JPH0830876B2 - Silver halide photographic light-sensitive material with improved fastness of dye image - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material in which a dye image to be formed is stable against heat and light and generation of stain is prevented.

[Background of the Invention]

The dye image obtained from the silver halide photographic light-sensitive material is
It is desired that the silver halide photographic light-sensitive material does not discolor even if it is exposed to light for a long period of time or is stored under high temperature and high humidity, and the uncolored part of the silver halide photographic light-sensitive material turns yellow due to light or wet heat (hereinafter, Y What is called stain) is desired.

As a coupler for forming a magenta dye image, for example, a pyrazolone, a pyrazolobenzimidazole, a pyrazolotriazole or an indazolone coupler is known.

However, in the case of a magenta coupler, Y-stain due to heat and humidity in the uncolored portion and fading due to light in the dye image portion are extremely large and often cause problems as compared with the yellow coupler and the cyan coupler.

Couplers widely used to form magenta dyes are the 1,2-pyrazolo-5-ones. This 1,2
-The major problem is that the dye formed from the pyrazolo-5-one type magenta coupler has a secondary absorption around 430 nm in addition to the primary absorption around 550 nm. Various studies have been conducted to solve this problem. Has been done.

For example, a magenta coupler having an anilino group at the 3-position of 1,2-pyrazolo-5-ones described in U.S. Pat. No. 2,343,703 and British Patent No. 1,059,994 has a small above-mentioned sub-absorption, and particularly a color image for printing is obtained. Useful to get.

However, the above-mentioned magenta coupler has a disadvantage that the image storability, particularly the fastness of the dye image to light, is remarkably inferior, and the Y-stain in the uncolored portion is large.

As another means for reducing the side absorption around 430 nm of the magenta coupler, pyrazolobenzimidazoles described in British Patent 1,047,612, U.S. Pat.
Indazolones described in 3,770,477 and 3,725,067
1H-described in British Patent Nos. 1,252,418 and 1,334,515
Pyrazolo [5,1-c] -1,2,4-triazole type couplers, 1H-pyrazolo [1,5-b] -1,2 described in JP-A-59-171956 and Research Disclosure No. 24,531. ,Four
-Triazole coupler, Research Disclosure
1H-pyrazolo [1,5-c] -1,2,3-described in No. 24,626
Triazole type couplers, 1H-imidazo [1,2-b] -pyrazole type couplers described in JP-A-59-162548 and Research Disclosure No. 24,531, JP-A-60-4365.
No. 9, 1H described in Research Disclosure No. 24,230
-Pyrazolo [1,5-b] pyrazole type coupler
Magenta couplers such as 1H-pyrazolo [1,5-d] tetrazole type couplers described in 0-33552 and Research Disclosure No. 24,220 have been proposed. Of these,
1H-pyrazolo [5,1-c] -1,2,4-triazole type coupler, 1H-pyrazolo [1,5-b] -1,2,4-triazole type coupler, 1H-pyrazolo [1,5- c] -1,2,3-triazole type coupler, 1H-imidazo [1,2-b] pyrazole type coupler, 1H-pyrazolo [1,5-d] pyrazole type coupler and 1H-pyrazolo [1,5-d The dye formed from the tetrazole type coupler has a 1,2-pyrazolo-5 group having an anilino group at the 3-position as a side absorption near 430 nm.
It is significantly smaller than dyes formed from -ones in terms of color reproduction, and further, Y-stain in the uncolored portion against light, heat and humidity is extremely small, which is a preferable advantage.

However, the fastness to light of azomethine dyes formed from these couplers is extremely low, and moreover,
The dye is liable to discolor by light, and particularly the performance of the print-type silver halide color photographic light-sensitive material is significantly impaired, and it has not been put to practical use in the print-type silver halide color photographic light-sensitive material.

Further, JP-A-59-125732 discloses that 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 to give 1H-pyrazolo [5,1-c] -1,
Techniques have been proposed for improving the light fastness of a magenta dye image obtained from a 2,4-triazole type magenta coupler. However, even with the above-mentioned technique, it cannot be said that it is still sufficient to prevent fading of the magenta dye image with respect to light, and it has been recognized that it is almost impossible to prevent discoloration with respect to light.

[Object of the Invention]

A first object of the present invention is to provide a silver halide photographic light-sensitive material which has no secondary absorption of the formed magenta dye and has a markedly improved fastness to light of a magenta dye image.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having a magenta dye image which is less discolored by light.

A third object of the present invention is to provide a silver halide photographic light-sensitive material in which generation of Y-stain in an uncolored portion is prevented by light and heat of heat.

[Structure of Invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material with at least one magenta coupler represented by the following general formula [MI] and at least one compound represented by the following general formula [A]. It is achieved by merging.

General formula [MI] In the formula, Z represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent.

 R represents a hydrogen atom or a substituent.

General formula [A] In the formula, R ¹ represents an aryl group or a heterocyclic group, and Z and
Z ₂ represents an alkylene group having 1 to 3 carbon atoms. However, the total number of carbon atoms of the alkylene group represented by Z ₁ and Z ₂ is 3 to 6.

 n represents 1 or 2.

[Specific configuration of the invention]

 Next, the present invention will be specifically described.

The above general formula [MI] according to the present invention In the magenta coupler represented by, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups , And spiro compound residues, bridged hydrocarbon compound residues and the like.

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

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

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

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

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5
The alkenyl group may be linear or branched.

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

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group. , An arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .; a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, etc .; As the acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; As the carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group Are alkyl ureido groups, aryl ureido groups, etc .; Sulfamoylamino groups are alkylsulfamoylamino groups, arylsulfamoylamino groups, etc .; Heterocyclic groups preferably have 5 to 7 members Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, for example, 3,4,5,6- Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group and the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazoli Ruthio group, 2,4-diphenoxy-zo-1,3-1,3,5-triazole-6-thio group, etc .; as siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethyl Chirushirokishi group or the like; succinimide imide group as a group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like. Examples of the spiro compound residue into spiro [3.3] heptane -
1-yl, etc .; as a bridged hydrocarbon compound residue, bicyclo [2.2.1]
Heptan-1-yl, tricyclo [3.3.1.1 ³⁷ ] decan-1-yl, 7,7 [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the group represented by X which can be eliminated by the reaction with the oxidized product of the color developing agent include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group). And a halogen atom, particularly a chlorine atom is preferable.

The nitrogen-containing heterocyclic ring formed by Z or Z'includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, and the like, and the substituent which the ring may have is the same as described above for R. Is mentioned.

What is represented by the general formula [MI] is more specifically represented by, for example, the following general formulas [M-II] to [M-VII].

General formula (M-II) General formula (M-III) General formula (M-IV) General formula [MV] General formula (M-VI) General formula (M-VII) In the formulas [M-II] to [M-VII], R _{1 to} R ₈ and X have the same meanings as R and X.

Further, among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

General formula (M-VIII) In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the formula [MI].

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], the magenta coupler represented by the general formula [M-II] is particularly preferable.

Most preferred as the substituents R and R ₁ on the heterocycle are those represented by the following general formula [M-IX].

General formula [M-IX] In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R above.

Two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ may combine to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), In addition to the ring
R ₁₁ may combine to form a bridged hydrocarbon compound residue.

Preferred are among the general formula [M-IX], (i) if at least two of the alkyl groups in the _{R 9 ~R 11, (ii)} 1 one example R ₁₁ in R ₉ to R ₁₁ are hydrogen An atom, when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) is 2 of R _{9 to} R _11.
One is an alkyl group and the other one is a hydrogen atom or an alkyl group.

Further, the ring formed by Z in the general formula [MI] and the substituent which the ring formed by Z ₁ in the general formula [M-VIII] may have, and the general formula [M-II] to (M-VI)
As R _{2 to} R _{8 in the} formula, those represented by the following general formula [MX] are preferable.

The general formula [M-X] -R ¹ -SO ^₂ -R ₂ Formula wherein R ¹ is an alkylene group, R ² represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has a carbon number of the linear portion of 2 or more, more preferably 3 to 6, and may be linear or branched.

The cycloalkyl group represented by R ² is preferably a 5- or 6-membered cycloalkyl group.

 The typical examples of the compounds according to the present invention are shown below.

In addition to the representative examples of the compound according to the present invention, specific examples of the compound according to the present invention include compounds described on pages 66 to 122 of Japanese Patent Application No. 61-9791. And N
o.1 to 4,6,8 to 17,19 to 24,26 to 43,45 to 59,61 to 104,106 to 1
The compound shown by 21,123-162,164-223 can be mentioned.

The magenta coupler represented by the general formula [MI] (hereinafter referred to as the magenta coupler of the present invention) is a journal of the chemical society.
he Chemical Society), Perkin; I (197
7), 2047-2052, U.S. Patent 3,725,067, JP-A-59-9943.
No. 7, No. 58-42045, No. 59-162548, No. 59-171956,
60-33552, 60-43659, 60-172982 and 60-
Those skilled in the art can easily synthesize the compound with reference to No. 190779 and the like.

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

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

The compound represented by the general formula [A] contained in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the magenta dye image stabilizer of the present invention) is used in combination with the magenta coupler of the present invention. In addition to having the effect of preventing fading of the magenta dye image due to light, it also has the effect of preventing discoloration due to light.

In the general formula [A], examples of the aryl group represented by R ¹ include a phenyl group and a 1-naphthyl group, and these aryl groups may have a substituent. Examples of the substituent include those mentioned as the substituent of R in the general formula [MI].

Examples of the heterocyclic group represented by R ¹ include a 2-furyl group and a 2-thienyl group, and these heterocyclic groups have a substituent such as those mentioned for R in the general formula [MI]. Including things.

Z ₁ and Z ₂ each represent an alkylene group having 1 to 3 carbon atoms, and the total number of carbon atoms of the alkylene group represented by Z ₁ and Z ₂ is 3 to 6. These alkylene groups may have a substituent as described for R in the general formula [MI].

 n represents 1 or 2.

In the present invention, a compound in which R ¹ is a phenyl group, Z ₁ and Z ₂ are each an ethylene group, and n is 2 in the formula [A] is particularly preferable.

Specific examples of the magenta dye image stabilizer of the present invention are shown below.

In addition to the above, the following compounds can be mentioned.

Next, typical synthesis examples of the magenta dye image stabilizer of the present invention will be shown.

Synthesis Example-1 (Synthesis of Compound (A-3)) 27 g of p-dodecyloxyaniline and 15 g of di-vinyl sulfone were dissolved in 200 ml of ethanol, and the mixture was boiled under reflux for 3 hours, cooled with ice, and precipitated crystals were formed. It was collected by filtration. Recrystallization from methanol gave 18 g of white scaly crystals.

The structure was confirmed by mass spectrum and nuclear magnetic resonance spectrum.

Synthesis Example-2 (Synthesis of Compound (A-17)) 20 g of p-benzyloxyaniline and 13 g of di-vinyl sulphoxide were dissolved in 150 ml of dioxane, and after boiling and refluxing for 5 hours, the mixture was allowed to stand at room temperature for one day to precipitate crystals. It was collected by filtration. Recrystallization from ethanol gave 15 g of white powder crystals.

The structure was confirmed by mass spectrum and nuclear magnetic resonance spectrum.

The amount of the magenta dye image stabilizer of the present invention used is preferably 5 to 400 mol%, more preferably 10 to 300 mol%, based on the magenta coupler of the present invention.

The magenta coupler of the present invention and the magenta dye image stabilizer of the present invention are preferably used in the same layer, but the stabilizer may be used in a layer adjacent to the layer in which the coupler is present.

The hydrophobic compound such as the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention can be prepared by various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water type emulsion dispersion method. Can be added to. For example, the oil-in-water emulsion dispersion method, a hydrophobic additive such as a magenta coupler is usually used in combination with a high-boiling organic solvent having a boiling point of about 150 ° C. or higher, and optionally a low-boiling point and / or a water-soluble organic solvent. It may be dissolved in the solution, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then added to the desired hydrophilic colloid layer.

In the silver halide photographic light-sensitive material of the present invention, in addition to the magenta dye image stabilizer of the present invention, JP-A-61-188
Magenta dye image stabilizers described on pages 106 to 120 of the specification No. 344, that is, the general formula [XIII] in the specification.
A phenolic compound and a phenyl ether compound represented by can also be used in combination.

When the phenol compound or the phenyl ether compound is used in combination, the amount thereof is preferably 200 mol% or less, more preferably 140 mol% or less, based on the magenta dye image stabilizer of the present invention.

The phenol compound and the phenyl ether compound have an effect of preventing fading of a magenta dye image obtained from the magenta coupler of the present invention, but have almost no effect of preventing discoloration. Therefore, it is not preferable to use the phenol compound and the phenyl ether compound in excess with respect to the magenta dye image stabilizer of the present invention.

Generally, the magenta dye image obtained from the magenta coupler of the present invention shows not only a marked fading to light, but also discoloration due to light, and the color tone of the dye image becomes magenta to yellowish.

The magenta dye image stabilizer of the present invention is capable of preventing fading and discoloration due to light of the magenta dye image obtained from the magenta coupler of the present invention, which is an effect that cannot be achieved by the phenol compound and the phenyl ether compound. have.

Therefore, when the above-mentioned phenol compound and phenyl ether compound are used in combination with the magenta dye image stabilizer of the present invention, the amounts of the phenol compound and phenyl ether compound should be selected so that discoloration by light is not noticeable. I have to.

When an appropriate amount of the phenol compound and the phenyl ether compound are used in combination with the magenta dye image stabilizer of the present invention, there may be a case where a synergistic effect of the combined use is recognized.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, and the like. In particular, the present invention is applied to a color photographic paper directly provided for viewing. The effect of is effectively exhibited.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention).
As the silver halide, any of silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride used in ordinary silver halide emulsions can be used.

The silver halide emulsion of the present invention is chemically sensitized by a sulfur sensitizing method, a selenium sensitizing method, a reduction sensitizing method, a noble metal sensitizing method or the like.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry.

The silver halide photographic light-sensitive material of the present invention includes a color antifoggant, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a mordant, a development accelerator, a development retarder, and a brightening agent, A matting agent, a lubricant, an antistatic agent, a surfactant and the like can be optionally used.

The silver halide photographic light-sensitive material of the present invention can form an image by performing various color development processes.

[Specific effects of the invention]

According to the silver halide photographic light-sensitive material containing the magenta coupler and the magenta dye image stabilizer of the present invention, conventionally, the fastness of a magenta dye image, which has low fastness to light, heat and humidity, is improved, Specifically, it is possible to favorably prevent discoloration with respect to light, fading, and generation of Y-stain in the uncolored portion against light, heat, and humidity.

〔Example〕

Example 1 On a paper support laminated on both sides with polyethylene,
Gelatin (12.0mg / 100cm ^2), tricresyl phosphate with the following comparative magenta coupler a (4.1mg / 100cm ²⁾ 2,5- di -t- octylhydroquinone ^{(0.2mg / 100cm 2) (4.0mg} / 100cm After dissolving in ² ) and emulsifying and dispersing, it was mixed with a silver chlorobromide emulsion (silver bromide 80 mol%, coating silver amount 3.8 mg / 100 cm ² ), coated and dried to obtain Sample 1.

As the magenta dye image stabilizer in Sample 1 above,
A sample 2 was obtained in which PH-1 was added in an amount 2.0 times the molar amount of the magenta coupler.

Sample 3, except that the magenta coupler of Sample 1 was replaced with the magenta couplers 4, 9 and 20 of the present invention, respectively.
Got 7,11.

In each of Samples 3, 7, and 11, the magenta dye image stabilizer PH-1 was added in an amount of 2.0 times mol of the coupler, and Sample 4, respectively.
8 and 12 were obtained, and the magenta dye image stabilizer A-3 of the present invention was added in an amount of 2.0 times the amount of the coupler in place of PH-1 to obtain samples 5, 9 and 13, respectively.

Further, in Samples 3, 7 and 11 described above, magenta dye image stabilizer A-16 was added in an amount of 2.0 times mol of the coupler, and Samples 6 and 1 were prepared.
I got 0,14.

The sample obtained above was exposed through an optical wedge according to a conventional method, and then processed in the following steps.

 [Processing step] Processing temperature Processing time Color development 33 ° C 3 minutes 30 seconds Bleach fixing 33 ° C 1 minute 30 seconds Water washing 33 ° C 3 minutes Drying 50 to 80 ° C 2 minutes The components of each processing solution are as follows.

[Color developer]

Benzyl alcohol 12 ml Diethylene glycol 10 ml Potassium carbonate 25 g Sodium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Hydroxyamine sulfate 2.5 g N-ethyl-N-β-methanesulfonamide ethyl-
4.5 g of 3-methyl-4-aminoaniline sulfate 4.5 g of water was added to adjust the pH to 1 and the pH was adjusted to 10.2 with NaOH.

[Bleaching fixer]

 Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g EDTA Ferric ammonium salt 65 g Water was added to adjust pH to 6.7-6.8.

The samples 1 to 14 treated as described above were measured for concentration under the following conditions using a densitometer (KD-7R type manufactured by Konishi Rokusha Kogyo Co., Ltd.).

Each treated sample was irradiated with a xenon fade meter for 10 days, and the light resistance of the dye image and the Y-stain of the uncolored part were examined, while each sample was exposed to a high temperature and high humidity atmosphere of 60 ° C and 80% RH. After leaving for 14 days, the dye image was examined for moisture resistance and Y-stain in the uncolored portion. The results obtained are shown in Table 1.

However, the evaluation of each item of light resistance and moisture resistance of the dye image is as follows.

〔Survival rate〕

Percentage of dye remaining after light resistance and humidity resistance test for initial density of 1.0.

[Y-Stain (Y-S)]

From the concentration of Y-stain after the light resistance and humidity resistance test,
The value obtained by subtracting the concentration of Y-stain before the moisture resistance test.

[Discoloration]

(Yellow density) / after light resistance test at initial density of 1.0
(Magenta density) to (yellow density) before lightfastness test /
The value obtained by subtracting (magenta density) means that the larger the value is, the more easily the color tone changes from magenta to yellowish color tone.

As is apparent from Table 1, Samples 3,7,11 prepared by using the magenta coupler of the present invention are conventional 4-equivalent 3-anilino-1,2-pyrazolo-5-one type couplers. Compared to the sample 1 made by using, Y in light and humidity resistance test
-It can be seen that stain is extremely unlikely to occur, but it can be seen from the residual ratio and the degree of discoloration of the dye image portion in the light fastness test that it is easily discolored by light. Samples 4,8,12 are
It is a test prepared by using the magenta coupler of the present invention in combination with a conventionally known magenta dye image stabilizer PH-1. Although this surely improves the fading of the dye image by light, Discoloration cannot be improved.

On the other hand, Samples 5, 6, 9, 10, 13, prepared by using the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention,
It can be seen that in No. 14, in the resistance test against light, heat, and humidity, discoloration or fading of the dye image is small, and Y-stain in the uncolored portion hardly occurs. This was not possible with the conventional 4-equivalent 3-anilino-1,2-pyrazolone-5-one type coupler and the dye image stabilizer PH-1 (Sample 2).

Example 2 Samples 15 to 30 were prepared by coating in exactly the same manner as in Example 1 except that the combination of magenta coupler and magenta dye image stabilizer was used as shown in Table 2. Samples 15-30 were processed as described in Example 1.

Further, 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.

The magenta dye image stabilizers PH-2 and PH-3 and the comparative magenta coupler b in the table have the following structures.

As is clear from Table 2, when the magenta dye image stabilizer of the present invention is used in combination with the conventionally used 4-equivalent 3-anilino-1,2-pyrazolo-5-one type coupler (sample 15, 16) and the magenta coupler of the present invention in combination with a magenta dye image stabilizer which has been often used conventionally (Sample-19, 20, 21, 22), discoloration, fading and uncoloring in the light resistance test. Some of the Y-stains and all of the Y-stains in the moisture resistance test cannot be improved, and the above-mentioned improvement by the combined use of the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention is annoying. It turns out that all the items can be achieved.

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 a sample 31 was obtained.

First layer: Blue-sensitive silver halide emulsion layer α-bivaloyl-α- (2,4 as a yellow coupler
-Dioxo-1-benzylimidazolidin-3-yl)
6.8 mg / 100c of 2-chloro-5- [γ- (2,4-di-t-amylphenoxy) butyramide] acetanilide
m ² , blue-sensitive silver chlorobromide emulsion (containing 85 mol% of silver bromide) converted to silver, 3.2 mg / 100 cm ² , di-butyl phthalate 3.5 mg /
100 cm ² and gelatin were coated so as to have a coating amount of 13.5 mg / 100 cm ² .

Second layer: intermediate layer 2,5-di-t-octylhydroquinone 0.5 mg / 100 cm
³ , 0.5 mg / 100 cm ^{2 of} di-butyl phthalate and 9.0 mg of gelatin were applied.

Third layer: green-sensitive silver halide emulsion layer The magenta coupler 1 was 3.5 mg / 100 cm ² , and the green-sensitive silver chlorobromide emulsion (containing 80 mol% of silver bromide) was 2.5 mg / silver.
100 cm ^2, di - butyl phthalate 3.0 mg / 100 cm ^2, and gelatin were coated so that 12.0 mg / 100 cm ^2.

Fourth layer: intermediate layer 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) benzotriazole which is an ultraviolet absorber is used.
5.0 mg / 100 cm ² , di-butyl phthalate 5.0 mg / 100 cm ² ,
2,5-di-t-octylhydroquinone 0.5 mg / 100 cm ²
And gelatin was applied at 12.0 mg / 100 cm ² .

Fifth layer: red-sensitive silver halide emulsion layer 2- [α- (2,4-di-t-pentylphenoxy) butanamide] -4,6-dichloro- as a cyan coupler
5-ethylphenol 4.2 mg / 100 cm ² , red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver 3.0 mg / 100c
m ^2, and coated with a tricresyl phosphate and 3.5 mg / 100 cm ² and gelatin so that 11.5 mg / 100 cm ^2.

Sixth layer: protective layer Gelatin was applied so as to be 8.0 mg / 100 cm ² .

In the above-mentioned Sample 31, the magenta dye image stabilizer of the present invention was added to the third layer in a ratio as shown in Table 3, multilayer samples 32 to 40 were prepared and exposed in the same manner as in Example 1, After the treatment, a light resistance test (a xenon fade meter was irradiated for 15 days) was performed.

The results are also shown in Table 3.

From this result, the magenta dye image stabilizer of the present invention is effective in stabilizing the dye image obtained from the magenta coupler of the present invention, and the result becomes larger as the addition amount is increased. In addition, in Samples 32 to 40, the color change of the dye image in the light fastness test was extremely small as compared with Sample 31.

Further, in the sample of the present invention, the discoloration and fading of the magenta dye were extremely small, and the color balance was good with the yellow and cyan couplers as the entire silver halide color photographic light-sensitive material after the light resistance test, and the color reproducibility was extremely good. I was in a state.

Claims (1)

[Claims] 1. A silver halide containing at least one magenta coupler represented by the following general formula [MI] and at least one compound represented by the following general formula [A]. Photographic material. General formula [MI] [In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. R represents a hydrogen atom or a substituent. ] General formula [A] [In the formula, R ¹ represents an aryl group or a heterocyclic group, and Z ₁ and
Z ₂ represents an alkylene group having 1 to 3 carbon atoms. However, the total number of carbon atoms of the alkylene group represented by Z ₁ and Z ₂ is 3 to 6. n represents 1 or 2. ]