the emulsion. For example, these sensitizing dyes can also be directly dispersed in the emulsion. or dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone or mixtures thereof,
Alternatively, it can be diluted or dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibrations can also be used during the dissolution process. Furthermore, as described in U.S. Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, this solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. how to,
As described in Japanese Patent Publication No. 46-24185, 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. The dye can also be added to the emulsion in the form of a dispersion by an acid dissolution/dispersion method. Other additions to emulsions include:
U.S. Patent No. 2,912,345;
No. 605, No. 2,996,287, and No. 3.
It is also possible to use the methods described in various specifications such as No. 425.835.

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 the sensitizing dye used in the present invention is 1.20xlQ-' to 0.15xlO-' mol per mol of silver halide, preferably 1.0xlO-' to 0.3xlO-'.
-'mol, more preferably 0.8xlO-' to 0.4x
1O'''4 moles.

The color photographic material of the present invention includes, 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 the cyan 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 may contain additional layers such as filter layers, interlayers,
It can have a protective layer, an undercoat layer, 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 a silver halide emulsion is used for color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains a chlorine atom, and at least 1% silver chloride. silver chloride,
Silver chlorobromide or silver chloroiodobromide is particularly preferred.

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) 1
The description in Vol. 76, pp. 22-31 (December 1978) can be referred to.

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

The color photographic 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 photographic material of the present invention is subjected to bleaching and fixing. 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.

[Example] 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. Note that the amount of the compound added is per 1 m'' unless otherwise specified (silver halide is a silver equivalent value).

1st layer: Emulsion layer Comparative cyan coupler aO,45 dissolved in 1.2 g of gelatin, 0.30 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 1.50 g of trioctyl phosphate.
A red-sensitive emulsion layer consisting of g.

Second layer: Protective layer Protective layer containing 0.50 g of gelatin. 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.

Next, Samples 2 to 9 were prepared in exactly the same manner except that the comparative coupler a in Sample 1 was replaced with the coupler of the present invention shown in Table 1 (the amount added was equimolar to that of Sample 1).

Samples 1 to 9 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 mA'
Ethylene glycol 15 mR 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)
) 2.5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g potassium hydroxide
Add 2.0g water to bring the total volume to 11 and adjust the pH to 10.
,20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100+l) Ammonium sulfite (40% solution) 27.5 mρ Potassium carbonate or glacial acetic acid pn 7.1 Add water and bring the total volume to 1℃.
shall be.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g Add water to make 11.

Spectral absorption maximum wavelength (λ□8) of each sample treated above
and λ,. 420 when the reflection density at is 1.0
Reflection density and spectral absorption half-width in nm (λII
The difference between a wavelength with a reflection density of 0.5 on the longer wavelength side than IIIK and a wavelength with a reflection density of 0.5 on the shorter wavelength side than λl1aX was measured. The smaller the value of Dλ42°, the less asymmetric absorption in the blue region, and the smaller the half-width, the sharper the absorption and the better the color reproducibility.

The absorption spectra of samples 1.2 and 6 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 and humidity resistance of the dye image was examined. The obtained results are also shown in Table-1. However, the heat-and-moisture resistance of the dye image is expressed as the percentage of dye remaining after the heat-and-moisture test with respect to an initial density of 1.0.

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

The above results are summarized in Table 1.

Comparative coupler a Shig Below Margin Table-1 As is clear from the results in Table-1, the samples using the coupler of the present invention all have a much smaller half-width than the samples using the comparative coupler. Since the asymmetric absorption represented by Dλ42° is also small, it can be seen that the spectral absorption characteristics are excellent.

Furthermore, it can be seen that the sample using the coupler of the present invention had a very high dye residual rate in the heat resistance/humidity test, and provided a solid cyan image.

In addition, FIG. 1 shows that the couplers of the present invention (Samples No. 002 and 6) are different from the conventional phenolic couplers (Sample No. 1).
This shows that there is less unfavorable asymmetric absorption in the green region and that the absorption near λ□8 is sharper than that in the green region.

Example 2 The following layers were sequentially coated on a triacetyl cellulose film support from the support side to prepare red-sensitive color reversal photographic materials 1O-16. Unless otherwise specified, values are shown per 1 m (silver halide is equivalent to silver).

1st layer: Emulsion layer 1.4 g of gelatin, 0.5 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 1.5 g of dioctyl phosphate.
The coupler shown in Table 2 (9, IX 1
A red-sensitive emulsion layer consisting of 0-'mol).

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-8-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℃ White 6 minutes 38
℃ fixation 4 minutes 38℃ water washing 4 minutes 38℃ cooling
Constant for 1 minute Normally wet and dry The composition of the drying solution used is as follows.

[First developer] Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (
monohydrate) 30 gl-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0
, 1% solution) 2 Add rnR water
1000mj! (p)I 10
．． 1) [Reversing solution] Nitrilo-N,N,N-trimethylenephos, fonic acid, hexasodium salt 3g 1st chloride
Tin (dihydrate) Igp-aminophenol 0.1g Sodium hydroxide
5g glacial acetic acid
Add 15 mβ water
1000 ml [Color developer] Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium tertiary phosphate (decahydrate) 36g Potassium bromide
1g potassium iodide (0.1% solution)
90 mA sodium hydroxide
3g Citrazic acid 1
．． 5 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11 g ethylenediamine 3 g Add water
1000 mR [Adjustment solution Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 mR glacial acetic acid
Add 3 mR water
1000 mA + [Bleach solution] Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ammonium iron(III) ethylenediaminetetraacetate (dihydrate) 120.
0g potassium bromide IQo, 0
g Add water to 1000 mN
[Fixer] Ammonium thiosulfate ao, og Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water
1000 mA' [stabilizer] Formalin (37% by weight) 5.0m
lConidax 5.0+n
j! (manufactured by Konica Corporation) Add water to 10100O Maximum spectral absorption wavelength (λwaaX) of the sample treated above
, half-width (114) and Dλ42° were measured by the same measuring method as in Example 1. The results are shown in Table-2.

Incidentally, in the various measurements in Example 2, a D-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-width and smaller asymmetric absorption than the sample using the comparative coupler, so it has excellent spectral absorption characteristics and color It provides cyan dye images with good reproducibility.

Furthermore, the sample using the coupler of the present invention had a much higher dye residual rate in the heat resistance test than the comparative sample, and gave a solid cyan image.

[Dispersion Stability Test] A mixed solution containing 2 x 10-' moles of comparative cyan coupler B, 3.0 g of dioctyl phthalate, and 3 g of ethyl acetate was heated to 60°C to dissolve it, and then this was dissolved in alkanol B (alkylnaphthalene sulfonate). 17 mj of a 5% aqueous gelatin solution containing 1.7 ml1 of a 5% aqueous solution (manufactured by DuPont). were mixed and emulsified and dispersed using an ultrasonic dispersion machine to prepare a dispersion liquid.

Ethyl acetate was distilled off under reduced pressure from these dispersions to obtain Dispersion Sample 1. To observe the dispersion stability of the cyan coupler, the dispersion was stored in a refrigerator (5°C) for 6 days, then kept warm in a 40°C water bath, and the state of crystal precipitation was observed using an optical microscope for 6 hours immediately after incubation. After that, each observation was made 12 hours later. Further, dispersion samples 2 to 5 were prepared in the same manner using the couplers shown in Table 3, and the dispersion stability of the couplers was examined. The results are shown in Table 3.

Comparison coupler b Table 3 *Evaluation of precipitation properties in the table was performed as follows.

○: No precipitation.

△D Some precipitation occurs, but there is no practical problem.

×: Precipitation occurs and there is a problem in use.

As is clear from Table 3, the cyan coupler of the present invention is
It was found that a dispersion with extremely good dispersion stability could be obtained because precipitation was less likely to occur than in the case of comparison.

Example 3 [Preparation of red-sensitive silver halide emulsion] 1xlO-11 mol of sodium thiosulfate was added per 1 mol of silver chlorobromide emulsion containing 96 mol% of silver chloride, and chemical ripening was performed. Before 5 minutes, add the following sensitizing dye a for the red-sensitive emulsion layer to 5.0 x lO-5 mol 0.5 x 1 mol per mol of silver halide.
1! was 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 a 0.5* aqueous solution. Thereafter, an aqueous gelatin solution of o* was added, stirred, and then cooled to prepare a red-sensitive silver halide emulsion.

[Preparation of Photosensitive Material] Red-sensitive color photosensitive material sample 17 was prepared by sequentially coating the following layers from the support side onto a paper support laminated on both sides with polyethylene. Incidentally, the amount of the compound added is shown per 1 m2 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 0.45 g of comparative cyan coupler a dissolved in 0.24 g of dioctyl phthalate (9,1xlO-'
A red-sensitive emulsion layer consisting of mol).

2nd layer: Protective layer Protective layer containing 0,-50 g of gelatin. In addition, 2,4-dichloro-6-hydroxy-S-triazine sodium salt was added as a hardening agent in an amount of 0.017 g per 1 g of gelatin.

Next, in Sample 17, comparative coupler a was replaced with the coupler of the present invention shown in Table 4, and sensitizing dye a was replaced with the sensitizing dye shown in Table 4. Sample 18 of the present invention was prepared in exactly the same manner except that the molar ratio was set to be equimolar.

In addition, in the above samples 17 and 18, in order to check the stability of the coating solution over time, each sample was coated after 1 hour and 5 hours after preparing the coating solution for the first emulsion layer. Two types of samples were prepared. Sample 1 obtained above
Samples No. 7 and No. 18 were each subjected to wedge exposure according to a conventional method, and then developed using the processing steps described in Example 1.

Spectral absorption maximum wavelength (λ□X) and reflection density at λ□8 of each sample coated after 1 hour of treatment above were 420 nm, , 550 nm and 7 when 1.0.
Reflection density at 00 nm (Dλ42°, Dλ6.

and Dλ7°. ) and the half-width of spectral absorption (λ□8
The wavelength with a reflection density of 0.5 on the longer wavelength side and λlIaM
The difference from the wavelength with a reflection density of 0.5 on the shorter wavelength side) was measured. The smaller the half-width, the sharper the absorption and the better the color reproducibility.

Furthermore, when λ□8 is the same, the smaller the value of Dλ42°, the less asymmetric absorption in the blue region, the smaller the value of Dλsso, the less asymmetric absorption in the green region, and the smaller the value of Dλ700, the less asymmetric absorption. This means that the image is sharp and has excellent color reproducibility.

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 4. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining after the heat resistance and humidity resistance test with respect to an 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 optical density reference point that determined the sensitivity was fog +0.2.
It was set as 0 point.

Note that the sensitivity ratio is based on the sample sensitivity of sample No. 17 using comparative coupler a and sensitizing dye a after the coating solution stagnates for 1 hour as 100.

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

The above results are summarized in Table 4.

Sensitizing dye a Table 4 As is clear from the results in Table 4, the samples using the coupler of the present invention all have smaller half-widths than the samples using the comparative coupler, Dλ420, Dλssa 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.

[Effects of the Invention] According to the present invention, a clear cyan image with excellent spectral absorption characteristics can be formed using a color photographic material containing a pyrazoloazole-based cyan coupler, and the cyan image is resistant to heat and humidity. It is very stable against Further, the coupler has excellent stability of the coupler dispersion even when stored in a refrigerator.

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 the drawing]

FIG. 1 shows absorption spectrum curves of developed samples No. 1.2 and 6. 1... Comparative coupler a (sample No. 1) 2... Coupler of the present invention (sample No. 2) 6... Coupler of the present invention (
Sample No. 6) Patent applicant Konica Co., Ltd. Representative Patent Attorney Miki Nakajima 1 person Figure 1 (nm)

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a compound represented by the general formula [I]. A silver halide color photographic material characterized by containing a coupler. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a cyano group, acyloxy group, oxycarbonyl group, or carbamoyl group, R_2 and Y represent a hydrogen atom or a substituent, X represents a hydrogen atom or a group that is released upon reaction with an oxidized product of a color developing agent. ]