JPH0417415B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light and stain generation is prevented. . [Prior Art] Conventionally, aromatic primary
The oxidized product of the amine-based color developing agent and the coloring agent undergo a coupling reaction to produce, for example, indophenol, indoaniline, indamine, azomethine,
It is well known that phenoxazine, phenazine, and pigments similar to them are produced to form color images. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow and magenta, are added to blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers, respectively. A silver halide color photographic light-sensitive material containing a coupler that develops a cyan color is also used. Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indazolone couplers. It is known,
Furthermore, as a coupler for cyan image formation,
For example, phenolic or naphthol couplers are commonly used. It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. In addition, uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) turn yellow due to light or moist heat (hereinafter referred to as Y
- A product that does not cause stains is desired. However, in the case of magenta couplers, fading of uncolored areas due to light, Y-stain due to moist heat, and color fading of dye image areas due to light is much larger than that of yellow couplers and cyan couplers, and often poses a problem. Couplers commonly used to form magenta dyes are 5-pyrazolones. The dye formed from this magenta coupler of 5-pyrazolones has a main absorption around 550 nm, as well as a wavelength of 430 nm.
The presence of side absorption in the vicinity is a major problem, and various studies have been conducted to solve this problem. Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption and are particularly useful for obtaining color images for printing. For these techniques, see e.g. US Patent 2343703
No. 1, British Patent No. 1059994, etc. However, the above-mentioned magenta coupler has the disadvantage that the image storage property, especially the fastness of the dye image to light, is extremely poor, and the Y-stain in the uncolored area is large. As another means for reducing the side absorption near 430 nm of the above magenta coupler,
Pyrazolobenzimidazoles described in US Pat. No. 1047612; indazolones described in US Pat. No. 3770447;
1H-pyrazolo [5,1
-c]-1,2,4-triazole type coupler,
1H− as described in Research Disclosure 24531 (1984)
Pyrazolo[1,5-b]-1,2,4-triazole coupler, Research Disclosure24626
(1984) 1H-pyrazolo[1,5-c]-
1,2,3-triazole type coupler, JP-A-59
−162548, Research Disclosure 24531 (mentioned above)
1H-imidazo[1,2-b]-pyrazole coupler described in Research Disclosure 24230
(1984), Research
Magenta couplers such as the 1H-pyrazolo[1,5-d]tetrazole type coupler described in Disclosure 24220 (1984) have been proposed. Among these,
1H-pyrazolo[5,1-c]-1,2,4-triazole coupler, 1H-pyrazolo[1,5-
b]-1,2,4-triazole coupler, 1H
-pyrazolo[1,5-c]-1,2,3-triazole coupler, 1H-imidazo[1,2-b]
Pyrazole type coupler, 1H-pyrazolo[1,5
-b] The dye formed from the pyrazole type coupler and the 1H-pyrazolo[1,5-d]tetrazole type coupler is formed from the 5-pyrazolones having the above-mentioned anilino group at the 3-position, and the sub-absorption near 430 nm. It is significantly smaller than pigments, which is preferable in terms of color reproduction.Furthermore, it has the favorable advantage that the generation of Y-stain in uncolored areas due to light, heat, and humidity is extremely small. However, the fastness of azomethine dyes formed from these couplers to light is extremely low, and in addition, the dyes are easily discolored by light, which significantly impairs the performance of color photographic materials, especially printed color photographic materials. , it has not been put to practical use in printed color photographic materials. Furthermore, JP-A-59-125732 discloses that a 1H-pyrazolo[5,1-c]-1,2,4-triazole type magenta coupler is used in combination with a phenol compound or a phenyl ether compound. 1H-pyrazolo[5,1-c]-1,2,4
- Techniques have been proposed to improve the light fastness of magenta dye images obtained from triazole type magenta couplers. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light. [Object of the invention] The present invention has been made in view of the above problems.
A first object of the present invention is to provide a color photographic material with excellent color reproducibility and significantly improved light fastness of magenta dye images. A second object of the present invention is to provide a color photographic material having a magenta dye image that is less discolored by light. A third object of the present invention is to provide a color photographic material in which the generation of Y-stain in undiscolored areas due to light, heat, and humidity is prevented. [Structure of the Invention] The above object of the present invention is to provide a silver halide color photograph characterized by containing a magenta dye-forming coupler represented by the following general formula [] and a compound represented by the following general formula []. This is accomplished using photosensitive materials. General formula []

[Formula] or

[Formula] In the formula, R is an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a bridged hydrocarbon compound residue,
represents an acylamino group or an alkylthio group,
These groups may have substituents. R ₁ and
R ₂ represents an alkyl group, an aryl group, an amino group, an acylamino group, a sulfonyl group, or an alkylthio group, and these groups may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. General formula [] In the formula, R ¹ represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y is a nonmetal necessary to form a piperazine ring, morpholine ring, thiamorpholine ring, imidazolidine ring, or homopiperazine ring together with the nitrogen atom. Represents a group of atoms. Next, the present invention will be specifically explained. In the magenta coupler represented by the general formula [] according to the present invention, the alkyl groups represented by R, R ₁ and R ₂ include those having 1 to 32 carbon atoms;
The cycloalkyl group has 3 to 12 carbon atoms, especially 5 carbon atoms.
-7 is preferred, and the alkyl group may be linear or branched. In addition, these alkyl groups and cycloalkyl groups include substituents [for example, aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, as well as acyl, carboxy, carbamoyl , alkoxycarbonyl, aryloxycarbonyl, which are substituted via a carbonyl group, and further substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy Substitution via an oxygen atom such as nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. Substitution via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, substitution via a phosphorus atom such as phosphonyl, etc.) . Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chloro-t-butyl group,
Trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3- m-butanesulfonaminophenoxypropyl group, 3-4'-{α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4′-[α-
(2″,4″-di-t-amylphenoxy)butanamide]phenyl}-propyl group, 4-[α-(o-
chlorophenoxy) tetradecaneamide phenoxy] propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. The aryl group represented by R, R ₁ and R ₂ is preferably a phenyl group, which may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamide phenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamide] phenyl group, etc. The heterocyclic group represented by R is 5- A 7-membered group is preferable, and may be substituted or condensed. Specific examples thereof include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the sulfonyl group represented by R ₁ and R ₂ include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group. Examples of the bridged hydrocarbon compound residue include bicyclo[2.2.1]heptan-1-yl,
tricyclo[3.3.1.1 ^3,7 ]decane-1-yl, 7,
7-dimethyl-bicyclo[2.2.1]heptane-1
-il etc. The amino group represented by R ₁ and R ₂ is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, m-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-
Examples include hexadecaneamide anilino group. Examples of the acylamino group represented by R, R ₁ and R ₂ include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent. acetamide group, α-ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxylene group. Examples include sibutanamide group. The alkylthio group represented by R, R ₁ and R ₂ is
It may further have a substituent, for example, an ethylthio group, a dodecylthio group, an octadecylthio group,
Examples include phenethylthio group and 3-phenoxypropylthio group. Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by and substituent groups. In addition to carboxyl groups, examples of groups substituted via a carbon atom include, for example, the general formula (R ₁ ' has the same meaning as R above, Z' is 1H-pyrazolo[5,1-c]-1,2,4-triazole or
Represents a group of nonmetallic atoms necessary to form a 1H-pyrazolo[1,5-b]-1,2,4-triazole ring, and R ₂ ′ and R ₃ ′ are hydrogen atoms, aryl groups, alkyl groups, or hetero Represents a ring group. ), a hydroxymethyl group, and a triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups,
Examples include alkoxyoxalyloxy groups. The alkoxy group may further have a substituent,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, p-chlorobenzyloxy group, and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4
-methanesulfonamidophenoxy group, 4-[α
-(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. in particular,
Examples include 1-phenyltetrazolyloxy group and 2-benzothiazolyloxy group. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoyloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of groups substituted via a sulfur atom include alkylthio groups, arylthio groups, heterocyclic thio groups, and alkyloxythiocarbonylthio groups. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes phenylthio group, 4
-Methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, etc. can be mentioned. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituted via the nitrogen atom include the general formula

[Specific effects of the invention]

Magenta coupler of the present invention and the general formula []
According to a color photographic material containing a magenta dye image stabilizer represented by fading, light,
The generation of Y-stain in uncolored areas due to heat and humidity can be effectively prevented. [Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Gelatin (15.0 mg/100 cm ² ) and comparative magenta coupler (1) (6.0 mg/100 cm ² ) shown below were applied to a paper support double-sided laminated with polyethylene.
-di-tert-octylhydroquinone (0.8mg/
100cm ² ) along with dibutyl phthalate (5.0mg/100cm 2 )
cm ² ) and emulsified and dispersed, mixed with a silver chlorobromide emulsion (silver bromide 80 mol %, coated silver amount 3.8 mg/100 cm ² ), coated, and dried to obtain Sample 1. A sample 2 was obtained by adding the above PH-13 as a magenta dye image stabilizer to the above sample 1 in an equimolar amount as the magenta coupler. Samples 3, 6, and 9 were obtained in the same manner except that the magenta coupler in Sample 1 was replaced with magenta couplers A-5, A-7, and A-96 of the present invention, respectively. In the above Samples 3, 6, and 9, PH-13 was added as the magenta dye image stabilizer in an equimolar amount to the coupler to obtain Samples 4, 7, and 10, respectively. Samples 5, 8, and 11 were obtained by adding magenta image stabilizer B-1 in equimolar amounts to the coupler. Comparison coupler (1) The sample obtained above was exposed to light through an optical wedge according to a conventional method, and then processed in the following steps. [Processing process] Processing temperature Processing time Color development 33°C 3 minutes 30 seconds Bleach-fixing 33°C 1 minute 30 seconds Washing with water 33°C 3 minutes Drying 50-80°C 2 minutes The components of each processing solution are as follows. [Color developer] Benzyl alcohol 12ml Diethylene glycol 10ml Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
Add 4.5g water to make 1, and adjust the pH to 10.2 with NaOH. [Bleach-fix solution] Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to 1 and adjust the pH to 6.7-6.8. The concentrations of Samples 1 to 11 treated above were measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions. Each of the above-treated samples was exposed to a xenon fade meter for 10 days to examine the light fastness of the dye image and the Y-stain in the uncolored area.
The image was left in a high pH and high humidity atmosphere for 14 days, and the moisture resistance of the dye image and the Y-stain in the uncolored area were examined. The results obtained are shown in Table 1. However, the evaluation of each item of light fastness and moisture fastness of the dye image is as follows. [Residual rate] Percentage of dye remaining after light and moisture resistance tests for initial density 1.0. [YS] From the concentration of Y-stain after light resistance and moisture resistance tests,
Value obtained by subtracting the Y-stain concentration before light and moisture resistance tests. [Degree of color change] The value obtained by subtracting (yellow density) / (magenta density) before the light fastness test from (yellow density) / (magenta density) after the light fastness test at an initial density of 1.0. The larger this value is, the more yellow the color changes from magenta to yellow. This means that the color tone tends to change easily.

[Table] As is clear from Table 1, Samples 3, 6, and 9 prepared using the coupler of the present invention are different from those prepared using the conventional 4-equivalent type 3-anilino-5-pyrazolone type coupler. Compared to the prepared sample 1, light resistance,
Although the moisture resistance test shows that Y-stain is extremely difficult to generate, the residual rate and degree of discoloration of the dye image area in the light resistance test shows that the color easily changes and fades when exposed to light. Samples 4, 7, and 10 were prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-13, which certainly prevented the dye image from fading due to light. is significantly improved, but discoloration cannot be improved. On the other hand, in samples 5, 8, and 11 prepared using the coupler and dye image stabilizer of the present invention, light, heat,
It can be seen that the resistance test against humidity shows that the color change and fading of the dye image is small, and that Y-stain hardly occurs in the uncolored areas. This could not be achieved with the conventional combination of a 4-equivalent type 3-anilino-5-pyrazolone type coupler and a dye image stabilizer (Sample 2). Example 2 Samples 12 to 27 were prepared by coating the couplers and magenta dye image stabilizers in combinations shown in Table 2 in exactly the same manner as in Example 1. Samples 12-27 were processed as described in Example 1. Furthermore, these samples were subjected to a light resistance test and a moisture resistance test in the same manner as in Example 1, and the results shown in Table 2 were obtained. Comparison coupler (2)

[Table] (In Table 2, Samples 25, 26, and 27 used B-2 and PH compound at a molar ratio of 2:1, and the total amount of dye image stabilizer was the same as that of the dye used in other samples. (The number of moles is the same as that of the image stabilizer.) As is clear from Table 2, the magenta dye image stabilizing agent of the present invention is added to the conventionally used 4-equivalent type 3-anilino-5-pyrazolone type coupler. (Samples-12, 13) and when a magenta dye image stabilizer, which has been commonly used in the coupler of the present invention, was used (Samples-16, 17,
18, 19), it was not possible to improve all of the discoloration, fading, Y-stain in uncolored areas in the light fastness test, and Y-stain in the moisture fastness test, and the coupler of the present invention and the magenta dye image of the present invention could not be improved. It can be seen that all of the above-mentioned improvements can be achieved only by using a stabilizer in combination. Furthermore, when the coupler of the present invention is used together with the dye image stabilizer of the present invention and the conventional dye image stabilizer (Samples-25, 26, and 27), the degree of discoloration in the light fastness test increases slightly, but the residual rate A mutually beneficial effect is clearly observed when used in combination. Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and Sample 28 was obtained. 1st layer: blue-sensitive silver halide emulsion layer α-pivaloyl-α as yellow coupler
-(2,4-dioxo-1-benzylimidazolidin-3-yl)-2-chloro-5-[γ-
(2,4-di-t-amylphenoxy)butylamide]acetanilide 6.8 mg/100 cm ² , blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver 3.2 mg/100 cm ² , dibutyl phthalate
3.5mg/100cm ² and gelatin were coated at a coating amount of 13.5mg/100cm ² . 2nd layer: middle layer 2,5-di-t-octylhydroquinone
0.5mg/ ^100cm2 , dibutyl phthalate 0.5mg/100cm2
100cm ² and gelatin was coated at 9.0mg/100cm ² . Third layer: green-sensitive silver halide emulsion layer containing the magenta coupler A-36 at 3.5 mg/100
cm ² , green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver is 2.5 mg/100 cm ² , dibutyl phthalate is 3.0 mg/100 cm ² and gelatin is 12.0
The coating was applied so that the amount was mg/100cm ² . 4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-
sec-butyl-5-t-butylphenyl)benzotriazole 7.0 mg/100 cm ² , dibutyl phthalate 6.0 mg/100 cm ² , 2,5-di-t-octylhydroquinone 0.5 mg/100 cm ² and gelatin 12.0 mg / ^100cm2 . 5th layer: red-sensitive silver halide emulsion layer 2-[α-(2,4-di-t-pentylphenoxy)butanamide]- as a cyan coupler
4,6-dichloro-5-ethylphenol
4.2mg/100cm ² , red-sensitive silver chlorobromide emulsion (silver bromide 80
The silver content (mol% content) was 3.0 mg/100 cm ² in terms of silver, tricresyl phosphate was 3.5 mg/100 cm ² , and gelatin was 11.5 mg/100 cm ² . 6th layer: Protective layer Gelatin was coated at 8.0 mg/100 cm ² . In the above sample 28, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3,
Multilayer samples 29 to 37 were prepared, exposed and treated in the same manner as in Example 1, and then subjected to a light resistance test (irradiated with a xenon fademeter for 15 days). The results are also shown in Table 3.

[Table] From this result, the dye image stabilizer of the present invention is
The magenta coupler of the present invention is effective in stabilizing dye images, and the effect becomes greater as the amount added increases. Further, Samples 29 to 37 showed extremely small discoloration of the dye images in the light fastness test compared to Sample 28.
Furthermore, in the sample of the present invention, discoloration of magenta pigment,
It can be seen that fading is extremely small, the color balance is good with the yellow and cyan couplers as an overall color photographic material, and the color reproducibility is extremely good.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material comprising a magenta image-forming coupler represented by the following general formula [] and a compound represented by the following general formula []. General formula [] [Formula] or [Formula] [In the formula, R is an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a bridged hydrocarbon compound residue,
represents an acylamino group or an alkylthio group,
These groups may have substituents. R ₁ and
R ₂ represents an alkyl group, an aryl group, an amino group, an acylamino group, a sulfonyl group, or an alkylthio group, and these groups may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. ] General formula [ ] [In the formula, R ¹ represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y represents a non-containing group necessary to form a piperazine ring, morpholine ring, thiamorpholine ring, imidazolidine ring, or homopiperazine ring together with the nitrogen atom. Represents a group of metal atoms. ]