JPH0713736B2 - 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 colored 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 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. 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, 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 sub-absorption, and a color image for printing is particularly preferable. 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-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-
The dye formed by d] pyrazole type coupler and 1H-pyrazo [1,5-d] tetrazole type coupler has 1,2-pyrazolo-5-one whose ancillary absorption near 430 nm has an anilino group at the 3-position. It is remarkably small as compared with a dye formed from an ON group and is preferable in 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 furthermore, 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, combined with phenol compound or phenyl ether compound, 1H-pyrazolo [5,1-c] -1,2,4-triazole type 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 was recognized 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 Invention]

The above-mentioned object of the present invention has the following general formula [M-II] or [M-
III] at least one of the magenta color image-forming couplers, at least one compound represented by the following general formula [A], and at least one compound selected from the compounds represented by the following general formula [B]. This is achieved by the silver halide photographic light-sensitive material containing.

General formula [M-II] General formula [M-III] X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product 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
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 and R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide. Represents a group, a cycloalkyl group or an alkoxycarbonyl group, R ³ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or Represents an alkoxycarbonyl group.

R ³ and R ⁴ may be ring-closed to each other to form a 5- or 6-membered hydrocarbon ring.

Y represents an atomic group necessary for forming an indane ring.

[Specific configuration of the invention]

 Next, the present invention will be specifically described.

The magenta coupler represented by the above general formula [M-II] or [M-III] according to the present invention will be described.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product 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, aryloxycarbonyl, heterocyclic thio groups, and spiro compound residues, Bridge hydrocarbon compound residues and the like are also included.

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.

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

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

The cycloalkenyl group represented by R has 3 to 10 carbon atoms.
12, especially 5 to 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,
Arylsulfamoyl group and the like; as the acyloxy group, an alkylcarbonyloxy group,
Arylcarbonyloxy group, etc .; Carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group; Ureido group as alkylureido group, arylureido group, etc .; Sulfamoylamino group as alkylsulfamoylamino group, arylsulfamoylamino group Famoylamino group; 5- to 7-membered heterocyclic groups are preferable, and specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc .; Those having a 5- to 7-membered heterocycle are preferred, 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-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 residues include 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
-Yl, 7,7 [2.2.1] heptan-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 ′ has the same meaning as R above, and Z ′ is 1H-pyrazolo [5,
1-c] [1,2,4] triazole or 1H-pyrazolo [1,5-
b] represents an atomic group necessary for forming a [1,2,4] triazole ring, and R ₂ ′ and R ₃ ′ 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.

R ₂ and R ₃ represent the same groups as the above R.

The most preferable substituent R 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), R in the ring
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 (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.

In addition, R ₂ , R in the general formula [M-II] or [M-III]
_{As 3} is preferable one 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 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. 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 above general formula [M-II] or [M-III] (hereinafter, referred to as the magenta coupler of the present invention) is referred to as Journal of the Chemical Society, Perkin ( Per
kin); I (1977), 2047-2052, U.S. Patent 3,725,067,
JP 59-99437, JP 58-42045, JP 59-162548, JP 5
9-171956, 60-33552, 60-43659, 60-17298
It can be easily synthesized by those skilled in the art with reference to No. 2 and No. 60-190779.

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 another is at least one represented by the general formula [B]. It is a compound of hydroxyindane type.

JP-A-61-184543 and JP-A-61-241753 disclose that the hydroxyindane represented by the above general formula [B] according to the present invention is used for stabilizing a magenta dye image obtained from the magenta coupler according to the present invention. It is stated that the compounds of the system are effective.

However, each of the above-mentioned specifications relates to stabilization of a magenta dye image obtained from the magenta coupler according to the present invention, and at least one of the hydroxyindane compounds represented by the general formula [B] according to the present invention. There is no description about the effect of using at least one compound represented by the general formula [A] according to the present invention.

As a result of earnest studies, the present inventor has found that at least one selected from the compounds represented by the general formula [A] and the general formula [A] together with the magenta coupler represented by the general formula [M-II] or [M-III]. It has been found that the stability of the magenta dye image obtained from the magenta coupler according to the present invention to light is drastically improved when it is used in combination with at least one selected from the compounds represented by B].

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. Examples of the substituent include those described as the substituent of R in the general formula [M-II] or [M-III].

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 include those having a substituent such as those mentioned for R in the general formula [M-II] or [M-III].

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
-II] or [M-III] may have a substituent as mentioned for R.

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.

Synthesis Example-2 (Synthesis of Compound (A-17)) p-Benzyloxyaniline (20 g) and di-vinyl sulfoxide (13 g) were dissolved in dioxane (150 ml), and the mixture was boiled under reflux for 5 hours and allowed to stand at room temperature for one day 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 in combination with the magenta dye image stabilizer of the general formula [A] according to the present invention is a hydroxyindane compound represented by the following general formula [B].

General formula [B] In the general formula [B], a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide represented by R ² and R ^4. Specific examples of the group, cycloalkyl group or alkoxycarbonyl group include general formula [M-II] or [M-III]
The groups described in detail for R can be mentioned.

Specific examples of the halogen atom, alkyl group, alkenyl group, aryl group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group represented by R ³ include those represented by the formula:
The group detailed in R of II] or [M-III] can be mentioned.

Further, R ³ and R ⁴ may be closed to each other to form a 5- or 6-membered hydrocarbon ring. The 5- or 6-membered hydrocarbon ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, or a heterocyclic group. And the like.

Y represents an atomic group necessary for forming an indane ring. This indane ring has a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a hydroxy group,
It may be substituted with an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formula [B], the compounds particularly useful in the present invention are included in the compounds represented by the general formulas [BI] to [B-III].

General formula [BI] General formula [B-II] General formula [B-III] R ² , R ³ , and R ^{4 in the} general formulas [B-1] to [B-III]
Has the same meaning as in formula [B], R ⁵ represents a substituent, m represents 0 or an integer of 1 to 6, and l represents 0 or 1.
Represents an integer of 4;

When m represents an integer of 2 to 6 and l represents an integer of 2 to 4, a plurality of R ^5's may be the same or different.
Specific examples of the substituent represented by R ⁵ include the above general formula [M-
The same groups as those mentioned for R in II] or [M-III] can be mentioned.

Further, in the present invention, the case where the carbon atom forming the indane ring is a spiro atom in the general formula [BI] is also included.

Furthermore, the case where a carbon atom other than the carbon atom which already exists as a spiro atom becomes a spiro atom in the general formulas [B-II] and [B-III] is also included.

In addition, general formulas [BI], [B-II] and [B-III]
In the present invention, the case where an indane ring is formed, and two carbon atoms adjacent to each other and two R ⁵ cooperate to form a 5- to 7-membered cycloalkyl ring.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereto.

In addition to the above, the compounds shown below can be mentioned.

The magenta dye image stabilizer represented by the general formula [B] according to the present invention is described in Journal of Chemical Society (J. Chem. Soc.), 1962, pages 415 to 417, JP-B-59-
No. 32785, Bulletin of Chemical Society of Japan (Bull.Chem.Soc.Japan), 1980, 5
3 , can be manufactured according to pages 555 to 556.

The amount of the magenta dye image stabilizer represented by the general formula [A] and the general formula [B] of the present invention is represented by the general formula [M-II] or [M-III] of the present invention. 5 to 400 mol%, more preferably 10 to 250 mol%, relative to the magenta coupler of the formula (1) and the magenta dye image stabilization represented by the general formula (A) and the general formula (B) of the present invention. The total amount of both agents used is preferably 10 to 500 mol%, more preferably 20 to 400 mol%, based on the magenta coupler of the present invention.

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 10 in molar ratio. 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 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.

〔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 The magenta coupler 9 of the present invention is 4.5 mg / 100 cm ^{2 and a} silver chlorobromide emulsion (containing 85 mol% of silver bromide) is converted to 3.5 mg / 100c 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 at a coating amount of 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, HI-7, HI-12 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 8 to 19, the two types of magenta dye image stabilizers used in combination were used in a molar ratio of 1: 1 respectively, 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.

(General Example) In Tables 1 to 3, the expression A-3 + Comparative compound a means the combination of both.

From the results in Table 1, the magenta coupler according to the present invention,
Samples (Samples 8, 9, 12, 13) 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 and the present invention. Samples prepared by using the magenta coupler of the present invention in combination with a hydroxyindane-based magenta dye image stabilizer represented by the general formula [B] according to the present invention and a conventional magenta dye image stabilizer (Samples 10, 11, 14, 15), the dye image residual rate in the light fastness test is certainly improved as compared with the samples (Samples 2 to 7) prepared by adding the magenta dye image stabilizer alone to the magenta coupler of the present invention. However, 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 the two hydroxyindane-based magenta dye image stabilizers represented by the general formula [B]. The prepared samples (Samples 16 to 19) can be predicted from the samples (Samples 2 to 5) prepared by individually adding the magenta dye image stabilizer of the present invention to the magenta coupler of the present invention. 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 greatly improved from the sample prepared by using the seed and the conventional magenta dye image stabilizer together.

Example 2 The couplers and magenta dye image stabilizer combinations shown in Table 2 were coated exactly as in Example 1 and samples 20-48 were coated.
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 indicator 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-pivaloyl-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: middle layer 2,5-di-t-octylhydroquinone 0.5 mg / 100 cm ² , dibutyl phthalate 0.5 mg / 100 cm ² and gelatin 9.0 mg /
It was coated so that it would be 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-pentylphenokii) butanamide] -4,6-dichloro-5-ethylphenol 4.2 mg / 100 cm as a cyan coupler ² , 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 fixed, two kinds of the present invention are used rather than the magenta dye image stabilizer according to the present invention 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 together 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 Magenta coupler 45 and magenta dye image stabilizer
The combinations shown in the table were applied in exactly the same manner as in Example 1,
Samples 60-78 were made.

Samples 60-78 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.

From the results of Table 4, prepared by using the magenta coupler according to the present invention in combination with the magenta dye image stabilizer represented by the general formula [A] according to the present invention and the conventional magenta dye image stabilizer. (Samples 67, 68, 71 and 72), the magenta coupler according to the present invention, the magenta dye image stabilizer of the hydroxyindane type represented by the general formula [B] according to the present invention, and the conventional magenta dye. In the case of the samples (samples 69, 70, 73 and 74) prepared by using the image stabilizer together, it is true that the samples prepared by adding the magenta dye image stabilizer to the magenta coupler of the present invention individually ( Compared with Samples 61 to 66), the residual ratio of the dye image in the light fastness test is improved, but it is recognized that the degree of discoloration is slightly large.

On the other hand, the magenta coupler according to 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 hydroxyindane type magenta dye image stabilizers represented by the general formula [B]. In the case of the prepared samples (Samples 75, 76, 77, 78), the samples prepared by adding the magenta dye image stabilizer of the present invention to the magenta couplers of the present invention independently (Samples 61, 62, 63, 64) shows that the residual rate of the dye image in the light fastness test is improved and the discoloration degree of the dye image in the light fastness test is extremely small, which cannot be predicted.

As described above, in the case of the sample prepared by using the coupler of the present invention in combination with the two kinds of magenta dye image stabilizers of the present invention, the coupler of the present invention is the same as the magenta dye image stabilizer of the present invention. It can be seen that the residual ratio and the degree of discoloration of the dye image in the light fastness test are significantly improved from the sample prepared by using 1 type and the conventional magenta dye image stabilizer together.

Example 5 Samples 79 to 107 were prepared by coating magenta couplers and magenta dye image stabilizers in the combinations shown in Table 5 in exactly the same manner as in Example 1.

Samples 79-107 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 5 were obtained.

From the results shown in Table 5, 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 same as the magenta dye 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 image stabilizers alone.

Claims (1)

[Claims] 1. A magenta color image-forming coupler represented by the following general formula [M-II] or [M-III] and at least one compound represented by the following general formula [A].
And a silver halide photographic light-sensitive material containing at least one selected from the compounds represented by the following general formula [B]. General formula [M-II] General formula [M-III] [In the formula, X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidation product of a color developing agent. Also R, R ₂ , R
₃ each 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. ] General formula [B] [In the formula, R ² and R ⁴ are each a hydrogen atom, a halogen atom,
Alkyl group, alkenyl group, alkoxy group, alkenyloxy group, hydroxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group, R ³ is hydrogen An atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group. R ³ and R ⁴ may be ring-closed to each other to form a 5- or 6-membered hydrocarbon ring. Y represents an atomic group necessary for forming an indane ring. ]