JPH0690474B2 - Silver halide photographic light-sensitive material with improved fastness of dye image - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides that the dye image formed is stable to heat and light.
Moreover, the present invention relates to a silver halide photographic light-sensitive material in which generation of stain is prevented.

BACKGROUND OF THE INVENTION It is desirable that a dye image obtained from a silver halide photographic light-sensitive material should not be discolored even if it is exposed to light for a long time or stored at high temperature and high humidity. It is desired that the uncolored part of the photographic light-sensitive material does not yellow (hereinafter referred to as Y-stain) due to light or wet heat.

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.

Widely used couplers for forming magenta dyes are the 1,2-pyrazolo-5-ones. This 1,2-
It is a big problem that the dye formed from the pyrazolo-5-one type magenta coupler has a secondary absorption around 430 nm in addition to the main absorption around 550 nm, and various studies have been made to solve this problem. It has been done.

For example, magenta couplers 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 have a small sub-absorption, and particularly color images for printing can be obtained. Useful to get.

However, the above-mentioned magenta coupler has the drawback that the image storability, particularly the fastness of the dye image to light, is extremely poor, 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 770,447, 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 coupler, 1H-pyrazolo [1,5-b] -1,2 described in JP-A-59-171956 and Research Disclosure No. 24,531. ,Four
-Triazole type coupler, 1H-pyrazolo [1,5-c] -1,2,3 described in Research Disclosure No. 24,626
-Triazole type couplers, JP-A-59-162548, 1H-imidazo [1,2-b] -pyrazole type couplers described in Research Disclosure No. 24,531, JP-A-60-43
No. 659, Research Disclosure No. 24,230
1H-pyrazolo [1,5-b] pyrazole type coupler, JP-A-60-33552, Research Disclosure No. 24,22
Magenta couplers such as 1H-pyrazolo [1,5-d] tetrazole type couplers described in 0 have been proposed. Of these, 1H-pyrazolo [5,1-c] -1,2,4-triazole type couplers, 1H-pyrazolo [1,5-b] -1,2,4-triazole type couplers, 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 The dye formed from a 5,5-d] tetrazole type coupler has a remarkably small side absorption at around 430 nm as compared with the dye formed from the 1,2-pyrazolo-5-ones having an anilino group at the 3-position. This is preferable in terms of color reproduction, and further, Y-stain generation in an 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 in addition, the dyes are prone to discoloration by light, which particularly impairs the performance of print silver halide photographic light-sensitive materials. It has not been put to practical use in print silver halide color photographic light-sensitive materials.

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 technique, it has been found that it is still not sufficient to prevent fading of the magenta dye image with respect to light, and 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 Y in the uncolored portion to light and wet heat.
-To provide a silver halide photographic light-sensitive material in which generation of stain is prevented.

[Constitution 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 formulas [M-II] and [M-III] and the following general formula [A].
It is achieved by incorporating at least one of the compounds represented by

General formula [M-II] General formula [M-III] [In the formula, X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent. ] General formula [A] In the formula, R ₁ , R ₂ and R ₃ each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Y represents a nonmetallic atom group necessary for forming an imidazolidine ring.

[Specific Structure of the Invention] The general formula [M-II] and the general formula [M-II] according to the present invention.
In I], X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent. Fork, R ₁ , R ₂
And R ₃ each represent a hydrogen atom or a substituent.

The substituent represented by R ₁ , R ₂ and R ₃ is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino,
Alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, etc. Can be mentioned.

The alkyl group represented by R ₁ , R ₂ and R ₃ preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group represented by R ₁ , R ₂ and R ₃ is preferably a phenyl group.

As the acylamino group represented by R ₁ , R ₂ and R ₃ ,
Examples thereof include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₁ , R ₂ and R ₃ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkylthio group represented by R ₁ , R ₂ and R ₃ , the alkyl component in the arylthio group, and the aryl component are the above R ₁ ,
Examples thereof include an alkyl group and an aryl group represented by R ₂ and R ₃ .

The alkenyl group represented by R ₁ , R ₂ and R _{3 has 2 to} 32 carbon atoms, and the cycloalkyl group has 3 to 3 carbon atoms.
12, particularly 5 to 7, are preferable, and the alkenyl group may be linear or branched.

As the cycloalkenyl group represented by R ₁ , R ₂ and R ₃ , those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms are preferable.

The sulfonyl group represented by R ₁ , R ₂ and R ₃ 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,
Arylsulfamoyl group and the like; as the acyloxy group, an alkylcarbonyloxy group,
Arylcarbonyloxy group, etc .; As carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .; As ureido group, alkylureido group, arylureido group, etc .; As sulfamoylamino group, alkylsulfamoylamino group, aryl Sulfamoylamino 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, etc .; heterocyclic oxy group Is preferably a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; , 5- to 7-membered heterocyclic thio groups are preferred, for example, 2-pyridylthio group, 2-benzothia Zolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group as succinimide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; as spiro compound residue, spiro [3.3] heptane-1
-Yl etc .; as the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decane-
1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the group represented by X which can be removed by the reaction with the oxidized product of the color developing agent include halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy. Carbonyloxy, 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 ″, R ₂ ″ and R ₃ ″ have the same meanings as R ₁ , R ₂ and R ₃ above, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group.) Each group such as
Preferred is a halogen atom, especially a chlorine atom.

Among the magenta couplers represented by the above general formulas [M-II] to [M-III], the most preferable one is the general formula [M-I
I] is a magenta coupler.

The most preferable substituent R ₁ on the heterocycle is 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), Further, R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

Among formulas [M-IX], (i) when at least two of R _{9 to} R ₁₁ are alkyl groups, (ii) one of R _{9 to} R ₁₁ such as R ₁₁ is 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 when two of R _{9 to} R ₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Further, as R _{2 to} R ₃ in the general formulas [M-II] to [M-III], 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 straight chain portion having 2 or more carbon atoms, more preferably 3 to 6 carbon atoms,
It doesn't matter whether it branches.

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. So NO.
1 to 4,6,8 to 17,19 to 24,26 to 43,45 to 59,61 to 104,106 to 12
The compound shown by 1,123-162,164-223 can be mentioned.

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. So NO.
1 to 4,6,8 to 17,19 to 24,26 to 43,45 to 59,61 to 104,106 to 12
The compound shown by 1,123-162,164-223 can be mentioned.

Also, the coupler is a Journal of the Chemical Society, Perkin I (1977), 2047-2052, US Pat.
25,067, JP-A-59-99437, JP-A-58-42045, and JP-A-59-162.
548, 59-171956, 60-33552, 60-43659,
It can be synthesized with reference to Nos. 60-172982 and 60-190779.

The coupler of the present invention usually contains 1 × 10 5 mol / mol of silver halide.
It can be used in the range of ^-3 mol to 1 mol, preferably 1 x 10 ^-2 mol to 8 x 10 ^-1 mol.

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

The magenta couplers represented by the general formulas [M-II] and [M-III] (hereinafter referred to as the magenta coupler of the present invention) are referred to as Journal of the Chemical Society, Perkin (Perki).
n) I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 58-42045, 59-162548, 59-.
171956, 60-33552, 60-43659, 60-172982
No. 60-190779 and the like can be easily synthesized by those skilled in the art.

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

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

When 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 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 alkyl group represented by R ₁ , R ₂ and R ₃ include a methyl group, an ethyl group, is
Examples thereof include o-propyl group, pentyl group, undecyl group and dodecyl group.

These alkyl groups include those having a substituent, and examples of the substituent include an aryl group such as a phenyl group.

Examples of the alkenyl group represented by R ₁ , R ₂ and R ₃ include a vinyl group and an allyl group. These alkenyl groups include those having a substituent, and examples of the substituent include:
Examples thereof include aryl such as phenyl group.

Examples of the cycloalkyl group represented by R ₁ , R ₂ and R ₃ include cyclohexyl and the like. These cycloalkyl groups include those having a substituent.

Examples of the aryl group represented by R ₁ , R ₂ and R ₃ include a phenyl group and the like, and these aryl groups include those having a substituent, and examples of the substituent include an alkoxy group such as a methoxy group. , A methylcarbamoyl group, a dodecylcarbamoyl group and the like.

Examples of the heterocyclic group represented by R ₁ , R ₂ and R ₃ include a 2-furyl group and a 3-indolyl group. These heterocyclic groups include those having a substituent.

Further, in the above general formula [A], the aryl group, heterocyclic group and the like represented by R _{3 have the} general formula: (Wherein, R _1, R ₂ and Y have the general formula is R _1, the same meaning as R ₂ and Y [A].) May have a group represented by the magenta dye image in this case the present invention The stabilizer can form a bis form.

In the above general formula [A], Y represents a group of non-metal atoms necessary for forming an imidazolidine ring in cooperation with two nitrogen atoms. In this case, the imidazolidine ring may have a substituent. Often, examples of the substituent include an alkyl group such as a methyl group and an aryl group such as a phenyl group.

In the present invention, an alkyl group or a cycloalkyl group so that the total number of carbon atoms including the substituents of the respective groups represented by R ₁ , R ₂ and R ₃ in the general formula [A] is 8 to 36. Alternatively, the case where each group is selected from the aryl group is particularly preferable.

Specific examples of the magenta dye image stabilizer of the present invention are shown below, but the present invention is not limited thereto.

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

Synthesis Example-1 (Synthesis of Compound A-9) 21 g of 1,2-dianilinoethane was dissolved in 50 ml of methanol,
3 ml of acetic acid was added. To this, 14 g of P-anisaldehyde was added, heated for several minutes and then left to stand, and 20 g of precipitated white powder crystals
Got

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

Synthesis Example-2 (Synthesis of Compound A-21) 24 g of N, N'-dibenzylethylenediamine was added to methanol 50
It was dissolved in 3 ml and 3 ml of acetic acid was added. To this, 6.7 g of terephthalaldehyde was added, and after boiling and refluxing for 10 minutes, 15 g of a white powder crystal precipitated after cooling was obtained.

The structure was confirmed by the magnetic resonance spectrum and mass 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, if necessary, a low-boiling point, and / or a water-soluble organic solvent. It may be dissolved, 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, Japanese Patent Application No. 61-18834.
The magenta dye image stabilizer described on pages 106 to 120 of the No. 4 specification, that is, the phenol compound represented by the general formula [XIII] and the phenyl ether compound can 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 the 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, a fluorescent whitening 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,
In particular, it improves the fastness of magenta dye images, which have low fastness to light, heat, and humidity. Specifically, discoloration to light,
It is possible to favorably prevent the generation of Y-stain in the uncolored part against fading, light, heat and humidity.

In EXAMPLES Example 1 Polyethylene both sides laminated paper support on gelatin (12.0mg / 100cm ^2), the following comparative magenta coupler a (4.1mg / 100cm ²⁾ 2,5- di -tert- octyl hydroquinone (0.2 mg / 100 cm ²⁾ after dissolved was emulsified and dispersed in tricresyl phosphate (4.0 mg / 100 cm ²⁾ with, silver chlorobromide emulsion (silver bromide 80 mol%, amount of coated silver 3.8 mg / 100 cm ² ) Was mixed, coated and dried to obtain Sample 1.

As the magenta dye image stabilizer in the above sample 1, the following PH
-1 was added to obtain a sample 2 in which 1.8 times the molar amount of the magenta coupler was added.

Samples 3, 7, 1 were similarly prepared except that the magenta coupler of Sample 1 was replaced with the magenta couplers 4, 9 and 20 of the present invention.
Got one.

In each of Samples 3, 7, and 11, the magenta dye image stabilizer PH-1 was added in an amount of 1.8 times the molar amount of the coupler, and Samples 4 and 5, respectively.
8 and 12 were obtained, and the magenta dye image stabilizer A-13 of the present invention was added in the amount of 1.8 times as much as the coupler in place of PH-1 to obtain samples 5, 9 and 13, respectively. Further, in Samples 3, 7, and 11, the magenta dye image stabilizer A-21 was added in an amount of 0.9 times the amount of the coupler to obtain Samples 6, 10 and 14, respectively.

Comparative magenta coupler a After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was performed in the next step.

[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 12ml Diethylene glycol 10ml Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-ethyl-N-β-methanesulfonamide ethyl-3
4.5 g of methyl-4-aminoaniline sulfate.

Add water to 1 and adjust to pH 10.2 with NaOH.

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

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 of the treated samples was irradiated with a xenon fade meter for 1 day to examine the light resistance of the dye image and the Y-stain of the undeveloped area, while each sample was exposed to a high temperature and high humidity atmosphere of 60 ° C and 80% RH. Leave it for 14 days, and the moisture resistance of the dye image and Y of the uncolored part
-Checked stain. 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.

[Residual ratio] Percentage of residual dye after the light resistance and humidity resistance test for the initial density of 1.0.

[Y-Stain (Y-S)] A value obtained by subtracting the concentration of Y-stain before the light resistance and humidity resistance test from the concentration of Y-stain after the light resistance and humidity resistance test.

[Discoloration] (Yellow density) / after light resistance test at initial density of 1.0
From (magenta density) to (yellow density) / before light resistance test
A value obtained by subtracting (magenta density) means that the larger this value is, the more easily magenta changes to a yellowish color tone.

As is apparent from Table 1, Samples 3, 7 and 11 prepared by using the magenta coupler of the present invention are conventional 4-equivalent type 3
-Compared to Sample 1 prepared using anilino-1,2-pyrazolo-5-one type coupler, Y-in light resistance 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 discoloration degree of the dye image portion in the light fastness test that the color is easily discolored by light. Samples 4, 8 and 12 are samples prepared by using the previously known magenta dye image stabilizer PH-1 in combination with the magenta coupler of the present invention. Fading is greatly improved, but not discoloration.

On the other hand, Samples 5, 6, 9, 10, 13, 14 prepared using the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention
It can be seen that, in the resistance test against light, heat and humidity, the color change or fading of the dye image is small, and the Y-stain in the uncolored portion hardly occurs. This is the conventional 4-equivalent type 3
This was not possible with the combination of -anilino-1,2-pyrazolo-5-one type coupler and 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 magenta coupler and the magenta dye image stabilizer were used in the combination 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.

In addition, the magenta dye image stabilizers PH-2 and PH-3 in the table
Also, the comparative magenta coupler b has the following structure.

Comparative magenta coupler b As is clear from Table 2, it is used conventionally.
It is conventionally used in combination with a 4-equivalent type 3-anilino-1,2-pyrazolo-5-one type coupler in combination with the magenta dye image stabilizer of the present invention (Samples 15 and 16) and in the magenta coupler of the present invention. When used with the magenta dye image stabilizer (Sample-19, 20, 21, 22), all of the discoloration in the light resistance test, fading, Y-stain of the uncolored part and Y-stain in the humidity resistance test It can be seen that all of the above-mentioned improvements can be achieved only by using the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention 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 a sample 31 was obtained.

First layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α- (2,4-
Dioxo-1-benzylimidazolidin-3-yl)-
2-chloro-5- [γ- (2,4-di-t-amylphenoxy) butyramide] acetanilide was added to 6.8 mg / 100 cm 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 c
m 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 / 100c
m ² , di-butyl phthalate was coated at 0.5 mg / 100 cm ^2, and gelatin was coated at 9.0 mg / 100 cm ² .

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 / 10 in terms of silver.
0 cm ^2, di - butyl phthalate 3.0 mg / 100 cm ^2, and gelatin were coated as a 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 added to 5.
0 mg / 100 cm ² , di-butyl phthalate 5.0 mg / 100 cm ² , 2,
5-di -t- octylhydroquinone was coated as a 0.5 mg / 100 cm ² and gelatin 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-5 as a cyan coupler
-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 a gelatin as a 11.5 mg / 100 cm ^2.

Sixth layer: protective layer Gelatin was applied so as to have a concentration of 8.0 mg / 100 cm ² .

In the above 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 to prepare multilayer samples 32 to 40, which were exposed to light and treated in the same manner as in Example 1. After that, 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,
It is effective for stabilizing a dye image obtained from the magenta coupler of the present invention, and the result becomes larger as the amount of addition is increased. Further, in Samples 32 to 40, the discoloration 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 are extremely small, and the color balance is good with the yellow and cyan couplers as the entire silver halide color photographic light-sensitive material after the light fastness test, and the color reproducibility is extremely good. It was in a good state.

Claims (1)

[Claims] 1. Containing at least one magenta coupler represented by the following general formula [M-II] and general formula [M-III] and at least one compound represented by the following general formula [A]. A silver halide photographic light-sensitive material characterized by being General formula [M-II] General formula [M-III] [In the formula, X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent. ] General formula [A] [In the formula, R ₁ , R ₂ and R ₃ each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Y represents a group of non-metal atoms necessary for forming an imidazolidine ring in cooperation with two nitrogen atoms. ]