JPH01553A - Silver halide color photographic material containing a new cyan coupler - Google Patents

Abstract

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

Description

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

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

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

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

However, cyan images obtained from conventionally used phenols and naphthols have serious problems in color reproduction. The reason is that the absorption is not sharp on the short wavelength side, and the edge region also has unnecessary absorption, that is, asymmetric absorption. 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, US special liver 2nd and 3rd
67.531 and 2,423,730, the dye images obtained with the 2-acylaminophenolic cyan couplers described in U.S. Pat. The dye images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 2,772,162 generally have poor light fastness, and the dye images obtained from the 1-hydroxy-2-natutamido cyan coupler have poor light fastness. , generally poor in both light and heat fastness.

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

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

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

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

[Structure of the Invention] The above object of the present invention has been achieved by incorporating a coupler represented by formula [I] into a photographic light-sensitive material having at least one silver halide emulsion layer on a support.

- Formula [I] In the formula, R represents an electron-withdrawing group, and X represents a hydrogen atom or a substituent that is released by reaction with an oxidized product of a color developing agent. Y represents a hydrogen atom or a substituent.

The present invention will be explained in detail below.

The novel cyan coupler represented by the general formula [I] used in the present invention is an IH-pyrazolo[I,5-d]-tetrazole compound having an electron-withdrawing group at a position adjacent to the active site.

In general formula [I], the electron-withdrawing group represented by R is preferably a substituent with a substituent constant δ defined by Hammett of +0.20 or more, and specifically, sulfonyl, sulfinyl , sulfonyloxy,
Sulfamoyl, phosphoryl, carbamoyl, acyl,
Examples include 8 groups such as acyloxy, oxycarbonyl, carboxyl, cyano, nitro, fluorinated alkyl having multiple fluorine atoms at α-position, halogenated alkoxy, halogenated aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms.

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

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

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

Examples of the sulfasoyl group include N,N-dialkylsulfamoyl such as N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl, N,N-diarylsulfamoyl, N-alkyl- Examples include groups such as N-arylsulfamoyl.

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

As the carbamoyl group, N,N-dialkylcarbamoyl, N,N-diarylcarbamoyl, N-alkyl-
Examples include groups such as N-arylcarbamoyl.

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

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

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

As the fluorinated alkyl group having multiple fluorine atoms at α-positions, trifluoromethyl is preferred.

As the halogenated alkoxy group, an α-halogenated alkoxy group is preferable.

As the halogenated aryloxy group, polygroups such as tetrafluoroaryloxy and pentafluoroaryloxy are preferred.

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

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

In addition to the above substituents, trifluoromethyl, heptafluoroisopropyl, nonylfluoro(1)butyl, tetrafluoroaryl, pentafluoroaryl, and the like are also preferably used.

In the compound used in the present invention, the group represented by R is preferably arylsulfonyl, halogenated substituted alkylsulfonyl, arylsulfinyl, halogenated substituted alkylsulfinyl, halogenated alkyl, and cyano, More preferred are arylsulfonyl, arylsulfinyl, and halogenated alkyl.

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

Examples of the group that is released by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
Examples include carboxyl, (R1 has the same meaning as R8 above, and R2 and R5 represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group), but preferably a halogen atom, especially a chlorine atom. be.

- Y in formula [I] represents a hydrogen atom or a substituent, and the preferable substituent represented by Y is one that is separated 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 vine group that leaves under alkaline conditions as described in JP-A No. 61-228444, or a vine group that leaves under alkaline conditions, as described in JP-A No. 56-133734.
Examples include substituents that are eliminated by reaction with the oxidized developing agent, as described in No. 1, etc. Preferably Y is a hydrogen atom.

The compound represented by the general formula [I1] is more preferably represented by the following formula [II].

-Math [! i] In general formula [I1], R and X are - formula [I]
has the same meaning as R and X.

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

The following margins These cyan couplers of the present invention are described in the Journal of
The Chemical Society
f the Chemical 5ociety
), Perkin I
(1977), 2047-2052, Chem.
Ber.

89, 2550 (1956),
Chem, Int, Ed, Eng.

21, 698 (1982), GB, 1,047,6
No. 12, tlsP3, 227゜No. 554, tlsP3, 3,41
No. 9,391, No. 3,725,067, No. 3,926
．． No. 631, JP-A-57-70817, JP-A No. 58-42
No. 045, No. 59-99437, No. 59-16254
No. 8, No. 59-171956.

No. 60-33552, No. 60-43659, No. 60
-172982.

Japanese Patent Application No. 60-190779, Japanese Patent Application No. 1983-120054, Japanese Patent Application No. 1982-122450, Japanese Patent Application No. 1987-3657
No. 7 and Hemisi z' Berichte (Ghem, Ber,
), 95.2861 and 2881 (1962), etc., and can be easily synthesized by those skilled in the art.

Typical synthesis examples are shown below.

Synthesis example 1 (synthesis of compound 3)! [Visiting] 0.075 mol of a synthesized with reference to Chem, Ber, 95.2861 (1982) was added to ethanol 3001, and 0.075 mol of 100% hydrazine hydrate was added.
g was added dropwise, heated under reflux for 8 hours, and then the solvent was distilled off to give 0.
．． 0.41 moles of each were obtained.

[Reciprocally] 0.041 mol of b in 6N hydrochloric acid 200++j! In addition, 0.045 mol of sodium nitrite was added to 8 mol of water at 0°C.
Dissolved in n+2 and added dropwise, after stirring for 30 minutes, 0.090
A mole of stannous chloride 2 was dissolved in concentrated hydrochloric acid (SQmff) and added dropwise at 0°C. The mixture was stirred at 0° C. for 1 hour and at room temperature for 1 hour, 450 mR of water was added, and hydrogen sulfide gas was passed through. The crushed crystals were washed with ethanol and water.
．． 0.029 mol of tan was obtained.

[Dan-Dan] c Dissolve 0.029 mol of O in 20 m2 of 6N hydrochloric acid, dissolve 0.031 mol of sodium nitrite in 30 mA' water, add dropwise at 0°C, stir for 1.5 hours, and then neutralize. did. After extracting the reaction solution with ethyl acetate, the solvent was distilled off,
The residue was recrystallized using acetonitrile and 0.012
Got a mole.

[Active-i] d O, 012 mol in acetic acid 50 mR, sulfuric acid 14 mA'
, and 1.5 mj of water, and the mixture was heated under reflux for 2 hours. Neutralized with aqueous sodium hydroxide solution, extracted with ethyl acetate, distilled off the solvent, added water and precipitated.
071 mol was taken as t2.

[i=Compound 3] Dissolve 0.0071 mol of e in 30 mj+ acetic acid, 3
5% hydrogen peroxide solution 10mj! Slowly drip 50
The mixture was stirred at ℃ for 3 hours. Thereafter, 100 ml of water was added, neutralized with an aqueous sodium hydroxide solution at about 5°C, extracted with ethyl acetate and distilled off, and the resulting precipitate was recrystallized with acetonitrile to form a compound in the form of white powder crystals. 3 to 0.
0059 mol was obtained.

Synthesis Example 2 (Synthesis of Compound 13) [! -dan] o, oao mole of a and 0.180 mole of b to 400
mI! After heating under reflux for 4 hours, the solvent was distilled off, acetic acid was added to the residue, insoluble matter was filtered out, and the solution was concentrated to obtain 048 mol of CO.

[Dan-sho] Add 500 mJ of ethanol to 0.048 mol of tan,
0.051 mol of 00% hydrazine hydrate was added dropwise.

After heating under reflux for 6 hours, the solvent was distilled off, and the residue was recrystallized from ethanol to obtain 0.026 mol of U.

[Mutual→Compound 13] [Mutual-tan] [Tan-sho] [Sho->mi] in Synthesis Example 1
Compound 13, white needle-like crystals, was prepared in the same manner as 0.009
Got a mole.

Synthesis Example 3 (Synthesis of Compound 21) ■ I described in JP-A-60-33552
Using H-6-amituvirazolo[I,5-d]tetrazole as a raw material, Org, 5ynth, , III
130 (1955),
IH-6-hydroxypyrazolo[I,5-d]tetrazole was synthesized.

0.075 mol of IH-6-hydroxypyrazolo[I,
700 mj of 5-dl tetrazole! of acetonitrile, dropwise added 0.080 mol of undecane carbonyl chloride, and after adding Q, 08Q mol of pyridine,
The mixture was stirred at room temperature for 2 hours. The reaction solution was drained, the precipitate was collected in a furnace, and dissolved in 150 Il+il of methylene chloride-tetrahydrofuran (1,5:1).
．． 077 moles of N-chlorosuccinimide are added,
After stirring at room temperature for 3.5 hours, 500 mj of methylene chloride was added, washed with a saturated aqueous sodium bicarbonate solution and water, and the solvent was distilled off.
．． 038 mol was obtained.

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

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.

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

The photosensitive materials of the present invention, including this color photographic paper,
It may be for a single color or for multiple colors. In a multicolor light-sensitive material, the cyan coupler of the present invention may be contained in any layer, but is preferably contained in a red-sensitive silver halide emulsion layer. Multicolor light-sensitive materials have dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum. Each building block can be comprised of a single or multiple emulsion layer sensitive to a certain region of the wave vector. The constituent layers of the photosensitive material, including the layers of image-forming units, may 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 is
Additional layers such as filter layers, interlayers, protective layers, subbing layers, etc. can be included.

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

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

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

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

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

Regarding these, for example, Research Disclosure w
-(Research Disclosure) 17
6, pp. 22-31 (December 1978) can be referred to.

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

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

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

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

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

[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 2 g of gelatin L, 0.30 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 0.3 g of dioctyl phthalate.
A red-sensitive emulsion layer consisting of 45 g of comparative cyan coupler aQ dissolved in 20 g.

Second layer: Protective layer Protective layer containing gelatin o, sog. In addition, as a hardening agent, 2
．． 4-dichloro-6-hydroxy-5-)-riazine sodium salt was added at 0.017 g per gram of gelatin.

Next, Samples 2 to 11 of the present invention were prepared in exactly the same manner as in Sample 1, except that comparative coupler a was replaced with the coupler shown in Table 1 (the amount added was the same molar amount as comparative a).

Samples 1 to 11 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 with lA, 3 minutes at 25°C to 30°C, drying at 75°C to 80 tons for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) Benzyl alcohol 15 mB Ethylene glycol 15 ml Potassium sulfite 2.0 g Bromide
Rium
0.7g sodium chloride 0.2g charcoal
potassium acid
30.0g hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS)
2.5g aniline sulfate
5.5g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g potassium hydroxide 2.0g water was added to bring the total amount to IIL,
Adjust the pH to 10,20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100mj! Ammonium sulfite (40% solution) Adjust the pH to 7.1 with 27.5 ai + potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.
shall be.

(Stabilizing solution) Add 1.0 g of 5-chloro-2-methyl-4-isothiazolin-3-one 10 g of ethylene glycol to I
Let's call it J2.

For Samples 1 to 11 treated above, the maximum spectral absorption wavelength (λ□X) and the reflection density at λ, , x are 1.
It is the difference between the reflection density at 420 nm (Dλ42o) at 0, and one point on the longer wavelength side than λ□8 and one point on the shorter wavelength side than λImAK, where the reflection density is 0.5. The half width (W%) was measured, and the spectral absorption characteristics and color reproducibility were examined. Dλ4. . The smaller the value of , the less irregular absorption in the green region, and the smaller the value of W %, the sharper the absorption and the better the color reproducibility.

Moreover, the absorption spectra of Samples 1 and 2 are shown in FIG.

In addition, each of the above treated samples was heated at high temperature (60℃, 80%R).
) I) The dye image was left in an 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-1. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining after the heat and humidity resistance test with respect to the initial density of 1.0. Incidentally, a D-7R type densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) was used for the measurement.

Comparative coupler a 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 and less asymmetric absorption than the samples using the comparative coupler. This shows that it has excellent spectral absorption characteristics. moreover,
It can be seen that the dye has a high residual rate, has excellent heat resistance and moisture resistance, and is robust.

Furthermore, Figure 1 shows that the coupler of the present invention has less undesirable asymmetric absorption in the green ft region and sharper absorption in the vicinity of λm□ compared to conventional phenolic couplers. .

Example 2 Red-sensitive color reversal photographic materials 12 to 16 were prepared by sequentially coating the following layers on a triacetyl cellulose film support from the support side. Incidentally, unless otherwise specified, the amount of the compound added is shown per 1 m2 (silver halide is a silver equivalent value).

1st layer: Emulsion layer 1.4 g of gelatin, red-sensitive silver chlorobromide emulsion (96 g of silver chloride)
mol%) 0.5g and dibutyl phthalate 0.2
4g of dissolved coupler shown in Table 2 (9,1X10
-4 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-5-1-riazine 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 First development 6 minutes 38℃ Water washing 2 minutes 38℃ Incubation
Transfer 2 minutes 38℃ Color development 6 minutes 38℃ Adjustment 2 minutes 38℃ bleaching
White 6 minutes 38℃
Fixation 4 minutes 38℃ water
Wash 4 minutes at 38℃
1 minute at room temperature
The composition of the drying treatment liquid used is as follows.

[First developer water
700 mg sodium tetrapolyphosphate
2g sodium sulfite 20
g Hydroquinone monosulfonate 30 g
Sodium carbonate (1 water temperature) 30 g
-phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone 2g Potassium Bromide
2.5g potassium thiocyanate
1.2g potassium iodide (0.1% solution) 2m
! Add water 1000rn
n (po to, t) [Reversal liquid] Water
700 ml Nitrilo-N, N, N-9I-
Rimethylenephosphonic acid-6. -Na salt
3g stannous chloride (dihydrate) Igp
-Aminophenol O, 1g sodium hydroxide 5g glacial acetic acid
Add 15 mA' water
1000 mN [Color developer C] Water
700 ml sodium tetrapolyphosphate
2g Sodium sulfite 7g
Tertiary sodium phosphate (12 hydrate) 36g Potassium bromide 1g Potassium iodide (0,1
% solution) 90 mJ sodium hydroxide
3g citradinic acid
1.5g-4-aminoaniline sulfate
11 g ethylenediamine
Add 3g water for 1000
tnR [adjustment solution] water
700 mf! sodium sulfite
12 g Sodium ethylenediaminetetraacetate (dihydrate) 11 g Thioglycerin 0.4 mR glacial acetic acid
Add 3 mR water
1000 mj+ [vote white night water
5ooornl! Sodium ethylenediaminetetraacetate, (dihydrate) 2.0g Ethylenediaminetetraacetate iron (III) 7% nium (dihydrate) 12Q, 0g Potassium bromide 100.0g Add water to 1000 mR [Fixer] Water
800 ml) ammonium thiosulfate
80.0 g sodium sulfite
5.0gm sodium sulfite
Add 5.0g water for 1000
mj! [Stabilizer] Water
800mj! Formalin C37mHk%)
Add 5.0+++1 water
1000 ml Sample 12~ treated above
Regarding No. 16, as in Example 1, the maximum spectral absorption wavelength (λ
□X) and half width (W34) ・Dλ4□0 were measured. The results are shown in Table-2.

Incidentally, in the various measurements in Example 2, a KD-7R type densitometer 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 Dλ42° than the sample using the comparative coupler, so it has excellent spectral absorption characteristics and color reproduction. It can be seen that the quality is good.

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

Example 2i1 Example 3 Sample 17, a red-sensitive color photosensitive material, was prepared in exactly the same manner as Sample 1 of Example 1, except that 0.2 g of dioctyl phthalate in Example 1 was replaced with 1.5 g of trioctyl phosphate. did.

Next, Samples 18 to 23 of the present invention were prepared in exactly the same manner as Sample 17, except that the comparative coupler a was replaced with the coupler of the present invention shown in Table 3.

Samples 17 to 23 obtained above were each subjected to wedge exposure according to a conventional method, and then subjected to the development process described in Example 1.

For samples 17 to 23 treated above, the spectral absorption maximum wavelength (λ11x) and the reflection at λ118 are 1
．． The reflection density (Dλ550 and Dλ700) at 550 nm and 700 nm at 0 was measured.

The smaller the value of Dλ550, the less irregular absorption in the green region, and the smaller the value of Dλ700, the sharper the absorption and the better the color reproducibility. Sample 17.1
The absorption spectra of 9 and 21 are shown in FIG.

In addition, each of the above treated samples was heated at high temperature (60℃, 80%R).
1() for 14 days, and the heat resistance and moisture resistance of the dye image were examined. The obtained results are also shown in Table 3. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining after the heat and humidity resistance test with respect to the initial density of 1.0. In addition, a KD-7R type densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) was used for various measurements.

(The following is a blank space) Table 3 Samples 18 to 3 using the couplers of the present invention from Table 13
It can be seen that both of No. 23 have small Dλ550 and Dλ700 and good color reproducibility. Furthermore, the heat resistance and humidity resistance of the dye image are also significantly improved compared to the comparative samples, as is clear from the dye residual rate, and it can be seen that fading is difficult to occur even when exposed to high temperatures.

FIG. 2 shows that the coupler of the present invention has less undesirable absorption in the green region (550 nm) and sharper absorption near max than conventional phenolic couplers.

[Effects of the Invention] By using the color photographic material containing the pyrazolotetrazole cyan coupler of the present invention, a clear cyan image with excellent spectral absorption characteristics can be formed, and the cyan image is resistant to heat and humidity. It is very stable.

[Brief explanation of drawings]

FIG. 1 shows absorption spectrum curves of developed samples No. 31 and No. 2. Sample No. 11: Comparative coupler a Sample No. 2: Invention coupler-1 FIG. 2 shows absorption spectrum curves of developed samples No. 17, 19, and 21. Sample No. 17... Comparison coupler a Sample No. 19... Invention coupler 32 Sample No. 2
1...Coupler 33 of the present invention Figure 1 Liquid length (nm)

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, which has the general formula [
A silver halide color photographic material containing a coupler represented by I. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. represent. Y represents a hydrogen atom or a substituent. ]