JPH0769595B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a dye image that 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 the dye image obtained from the silver halide photographic light-sensitive material does not deteriorate even when it is exposed to light for a long time or stored at high temperature and high humidity. It is desired that the coloring portion 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 wet heat in the uncolored portion and fading due to light in the dye image portion are very 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. It is a major problem that the dye formed from the magenta coupler of 1,2-pyrazolo-5-ones has a side absorption near 430 nm in addition to the main absorption around 550 nm. Various studies have been made.

For example, magenta couplers having an anilino group at the 3-position of 1,2-pyrazolo-5-ones described in U.S. Pat. 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,
JP 59-171956, Research Disclosure No.
24,531 1H-pyrazolo [1,5-b] -1,2,4-triazole type coupler, Research Disclosure No. 24,626
1H-pyrazolo [1,5-c] -1,2,3-triazole type couplers described in JP-A-59-162548, Research Disclosure No. 24,531, 1H-imidazo [1,2-b] ] -Pyrazole coupler, 1H-pyrazolo [1,5-as described in JP-A-60-43659 and Research Disclosure No. 24,230]
b] Pyrazole couplers, magenta couplers such as 1H-pyrazolo [1,5-d] tetrazole couplers described in JP-A-60-33552 and Research Disclosure No. 24,220 have been proposed. Of these, 1H-pyrazolo [5,1-
c] -1,2,4-trizole type coupler, 1H-pyrazolo [1,5-
b] -1,2,4-Trizole type coupler, 1H-pyrazolo [1,5-
c] -1,2,3-Trizole type coupler, 1H-imidazo [1,2-
The dye formed from b] pyrazole type coupler, 1H-pyrazolo [1,5-d] pyrazole type coupler and 1H-pyrazo [1,5-d] tetrazole type coupler has a sub-absorption near 430 nm at the above-mentioned 3rd position. 1,2-pyrazolo-5-containing anilino group
Remarkably smaller than dyes formed from on-type compounds and preferable for color reproduction. In addition, Y in the uncolored part against light, heat and humidity.
-The generation of stain is extremely small, and it has 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, and particularly the performance of print silver halide color photographic light-sensitive materials is significantly impaired. However, it has not been put to practical use in print silver halide color photographic light-sensitive materials.

In addition, JP-A-59-125732 describes 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] -1,2,4-triazole magenta coupler. Have been proposed for improving the light fastness of magenta dye images obtained from However, even in the above technique, it cannot be said that it is still sufficient to prevent fading of the magenta dye image to light.
Moreover, it has been found that it is almost impossible to prevent discoloration due 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.

[Structure of the Invention] The above object of the present invention is represented by at least one magenta color image-forming coupler represented by the following general formula [M-II] or [M-III] and the following general formula [A]. It is achieved by a silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [B].

In the formula, R ₁ , R ₂ and R ₃ each represent a substituent, and X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidant of a color developing agent.

General formula [A] In the formula, R ¹ represents an aryl group or a heterocyclic group, and Z ₁ and Z ₂
Each 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
~ 6.

n represents 1 or 2.

General formula [B] In the formula, R ² represents an aliphatic group, a cycloalkyl group, an aryl group or a heterocyclic group, and Y represents a nonmetallic atom group necessary for forming a piperazine ring or a homopiperazine ring together with a nitrogen atom.

[Specific configuration of the invention]

 Next, the present invention will be specifically described.

The general formula [M-II] or the general formula [M-II] according to the present invention.
In the magenta coupler represented by [I], R ₁ , R ₂ and R
₃ represents a substituent, and X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent.

The substituent represented by R ₁ , R ₂ and R ₃ is not particularly limited,
Typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Examples of the groups include alkenyl and cycloalkyl,
In addition to these, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, arylyloxy, heterocycleoxy, siloxy,
Acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro compound residues,
Examples include bridged hydrocarbon compound residues.

The alkyl group represented by R ₁ , R ₂ and R ₃ has 1 carbon atom
Those having a molecular weight of up to 32 are preferable, and they may be linear or branched.

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

Examples of the acylamino group represented by R ₁ , R ₂ and R ₃ 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.

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

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 1 carbon atoms.
2, especially 5 to 7, are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R ₁ , R ₂ and R ₃ includes
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, aryloxyphosphonyl group, arylphosphonyl group, etc .; acylcarbonyl group, arylcarbonyl group, etc .; carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group, alkylsulfamoyl group,
Arylsulfamoyl group and the like; as the acyloxy group, an alkylcarbonyloxy group,
Arylcarbonyloxy group etc .; Carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group etc .; Ureido group as alkylureido group, arylureido group etc .; Sulfamoylamino group as 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. As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4 -Diphenoxy-zo-1,3-1,3,5-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 .; Spiro compound residue is 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 ³⁷ ] decane-1-
Il, 7,7 [2.2.1] heptane-1-yl and the like.

Examples of the group capable of splitting off upon reaction with the oxidation product of the color developing agent represented by X include a 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 , respectively, and R ₄ and R ₅ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group. ) And other groups,
Preferred is a halogen atom, especially a chlorine atom.

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 each have the same meaning as R ₁ .

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.

Among the general formula [M-IX], preferred are (i) R _{9 to} R
_When at least two of ₁₁ are alkyl groups, (ii) R ₉
One example R ₁₁ in to R ₁₁ is a hydrogen atom, the other 2
Where R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further preferred among () 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, in the general formulas [M-II] and [M-III], R ₂ , R ₃
Is preferably represented by the following general formula [MX].

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 typical examples of the compound according to the present invention described above, 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. Then, 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.

The magenta coupler represented by the general formula [MI] (hereinafter referred to as the magenta coupler of the present invention) is a journal
Journal of the C
hemical Society), Perkin; I (1977), 20
47-2052, U.S. Patent 3,725,067, JP-A-59-99437,
58-42045, 59-162548, 59-171956, 60-3
No. 3552, No. 60-43659, No. 60-172982 and No. 60-19077
It can be easily synthesized by those skilled in the art with reference to No. 9 and the like.

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

Of the two magenta color image stabilizers according to the present invention, one is at least one compound represented by the general formula [A], and the other is piperazine represented by the general formula [B]. Alternatively, it is at least one of the homopiperazine compounds.

JP-A-61-189539 and JP-A-61-241754 describe piperazine represented by the above general formula [B] according to the present invention for stabilizing a magenta dye image obtained from the magenta coupler according to the present invention. Alternatively, it is described that a homopiperazine compound is effective.

However, in each of the above specifications, regarding stabilization of a magenta dye image obtained from the magenta coupler according to the present invention, at least a piperazine or homopiperazine-based compound represented by the general formula [B] according to the present invention is disclosed. There is no description about the effect when at least one compound represented by the general formula [A] according to the present invention is used together.

As a result of earnest studies, the present inventors have shown that at least one compound selected from the compounds represented by the general formula [A] together with the magenta coupler represented by the general formula [MI] and the general formula [B]. It has been found that when used in combination with at least one selected from the compounds, the stability of the magenta dye image obtained from the magenta coupler according to the present invention to light is dramatically improved.

Hereinafter, unless otherwise specified, the compounds represented by the general formulas [A] and [B] according to the present invention are referred to as the magenta dye image stabilizer according to the present invention.

The magenta dye image stabilizer according to the present invention used together with the magenta coupler according to the present invention not only has the effect of preventing fading of the magenta dye image by light, but also has the effect of preventing discoloration by light. .

One of them is a compound represented by the following general formula [A].

General formula [A] 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. As the substituent, as described above as the substituent of R in the general formula [MI],
A substituent can be mentioned.

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

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 have the general formula [M
It may have a substituent as described for R in -I].

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 represented by the general formula [A] 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 represented by the general formula [A] 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 and then cooled with ice to precipitate crystals. 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.

Synthetic Example-2 (Synthesis of Compound (A-17)) 20 g of p-benzyloxyaniline and 13 g of di-vinyl sulfoxide were dissolved in 150 ml of dioxane, followed by boiling and refluxing for 5 hours and then leaving at room temperature for a day and night to precipitate crystals. 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.

On the other hand, the magenta dye image stabilizer used together with the magenta dye image stabilizer of the general formula [A] according to the present invention is a piperazine or homopiperazine compound represented by the following general formula [B].

General formula [B] In formula [B], R ² represents an aliphatic group, a cycloalkyl group, an aryl group or a heterocyclic group. Examples of the aliphatic group represented by R ² include a saturated alkyl group and an unsaturated alkyl group. These include those having a substituent. Examples of the saturated alkyl group include, for example, a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group, and examples of the unsaturated alkyl group include an ethynyl group and a propenyl group. .

The cycloalkyl group represented by R ² is, for example, 5 to 7
Specific examples of the cycloalkyl group on the page include a cyclopentyl group and a cyclohexyl group, and these include those having a substituent.

Examples of the aryl group represented by R ² include a phenyl group,
Examples thereof include a naphthyl group, and these include those having a substituent.

The heterocyclic group represented by R ² , for example, 2-pyridyl group,
4-piperidyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group and the like can be mentioned, and those having a substituent are also included.

In the general formula [B], Y represents a non-metal atom group necessary for forming a piperazine ring or a homopiperazine ring together with a nitrogen atom, but the piperazine ring or the homopiperazine ring may have a substituent. .

Among the compounds according to the present invention represented by the general formula [B], the piperazine-based compound has the following general formula [B-
The piperazine-based compound represented by I] is particularly preferable.

General formula [BI] In the formula, R ² ′ represents an alkyl group, a cycloalkyl group or an aryl group. R ² ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

Among the compounds of the present invention represented by the general formula [B], the homopiperazine-based compound is particularly preferably a homopiperazine-based compound represented by the following general formula [B-II].

General formula [B-II] In the formula, R ² ′ and R ² ″ are the same as those in the above general formula [BI].
Synonymous with R ² ′ and R ² ″.

In addition, R ² ′ in the general formulas [BI] and [B-II]
The total number of carbon atoms including the substituent of R ² ″ is preferably 6 to 40.

The typical examples of the compound represented by the above general formula [B] of the present invention are shown below, but the present invention is not limited thereto.

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

The magenta dye image stabilizer represented by the general formula [B] according to the present invention is disclosed in JP-A-61-189539 and JP-A-61-2417.
It can be synthesized by the synthetic method described in No. 54.

The amount of the magenta dye image stabilizer represented by the general formula [A] and the general formula [B] of the present invention is the same as that of the magenta coupler represented by the general formula [MI] of the present invention. Each is preferably 5 to 400 mol%, more preferably 10 to 2
It is 50 mol%, and the total amount of both the magenta dye image stabilizers represented by the general formula [A] and the general formula [B] of the present invention combined is based on the magenta coupler of the present invention. 10-500 mol% is preferred, more preferably 20-400
Mol%.

Further, the use ratio of the magenta dye image stabilizer represented by the general formula [A] and the magenta dye image stabilizer represented by the general formula [B] according to the present invention is 0.1 to mol. Ten
Is preferable, and more preferably in the range of 0.25 to 4.0.

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-61-18834 is also available.
No. 4, page 106 to page 120, a magenta dye image stabilizer, that is, a combination of a phenolic compound and a phenyl ether compound represented by the general formula [XIII] in the specification. You can also

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 range 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.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side.

First layer: Emulsion layer Magenta coupler 9 of the present invention is 4.5 mg / 100 cm ² Silver chlorobromide emulsion (containing 85 mol% of silver bromide) is 3.5 mg / 100c in terms of silver.
m ² , 4.5 mg / 100 cm ^{2 of} dibutyl phthalate and gelatin
The coating amount was 12.0 mg / 100 cm ² .

Second layer: Intermediate layer (ultraviolet absorber-containing layer) 2- (2-hydroxy-3-sec-butyl-
5-t-butylphenyl) benzotriazole 5.0 mg / 100c
5.0 mg / 100 cm ^{2 of} m ² di-butyl phthalate and gelatin 1
The coating amount was 2.0 mg / 100 cm ² .

Third layer: protective layer Gelatin was applied so that the coating amount was 8.0 mg / 100 cm ² .

The sample obtained as described above was designated as sample 1.

A sample prepared by adding, to the sample 1 as a magenta dye image stabilizer, the exemplary compounds A-3, A-16, P-1, P-22 of the present invention and the comparative compounds a and b shown below in an equimolar amount with a magenta coupler. 2,3,4,5,6 and 7 were obtained.

In addition, the above six types of magenta dye image stabilizers are
Samples 8,9,10,11 and
12,13,14,15,16,17,18 and 19 were obtained.

In Samples 18 to 19, the two types of magenta dye image stabilizers used in combination were used at a molar ratio of 1: 1 and the total amount was equimolar to the magenta coupler.

Comparative compound a (compound described in JP-A-54-48538) Comparative compound b (compound described in JP-A-56-159644) After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was performed in the next step.

[Treatment Step] Treatment temperature Treatment time Color development 33 ° C. 3 minutes 30 seconds Bleach fixing 33 ° C. 1 minute 30 seconds 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-3-methyl-4-aminoaniline sulfate 4.5 g Water Add 1 to adjust pH to 10.2 with NaOH.

[Bleaching fixer]

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

The samples 1 to 19 treated as described above were measured for the 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 12 days, and the light resistance of the dye image was examined.

However, the evaluation of each item of light 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.

[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.

The results are shown in Table 1.

From the results in Table 1, the magenta coupler according to the present invention,
Samples prepared by using the magenta dye image stabilizer represented by the general formula [A] according to the present invention in combination with a conventional magenta dye image stabilizer (Samples 8, 9, 12, 13) and the present invention. A sample prepared by using such a magenta coupler in combination with a piperazine or homopiperazine-based magenta dye image stabilizer represented by the general formula [B] according to the present invention and a conventional magenta dye image stabilizer (Sample 10, 11, 14, 15), the dye image residual ratio in the light fastness test is certainly higher than that of the samples (Samples 2 to 7) prepared by adding the magenta dye image stabilizer to the magenta coupler of the present invention. Although it is improved, it is recognized that the degree of discoloration is rather large.

On the other hand, the magenta coupler of the present invention is used in combination with the compound represented by the general formula [A] according to the present invention and two types of piperazine or homopiperazine-based magenta dye image stabilizers represented by the general formula [B]. In the case of the samples (Samples 16 to 19) prepared in accordance with the present invention, the samples (Samples 2 to 5) prepared by adding the magenta dye image stabilizer of the present invention to the magenta coupler of the present invention are It can be seen that the residual rate of the dye image in the light fastness test is improved and the degree of discoloration of the dye image in the light fastness test is extremely small. As described above, in the case of a sample prepared by using two kinds of the magenta dye image stabilizers of the present invention in combination with the coupler of the present invention, one of the magenta dye image stabilizers of the present invention was added to the coupler of the present invention. It can be seen that the residual ratio and the discoloration degree of the dye image in the light fastness test are significantly improved from the sample prepared by using the seed and the conventional magenta dye image stabilizer in combination.

Example 2 Couplings of coupler and magenta dye image stabilizer in the combinations shown in Table 2 were coated exactly as in Example 1 and samples 20-48 were applied.
It was created.

Samples 20-48 were processed as described in Example 1.

Further, these samples were subjected to a light resistance test in the same manner as in Example 1 and the results shown in Table 2 were obtained.

From the results shown in Table 2, samples prepared by using the magenta coupler according to the present invention in combination with the two types of magenta dye image stabilizers according to the present invention are the two types of magenta couplers according to the present invention. It can be seen that the light resistance is remarkably improved as compared with the sample prepared by adding one of the dye image stabilizers alone.

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 49 was obtained.

First layer: blue-sensitive silver halide emulsion layer α-bivaloyl-α- (2,4-dioxo-1-benzylimidazolidin-3-yl) -2-chloro-5- [γ- (2, 4-di-t-amylphenoxy) butyramide] acetanilide 6.8 mg / 100 cm ² , blue-sensitive silver chlorobromide emulsion (containing 85 mol% of silver bromide) in terms of silver 3.2 mg / 100 c
m ² , dibutyl phthalate was 3.5 mg / 100 cm ² , and gelatin was 13.5 mg / 100 cm ² .

Second layer: intermediate layer 2,5-di-t-octylhydroquinone 0.5 mg / 100 cm ² , di-butyl phthalate 0.5 mg / 100 cm ² and gelatin 9.0 m
It was applied so as to be g / 100 cm ² .

Third layer: Green-sensitive silver halide emulsion layer 4.2 mg / 100 cm ^{2 of} magenta coupler 11 according to the present invention, and green-sensitive silver chlorobromide emulsion (containing 80 mol% of silver bromide) are converted into silver.
2.5 mg / 100 cm ^2, was coated with a dioctyl phthalate as a 4.0 mg / 100 cm ² and gelatin 12.0 mg / 100 cm ^2.

4th layer: middle layer 2- (2-hydroxy-3-sec-butyl-
5-t-butylphenyl) benzotriazole 3.0 mg / 100c
m ² , di-butyl phthalate 3.0 mg / 100 cm ² , 2.5-di-t-
Octyl hydroquinone 0.5 mg / 100 cm ² and gelatin 1
It was applied so as to be 2.0 mg / 100 cm ² .

Fifth layer: Red-sensitive silver halide emulsion layer 2- [α- (2,4-di-t-pentylphenoxy) butanamide] -4,6-dichloro-5-ethylphenol 4.2 mg / 100 cm ² as a cyan coupler , Red-sensitive silver chlorobromide emulsion (silver bromide
(80 mol% content) converted to silver 3.0 mg / 100 cm ² , tricresyl phosphate 3.5 mg / 100 cm ² and gelatin 11.5 mg
It was coated so that it would be / 100 cm ² .

Sixth layer: intermediate layer A layer having exactly the same composition as the fourth layer.

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

In the above sample 49, the magenta dye image stabilizer according to the present invention was added to the third layer in a ratio as shown in Table 3, multilayer samples 50 to 59 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 14 days) was performed.

The results are also shown in Table 3.

From the results shown in Table 3, when the total amount of the magenta dye image stabilizer according to the present invention is constant, two kinds of the present invention are used rather than the magenta dye image stabilizer according to the present invention is used alone. It can be seen that the light resistance of the magenta dye image can be greatly improved by using the magenta dye image stabilizer in an appropriate ratio.

Further, the silver halide photographic light-sensitive material of the present invention was excellent in color reproducibility and generated little Y-stain.

Example 4 The couplers and magenta dye image stabilizer combinations shown in Table 4 were coated exactly as in Example 1 and samples 60-77 were coated.
It was created.

Samples 60-77 were processed as described in Example 1.

Further, these samples were subjected to a light resistance test in the same manner as in Example 1 and the results shown in Table 4 were obtained.

The total amount of the dye image stabilizer added to each sample is 1.5 times the molar amount of the coupler, either alone or in combination, and in the case of combined use, the amount of each dye image stabilizer used. The ratios were equal in each case.

From the results of Table 4, the magenta coupler according to the present invention,
The sample of the present invention prepared by using the two magenta dye image stabilizers of the present invention in combination is one of the two magenta dye image stabilizers of the present invention in the magenta coupler of the present invention. It can be seen that the light resistance is remarkably improved as compared with the sample prepared by adding one kind alone.

Claims (1)

[Claims] 1. The following general formula [M-II] or general formula [III]
At least one of magenta color image forming couplers represented by
And at least one compound represented by the following general formula [A], and at least one compound represented by the following general formula [B]. [In the formula, R ₁ , R ₂ and R ₃ each represent a substituent, and X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidation product of a color developing agent. ] 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. ] General formula [B] [In the formula, R ² represents an aliphatic group, a cycloalkyl group, an aryl group or a heterocyclic group, and Y represents a group of non-metal atoms necessary to form a piperazine ring or a homopiperazine ring together with a nitrogen atom. ]