JPH0713735B2 - 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 heat of moisture.

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

However, the above-mentioned magenta coupler has 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 coupler, Research Disclosure
1H-pyrazolo [1,5-c] -1,2,3-described in No. 24,626
Triazole type couplers, 1H-imidazo [1,2-b] -pyrazole type couplers described in JP-A-59-162548 and Research Disclosure No. 24,531, JP-A-60-436.
No. 59, 1 of Research Disclosure No. 24,230
H-pyrazolo [1,5-b] pyrazole type coupler
No. 60-33552, Research Disclosure No. 24,220
Magenta couplers such as the described 1H-pyrazolo [1,5-d] tetrazole type couplers 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-pyrazo [1 The dye formed from a 5,5-d] tetrazole-type coupler has a 1,2-pyrazolo-group having an anilino group at the 3-position as a side absorption near 430 nm.
It is significantly smaller than dyes formed from 5-ones in terms of color reproducibility, and has extremely small Y-stain generation in the uncolored portion against light, heat and humidity, 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.

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

[Object of the Invention]

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

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

A third object of the present invention is to provide 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 object of the present invention is to provide at least one magenta color image forming coupler represented by the following general formula [MI], at least one compound represented by the following general formula [A], and the following general formula [B And a silver halide photographic light-sensitive material containing at least one compound selected from the following:

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

X represents a hydrogen atom or a 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 ⁵ 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,
Represents a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group, R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, and R ⁴ represents a hydrogen atom or a halogen atom. Represents an alkyl group, an alkenyl group, an aryl group, an aryloxy 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 ring.

Further, R ³ and R ⁴ may be closed to form a methylenedioxy ring.

Y represents an atomic group necessary for forming a chroman or coumaran ring.

[Specific configuration of the invention]

 Next, the present invention will be specifically described.

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

X represents a hydrogen atom or a group capable of 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, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups , And spiro compound residues, bridged hydrocarbon compound residues and the like.

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

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

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

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

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 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 .; trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group etc. as siloxy group; succinimide as imide group Group, 3-heptadecyl succinimide group, phthalimido group, glutarimide group, etc .; spiro [3,3] heptane-1 as a spiro compound residue
-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 can be mentioned.

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, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group). And a halogen atom, particularly a chlorine atom is preferable.

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

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

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

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

General formula [M-VIII] In the formula, R ₁ , X and Z ₁ are R, X and Z in the general formula [M-1].
Is synonymous with.

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

The most preferable substituents R and R ₁ on the heterocycle are represented by the following general formula [M-IX].

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

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

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.

Further, the ring formed by Z in the general formula [M-I] and the substituent which the ring formed by Z ₁ in the general formula [M-VIII] may have; and the general formula [M-II] to [M-
As R _{2 to} R ₈ in VI], 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 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. Pat.No. 3,725,067, JP-A-59-99437,
58-42045, 59-162548, 59-171956, 6
0-33552, 60-43659, 60-172982 and 60
It can be easily synthesized by those skilled in the art with reference to No. 190779 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 types of 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 coumaran or chroman compound.

JP-A-61-158330 and JP-A-61-241755 disclose in which the magenta dye image obtained from the magenta coupler according to the present invention is stabilized by a coumarane or chroman represented by the above general formula [B]. 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 coumarane or chroman-based 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 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 1-naphthyl group and the like, 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 a 2-furyl group,
Examples thereof include 2-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-vinylsulfone were dissolved in 200 ml of ethanol, and the mixture was boiled under reflux for 3 hours, cooled with ice, and precipitated crystals were formed. It was collected by filtration. Recrystallization from methanol gave 18 g of white scaly crystals.

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

Synthesis Example-2 (Synthesis of Compound (A-17)) 20 g of p-benzyloxyaniline and 13 g of di-vinylsulfoxide were dissolved in 150 ml of dioxane, and after boiling and refluxing for 5 hours, the mixture was left standing overnight at room temperature 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 coumaran or chroman 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 ^5. Group, a cycloalkyl group or an alkoxycarbonyl group; an alkyl group represented by R ³ , an alkenyl group, an aryl group,
Acyl group, cycloalkyl group or heterocyclic group: a halogen atom represented by R ⁴ , an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or Specific examples of each group of the alkoxycarbonyl group include the groups described in detail for R in the general formula [MI].

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

Y represents an atomic group necessary for forming a chroman or coumaran ring.

This chroman or coumaran ring has a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group,
It may be substituted with 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 include compounds represented by the general formulas [BI], [B-II], [B
-III], [B-IV] and [BV] are included in the compound.

General formula [BI] General formula [B-II] General formula [B-III] General formula [B-IV] General formula [BV] General formulas [B-1], [B-II], [B-III], [BI]
R ^2, R ³ in the V] and [B-V], R ⁴ and R ⁵ have the same meaning as in formula (B), R ⁶ represents a substituent, m is 0 or 1 to 4 Represents the integer, and l is 0 or 1
Represents an integer of 6.

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

In the present invention, the general formulas [BI] and [BI]
In I] and [BV], the case where the carbon atom forming the coumaran ring or the chroman ring becomes a spiro atom is also included.

Furthermore, the case where a carbon atom other than the carbon atom already existing as a spiro atom in the general formulas [B-III] and [B-IV] forms a spiro atom is also included.

Further, in the general formulas [BI], [B-II], [B-III], and [BV], a coumaran or chroman ring is formed and two carbon atoms and two R ⁶ which are adjacent to each other are formed. The present invention also includes the case where the above-mentioned groups 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] is tetrahedron (Tetrahedron), 1970, vol 26,4743.
~ 4751, Journal of the Chemical Society of Japan, 1972, No. 10, 1987-1990;
It can be synthesized according to the methods described in Chemical Letter (Chem. Lett), 1972 (4) pages 315 to 316 and JP-A-55-139383.

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-61-1883
Magenta dye image stabilizer described on pages 106 to 120 of No. 44 specification, that is, the combined use of a phenol 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-) as an ultraviolet absorber
Butyl -5-t-butylphenyl) benzotriazole and 5.0 mg / 100 cm ² di - by coating as butyl phthalate becomes 5.0 mg / 100 cm ² and the coating with the amount of gelatin 12.0 mg / 100 cm ^2.

Third layer: Protective layer Gelatin was applied at a coating amount of 8.0 mg / 100 cm ² .

Samples 1 and 201, 301, 401, 501 were obtained by replacing the magenta coupler 9 of Sample 1 and the couplers shown in Tables 2 to 6 with the samples obtained as described above.

In each of the above-mentioned samples, as the magenta dye image stabilizer, the exemplified compounds A-3, A-16, CH-2 and CH- of the present invention were used.
11 and Samples 2, 3, 4, 5, 6 and 7, 102, 103, 10 in which equimolar amounts of 11 and the comparative compounds a and b shown below were added to the magenta coupler.
4,105,106 and 107,202,203,204,205,206 and 207,30
2,303,304,305,306 and 307,402,403,404,405,406 and 407,502,503,504,505,506 and 507 were obtained.

In addition, the above six types of magenta dye image stabilizers are
Samples 8 and 2 are used in combination as shown in Table 6 to Table 6.
9,10,11,12,13,14,15,16,17,18 and 19,108,109,110,1
11,112,113,114,115,116,117,118 and 119,208,209,21
0,211,212,213,214,215,216,217,218 and 219,308,30
9,310,311,312,313,314,315,316,317,318 and 319,40
8,409,410,411,412,413,414,415,416,417,418 and 41
9,508,509,510,511,512,513,514,515,516,517,518 and 519 were obtained.

In Samples 8 to 19,108 to 119,208 to 219,308 to 319,408 to 419 and 508 to 519, the two magenta dye image stabilizers used in combination were used at a molar ratio of 1: 1 respectively, and the total amount was the same as the magenta coupler. It is used.

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 was added to adjust the pH to 1 and the pH was adjusted 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.

Samples treated above 1-19,101-119,201-219,301-
The concentrations of 319, 401 to 419 and 501 to 519 were measured under the following conditions using a densitometer (Konishi Rokusha Kogyo KD-7R type).

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 Tables 1 to 6.

(General example) In Tables 1 to 12, for example, the expression A-3 + comparative compound a means the combination of both.

From the results of Tables 1 to 6, the magenta coupler according to the present invention is used 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 created by (samples 8, 9, 12, 13, 108, 109, 112,
113,208,209,212,213,308,309,312,313,408,409,412,41
3,508,509,512,513) and a magenta coupler according to the present invention, and a magenta dye image stabilizer of the chroman and spirochroman type represented by the general formula [B] according to the present invention and a conventional magenta dye image stabilizer were used in combination. Samples (Samples 10,11,14,15,110,111,114,115,210,211,214,215,
310,311,314,315,410,411,414,415,510,511,514,515)
In the case of, the light fastness test is surely compared with the samples (Samples 2 to 7,102 to 107,202 to 207,302 to 307,402 to 407 and 502 to 507) prepared by adding the magenta dye image stabilizer to the magenta coupler of the present invention. The residual rate of the dye image is improved, but the degree of discoloration is slightly 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 chroman- or spirochroman-based magenta dye image stabilizers represented by the general formula [B]. Samples created by
119,216 to 219,316 to 319,416 to 419 and 516 to 519), samples prepared by adding the magenta dye image stabilizer according to the present invention to the magenta coupler according to the present invention alone (Samples 2 to 5,102 to 105,202). ~ 205,302 ~ 305,402
405 and 502 to 505), it can be predicted that the residual ratio 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 A coupler and a magenta dye image stabilizer were applied in exactly the same manner as in Example 1 in the combinations shown in Tables 7 to 10 to prepare Samples 20 to 48,600 to 628,700 to 715 and 800 to 815. .

Samples 20-48,600-628,700-715,800-815 were processed by the method 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 Tables 7 to 10 were obtained.

From the results shown in Tables 7 to 10, the samples prepared by using the magenta coupler according to the present invention in combination with the two magenta dye image stabilizers according to the present invention are the 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 two kinds of magenta 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 multi-color 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 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 , dibutyl phthalate 3.5 mg / 100 c
m ² and gelatin were coated so as to be 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-pentylphenoxy) 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 .

The sample 49 and the sample 60 in which the magenta coupler 11 of the sample is replaced with the magenta coupler 47 of the present invention, the magenta dye image stabilizer of the present invention is contained in the third layer as shown in Tables 11 to 12. The multilayer samples 50 to 59 and 61 to 70 were added in various proportions, exposed and processed in the same manner as in Example 1 and then subjected to a light resistance test (a xenon fade meter was irradiated for 14 days).

The results are also shown in Tables 11 to 12.

From the results of Tables 11 to 12, when the total amount of the magenta dye image stabilizer according to the present invention is fixed, two kinds of magenta dye image stabilizers according to the present invention are used. It can be seen that the light resistance of the magenta dye image can be greatly improved by using the magenta dye image stabilizer according to the present invention 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.

Claims (1)

[Claims] 1. At least one magenta color image-forming coupler represented by the following general formula [MI], at least one compound represented by the following general formula [A], and the following general formula [B]. A silver halide photographic light-sensitive material containing at least one selected from the compounds represented. General formula [MI] [In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a 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 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 ⁵ 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,
Represents a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group, R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, and R ⁴ represents a hydrogen atom or a halogen atom. Represents an alkyl group, an alkenyl group, an aryl group, an aryloxy 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 ring. Further, R ³ and R ⁴ may be closed to form a methylenedioxy ring. Y represents an atomic group necessary for forming a chroman or coumaran ring. ]