JPS6385548A - Silver halide photographic sensitive material having improved fastness of dye image - Google Patents

Abstract

PURPOSE:To prevent decoloration and discoloration of a magenta color image due to light by using jointly a specific magenta coupler with a magenta tone stabilizer for the titled material. CONSTITUTION:The titled material comprises one or more kind of the magenta coupler shown by formula I and the magenta tone stabilizer shown by formula II, respectively. In the formulas, Z is a nonmetallic atom group necessary for forming a nitrogen contg. heterocyclic ring, X is H or a group capable of releasing by reacting with the oxidant of a developing agent, R is H or a substituent, R<1>-R<3> are each H or alkyl, cycloalkyl or aryl, etc. In case that the total numbers of R<1>-R<3> groups are less than 8, said coupler and stabilizer flow into a processing solution from the photosensitive material. So that, the total of said carbon numbers is necessary to be >=8. Thus, the fastness of the magenta dye image with respect to light, heat and moisture is improved, and the generation of a yellow stain is prevented in the noncolored part of the image.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a dye image that is stable against heat and light,
Moreover, the present invention relates to a silver halide photographic material in which staining is prevented from occurring.

[Background of the Invention] It is desirable that a dye image obtained from a silver halide photographic light-sensitive material does not undergo discoloration even when exposed to light for a long time or stored under high temperature and high humidity. It is desired that the uncolored areas of photographic light-sensitive materials do not turn yellow (hereinafter referred to as Y-stain) due to light or moist heat.

Known couplers for forming magenta dye images include, for example, pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, or indacylon couplers.

However, in the case of magenta couplers, Y-staining due to moist heat in uncolored areas and fading due to light in dye image areas are much larger than with yellow couplers and cyan couplers, and often become a problem.

Couplers commonly used to form magenta dyes are 1,2-pyrazolo-5-ones. This one
．． In addition to the main absorption near 550 nm, the dye formed from magenta couplers of 2-pyrazolo-5-ones has an absorption wavelength of 430 nm.
Having DI absorption near rv is a major problem, and various studies have been conducted to solve this problem.

For example, US Patent No. 2.343.703, British Patent No. 1.
Magenta couplers having an anilino group at the 3-position of 1,2-pyrazolo-5-ones described in No. 059,994 and the like have small side absorptions, and are particularly useful for obtaining color images for printing.

However, the above-mentioned magenta coupler has the disadvantage that the image storage property, particularly the fastness of the dye image to light, is extremely poor, and the Y-stain in the uncolored area is large.

As another means for reducing the side absorption near 430nrA of the above magenta coupler, British Patent No. 1,047.
Pyrazolobenzimidazoles described in US Pat. No. 612, indasilones described in US Pat. No. 3.770.447, and US Pat.
1H- described in No. 2.418 and No. 1.334.515
Pyrazolo[5,1-C]-]1,2,4-triazole type coupler 1H- described in JP-A-59-171956, Research Disclosure No. 24,531
Pyrazolo[1,5-b]-]1.2.4-triazole type coupler Research Disclosure NO,2
1H-pyrazolo[1,5-c]- as described in 4,626
1,2゜3-triazole type coupler, JP-A-59-1
No. 62548, Research Disclosure No. 2
1H-imidazo[1,2-b rhopyrazole type coupler described in JP-A-60-43659, Research Disclosure No. 24.230; Pyrazole type coupler, 1H-pyrazolo [described in JP-A-60-33552, Research Disclosure No. 24,220]
Magenta couplers such as 1,5-d ]tetrazole type couplers have been proposed. Among these, 1H-pyrazolo[5,1-c]-]1.2.4-triazole type coupler 1H-pyrazolo M, 5-b]-1,2°4-triazole type coupler, 1H-pyrazolo N, 5-c rho 1.2.3-triazole type coupler, 1H-imidazo[1,2-b]pyrazole type coupler 1H-pyrazolo[1,5-d]pyrazole type coupler and 1H-
The dye formed from the pyrazolo[1°5-d]tetrazole type blur has a sub-absorption around 430 nm that is similar to the dye formed from the 1,2-grabro 5-ones having an anilino group at the 3-position. It is considerably smaller than that, which is preferable in terms of color reproduction, and furthermore, the generation of Y-stin in uncolored areas due to light, heat, and humidity is also extremely small, which is a desirable advantage.

However, the fastness of azomethine dyes formed from these couplers to light is extremely low, and in addition, the dyes are easily discolored by light, which significantly impairs the performance of print-based silver halide color photographic light-sensitive materials in particular. However, it has not been put to practical use in printed silver halide color photographic materials.

Furthermore, in JP-A-59-1257-32, a 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. A technique has been proposed for improving the light fastness of a magenta dye image obtained from a 1H-pyrazolo[5,1-c rho1.2°4-triazole type magenta coupler. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light.

[Object of the Invention] The first object of the present invention is to provide a silver halide photographic material in which the formed magenta dye does not exhibit shear absorption and the fastness of the magenta dye image to light is significantly improved. .

A second object of the present invention is to provide a silver halide photographic material having a magenta dye image with little discoloration due to light.

The third object of the present invention is to reduce Y in uncolored areas against light and moist heat.
- It is an object of the present invention to provide a silver halide photographic material in which staining is prevented from occurring.

[Constitution of the Invention] The above object of the present invention is to provide a silver halide photographic light-sensitive material with at least one magenta coupler represented by the following general formula [M-IF] and at least one compound represented by the following general formula [A]. is coupled by containing.

General formula [M-IF In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Further, R represents a hydrogen atom or a substituent.

General formula [A] N-〇-R3 In the formula, R1, R2 and R3 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. However, the total number of carbon atoms in the groups represented by R1, R2 and R3 is 8 or more.

[Specific structure of the invention] Next, the present invention will be specifically explained.

In the magenta coupler represented by the general formula [M-N general formula [M-11] according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and The ring may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Further, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, cararyloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, ami7, alkylamino, imide, ureido, sulf7amoylamino, alph pheasant carbonylamine/, aryloxycarbonylamide/, alkoxycarbonyl, aryloxycarbonyl, heterocyclic groups, and spiro compound residues,
Also included are 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″C is preferably a phenyl group.

R1'! Examples of the acylamine 7 groups to be used include alkylcarbonylamino groups, arylcarbonylamino groups, and the like.

Examples of the sulfonamide group represented by R include 7 alkylsulfonylamide groups and 7 arylsulfonylamide groups.

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.
The cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

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

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, Arylphosphonyl group ring; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; For a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a 77 moyl group, an alkylsulfamoyl group,
Arylsulfamoyl group ring; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc.; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, aryl Ureido group, etc.; Examples of sulfamoyl 7 groups include 7 alkylsul 7 amoylamides, 7 arylsul 7 amoylamides, etc.; As heterocyclic groups, 5 to 7 mol groups are preferable, specifically 2-7 lyl groups, 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; the heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,4,5.6-tetrahydropyranyl-2 -oxy group, 1-7゜enyltetrazol-5-oxy group, etc.; as the heterocyclic thio group, a 5- to 7-shell heterocyclic group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, etc. groups, 2.4-97 dinoxy 1.3.5-triazole-6 monothio groups, etc.; siloxy groups include trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxy, etc.; imide groups include succinimide, 3-heptadecylsuccinimide group, 7talimide group, glutarimide group, etc.; Spiro compound residues include spiro [3,3]heptan-1-yl, etc.; monohydrocarbon compound residues include bicyclo [2゜2.1] Heptan-1-yl, tricyclo [3゜3.
Examples thereof include 1.1co7]decane-1-yl, 7,7-nomethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

Examples of the group represented by X which can be separated by reaction with the oxidized product of the color developing agent include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, azinyloxy, aryloxycarbonyl, Flukyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxycarbonylami/, aryloxycarbonyl amino, carboxyl, (R1' is the same as the above R, Z' is the same as the above Z, R2' and R3
'' may be a hydrogen atom, an atomyl group, an alkyl group or a heterocyclic group, and is preferably a halogen atom, especially a chlorine atom.

In addition, as the nitrogen-containing heterocycle formed by Z or Z',
Examples include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and the above-mentioned example Jl.
, I'm so excited! ↓One by one +", + + I mentioned above.

More specifically, what is represented by the general formula [M-II] is represented by, for example, the following general formulas [M-I[] to [M-■].

General formula [M-[1 General formula [M-I [[] General formula [M-■] General formula [M-VI General formula [M-VI] General formula [M-■] General formula [M-II] ] ~ [M-■] R8-R
1 and X have the same meanings as R and X above.

Also, preferred among the general formulas [M-II] are those represented by the following general formula [M-■].

In the formula, R, , X and Zl represent the general formula [R in M-II,
It is synonymous with X and Z.

Among the magenta couplers represented by the general formulas [M-n] to [M-■], particularly preferred ones are those represented by the general formula [M-I
It is a magenta coupler represented by II.

The most preferred substituents R and R3 on the i elemental ring are those represented by the following general formula [M-[1].

General formula [M-III R.

R3゜−C− R1+ where R! l Rl O and R1+ each have the same meaning as R above.

Also, the above R,,R,. and two of R1+, for example R1
and RIo may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1 may be further combined with the chain ring to constitute a bridged hydrocarbon compound residue. Good too.

Among the general formula [M-ffl, (i')R
, ~ When at least two of the R groups are furkyl groups,
(ii) One of R, to R1, for example Rl1, is a hydrogen atom, and the other two R1 and R1° combine to form a cycloalkyl together with the root carbon atom.

Furthermore, in (i), it is preferable that two of Rs to R are alkyl groups and the other one is a hydrogen atom or an alkyl group.

V -JJ)d' rυ -I 1 1-
Ladle I+? 7 1- & n XS
The substituent that the ring formed by R and the ring formed by Z in the general formula [M-■] may have, and the general formula [
R2 to R8 in M-I11 to [M-VI] are preferably represented by the following general formula [M-X].

General formula [M -X ] -R'-6Q2-R2 In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R' preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and does not matter if the straight chain has 9 branches.

The cycloalkyl group represented by R2 is preferably 5 to 6 true.

Typical specific examples of the compounds according to the present invention are shown below.

1ρ/JII 夷CH り剮white IN-HE-N In addition to the above representative examples of the compounds according to the present invention, specific examples of the compounds according to the present invention include
Among the compounds described on pages 66 to 122 of the specification, No. 1 to 4, 6.8 to 17, 19 to 24.
28~43.45~59.61~104*toe~
Compounds represented by 121.123 to 162.164 to 223 can be mentioned.

The magenta coupler represented by the general formula [M-I] (hereinafter referred to as the magenta coupler of the present invention) is described in the Journal of the Chemical Society (Jour
nal of the Chf31iCal
3ocrity), Perkin (Per
kin) I (1977), 2047-205
2. U.S. Patent No. 3,725,067, JP-A-59-99
No. 437, No. 58-42045, No. 59-1625
No. 48, No. 59-171956, No. 6゜-3355
2, No. 60-43659, No. 60-172982, No. 60-190779, etc., and can be easily synthesized by those skilled in the art.

The magenta couplers of the present invention usually have IX 10-3 to 1 mole per mole of silver halide, preferably 1X10
It can be used in the range of -2 mol - 8 x 10 -1 mol.

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

When the compound represented by the general formula [A] (hereinafter referred to as the magenta dye image stabilizer of the present invention) contained in the silver halide photographic light-sensitive material of the present invention is used in conjunction with the magenta coupler of the present invention, , has the effect of preventing not only macenta dye images from fading due to light but also discoloration due to light.

In the general formula [A], examples of the alkyl group represented by R+, R2 and R3 include methyl group, ethyl group, butyl group, hexyl group, octyl group, dodecyl group, and octadecyl group.

These alkyl groups include those having a substituent, and examples of the substituent include aryl groups such as a phenyl group, p-chlorophenyl group, and p-perfluoromethylphenyl group.

Examples of the alkenyl group represented by R+, R2, and R3 include a vinyl group and an allyl group. These alkenyl groups also include those having a substituent, and examples of the substituent include an aryl group.

Examples of the cycloalkyl group represented by R1, R2 and R3 include a cyclopentyl group and a cyclohexyl group, and these cycloalkyl groups also include those having a substituent.

Examples of the aryl group represented by R+, R2, and R3 include phenyl group, naphthyl group, etc. These aryl groups also include those having substituents, and examples of the substituent include alkyl groups (methyl group, etc.) , an alkoxy group (such as a methoxy group), an acylamino group (such as an acetylamino group), and the like.

As the heterocyclic group represented by R1, R2 and R3,
Examples include 2-furyl group and 2-pyridyl group, and these heterocyclic groups also include those having substituents.

In the general formula [A], the total number of carbon atoms in the groups represented by R1, R2 and R3 is 8 or more. This number of carbon atoms includes the number of carbon atoms of the substituent when the group represented by R1, R2 and R3 has a substituent.

If the total number of carbon atoms in the groups represented by R1, R2, and R3 is less than 8, the compound represented by the general formula [A] will flow out from the light-sensitive material into the processing solution during the processing step. The object of the invention cannot be achieved.

In the present invention, in the general formula [A], R1, R2 and R3 are each a hydrogen atom (however, R1, R2 and R3 are not hydrogen atoms at the same time), an alkyl group,
Particularly preferred is a cycloalkyl group or an aryl group.

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

Synthesis Example 1 (Synthesis of Compound A-6) After dissolving 14 g of human O-xylamine hydrochloride and 50 g of benzyl chloride in 200 d of a 70% ethyl alcohol aqueous solution, 60 g of anhydrous sodium carbonate was added, and boiling and refluxing was continued for 2 hours. The reaction solution was poured into ice water, and the precipitated crystals were collected by filtration and recrystallized from methanol to obtain white needle-like crystals 24a.

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

Synthesis Example-2 (Synthesis of Compound A-2) Hydroxylamine hydrochloride 14g1 Octyl bromide 7
After boiling and refluxing 160 g of an ethyl alcohol solution containing 6 g of anhydrous sodium carbonate and 60 o of anhydrous sodium carbonate for 3 hours, it was poured into ice water, the precipitated crystals were collected by filtration, and then recrystallized from methanol to obtain 32 g of white needle-like crystals.

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

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

Although it is preferred that the magenta couplers of the invention and the magenta dye image stabilizers of the invention are used in the same layer, the stabilizers may be used in layers adjacent to the layer in which the couplers are present.

Hydrophobic compounds such as the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention can be prepared in silver halide photographic light-sensitive materials using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. Can be added to. For example, in the oil-in-water emulsion dispersion method, a hydrophobic additive such as a magenta coupler is usually used in a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary, a low-boiling point and/or water-soluble solvent is used in combination. After dissolving and emulsifying and dispersing in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, it may be 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, in addition to the magenta dye image stabilizer of the present invention,
The magenta dye image stabilizer described on pages 106 to 120 of Specification No. 88344, namely, the compound of general formula [XI
A phenol compound and a phenyl ether compound represented by [ ] can also be used in combination.

When this phenol compound or phenyl ether compound is used in combination, it is preferably used in an amount a of 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 phenyl ether compound have the effect of preventing fading of the magenta dye image obtained from the magenta coupler of the present invention, but have almost no effect of preventing discoloration. Therefore, it is not preferable to use an excessive amount of the phenol compound and phenyl ether compound in the magenta dye image stabilizer of the present invention.

In general, the magenta dye image obtained from the magenta coupler of the present invention not only shows significant fading when exposed to light, but also undergoes discoloration due to light, and the color tone of the dye image changes from magenta to yellowish. The magenta dye image stabilizer of the present invention can prevent the magenta dye image obtained from the magenta coupler of the present invention from fading and discoloration due to light, an effect that cannot be achieved with the phenolic compounds and phenyl ether compounds. 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 amount of the phenol compound and phenyl ether compound must be selected to such an extent that the discoloration caused by light is not noticeable. Must be.

When appropriate amounts of the phenolic compound and phenyl ether compound are used in combination with the magenta dye image stabilizer of the present invention, a mutually beneficial effect may be observed due to the combined use.

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, etc., but the present invention particularly applies when it is applicable to color photographic paper used for direct viewing. The effects of this will be effectively demonstrated.

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

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

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

The silver halide photographic material of the present invention includes a color antifoggant, a hardening agent, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger 1 mordant, a development accelerator,
Development retardants, optical brighteners, matting agents, lubricants, antistatic agents, surfactants, and the like can be optionally used.

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

[Specific Effects of the Invention] According to the silver halide photographic material containing the magenta coupler and magenta dye image stabilizer of the present invention, conventionally,
In particular, it improves the fastness of magenta dye images, which have low fastness to light, heat, and humidity.
Fading and generation of Y-stain in uncolored areas due to light, heat, and humidity can be effectively prevented.

[Examples] Example 1 Gelatin (12,0 mg/100 cf) and the following comparative magenta coupler a (4,1 mg/100 cf) were placed on a paper support laminated on both sides with polyethylene.
) was dissolved and emulsified in tricresyl phosphate (a, oII 1 g/100 cf) together with 5-di-tert-octylhydroquinone (o, 2 mg/100 cf), and then silver chlorobromide emulsion silver bromide 80 mole%,
Sample 1 was obtained by mixing with a coated silver amount of 3.8 mg/100 Cf), coating, and drying.

The following P was added to Sample 1 as a magenta dye image stabilizer.
Sample 2 was obtained in which H-1 was added in a molar amount 1.8 times that of the magenta coupler.

Samples 3 and 7.11 were obtained in the same manner except that the magenta coupler in Sample 1 was replaced with magenta couplers 4.9 and 20 of the present invention, respectively.

Samples 4 and 8.12 were obtained by adding the magenta dye image stabilizer PH-1 in 1.8 times the mole of the coupler to the above samples 3.7.11, and then replacing PH-1 with the present invention. The inventive magenta dye image stabilizer A-2 is combined with coupler 1.
Eight times the molar amount was added to obtain samples 5, 9, and 13, respectively. In addition, to the sample 3.7.11, magenta dye image stabilizer A-19 was added in an amount of 0.9 times the mole of the coupler to obtain sample 6.10.14, respectively.

H-1 Comparative magenta coupler a CII I After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps.

[Processing process 1 Processing temperature Processing time For color development @
Bleach and fix at 33°C for 3 minutes and 30 seconds 33
℃ Wash with water for 1 minute 30 seconds 33℃
3 divisions Drying 50-80℃
The components of each 2-minute treatment solution are as follows.

[Color developer] Benzyl alcohol 12i12 diethylene glycol 101g Potassium carbonate 25g Sodium bromide
o, eg anhydrous sodium sulfite
2.0g hydroxylamine sulfate
2.5ON-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4=aminoaniline sulfate 4.5g Add water to make 111, adjust to NaOH with T1)Hlo, 2.

[Bleach-fix solution] Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g EDTA ferric ammonium salt 65 g Water was added to bring the solution to 111, and the pH was adjusted to 6.7 to 6.8.

The concentrations of Samples 1 to 14 treated above were measured using a densitometer (KO-7R model manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned processed samples was exposed to a xenon fade meter for one day to examine the light fastness of the dye image and the Y-stin of the uncolored area, while each sample was exposed to a high temperature and high humidity atmosphere of 60°C and 80% RH. The dye image was left to stand for 14 days, and the moisture resistance of the dye image and the Y-stain of the uncolored area were examined. The results obtained are shown in Table 1.

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

[Residual rate] Percentage of dye remaining after side light and moisture resistance test with respect to initial density 1.0.

[Y-Stin (Y-8)] Value obtained by subtracting the Y-Stin concentration before the sub-light and humidity resistance test from the Y-stin concentration after the sub-light and humidity resistance test.

[Degree of discoloration] Yellow density after light exposure test at initial density 1.0)/
(magenta 1 degree) to yellow density before the light test) /
(magenta density), the larger this value, the more yellowish the magenta becomes.As is clear from Table 1 below, the magenta coupler produced using the magenta coupler of the present invention Sample 3, 7.11 is the conventional 4 equivalent
It can be seen that Y-stin is extremely less likely to occur in the side light and M humidity tests compared to Sample 1, which was fabricated using a 3-anilino-1,2-pyrazol-5-one type coupler. It can be seen from the residual rate and degree of discoloration of the dye image area in the test that it easily discolors and fades when exposed to light. Sample 4゜8.12 was prepared by using the magenta coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-1, which certainly improved the dye image caused by light. Although fading is greatly improved, discoloration cannot be improved.

On the other hand, samples 5.6, 9, and 1 were prepared using the 7 zenta coupler of the present invention and the magenta dye image stabilizer of the present invention.
0.13.14, the color change and fading of the dye image was slight in the light, heat, and humidity resistance tests, and it was found that almost no Y-stain occurred in the uncolored areas. This is possible because the combination of the conventional 4-type 3-anilino-1,2-pyrazolo-5-one type coupler and the dye image stabilizer PH-1 (Sample 2) could not achieve this.

Example 2 Samples 15 to 30 were prepared in the same manner as in Example 1 except that magenta couplers and magenta dye image stabilizers were used in combinations shown in Table 2. Sample 15~
No. 30 was treated as described in Example 1. Furthermore, these samples were subjected to a light resistance test and a moisture resistance test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

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

H-2 H-3 Comparative Magenta Coupler b Table 2 7 Os Koshin As is clear from Table 2, conventionally used
4. When the magenta dye image stabilizer of the present invention is used in combination with the 3-anilino-1,2-pyrazolo-5-one type coupler of this model (Sample 15.16), and when the magenta dye image stabilizer of the present invention is used in combination with the magenta coupler of the present invention, When using a magenta dye image stabilizer (Samples-19, 20, 21, 22), there was no discoloration or fading in the side light test, Y-stin in the uncolored area, and Y-stin in the moisture resistance test. It is understood that it is not possible to improve all of the above, and that all of the above-mentioned improvements can only be achieved by using the magenta coupler of the present invention in combination with the magenta dye image stabilizer of the present invention.

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 Sample 31 was obtained.

111th! : Blue-sensitive silver halide emulsion layer Yellow coupler: α-pivaloyl-α-(2,4-dioxo-1
-benzylimidazolidin-3-yl)-2-chloro-
5-[7-(2゜4-di℃-amylphenoxy)butylamitocoacetanilide 6.8n+g/100c
12. Blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) is converted into silver, 3.2 m (1/100 Ct'), di-butyl phthalate: 3.5 mg/100 Cf, and gelatin: 13.5010 / The coating was applied so that the coating depth was 100 cr.

2nd layer: Intermediate layer 2.5-G℃-octylhydroquinone 0.5+a
g/100cf, 0.5mg dibutyl phthalate
/100C,? And 9.0m of gelatin! +/ 1 o
It was painted so that it became oc112.

Third layer: Green-sensitive silver halide emulsion layer The magenta coupler 1 is 3.5 m thick/100c12
, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) is converted into silver to be 2.5111a/100Cf, di-butyl phthalate is 3.0mg/100cf, and gelatin is 12.0mg/100cf. It was painted like this.

4th Wi: 5.01110/100Cf of 2-(2-hydroxy-3-sec-butyl-5-t-butylphenyl)benzotriazole and 5.0ttl (1/100Cv of di-butyl phthalate) of the intermediate layer UV absorber. ”, 2, 5-di[-octylhydroquinone 0.5+n+J/1
100c1 and gelatin 12.011IQ/100c
It was painted so that it became f.

5th layer: red-sensitive silver halide emulsion layer 4.2 mg/100 cf of 2-[α-(2,4-di-1-pentylphenoxy)butanamide]-4°6-dichloro-5-ethylphenol as a cyan coupler; Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was converted into silver to be 3.0ffl/100Cf 1t' licresyl phosphate 3.5mg/100C1' and gelatin 11.5mQ/ It was painted so that it became 100c12.

6th layer: Protective layer Gelatin was coated to a thickness of 8.0111 (+/100 cf).

In the sample 31, the 31st! ! to which the magenta dye image stabilizer of the present invention is added in the proportions shown in Table 3,
Multilayer samples 32 to 4o were prepared, exposed and processed in the same manner as in Example 1, and then subjected to a double-light test (1 xenon fade meter).
irradiated for 5 days). The results are also shown in Table 3.

Table 3 Based on the results, the magenta dye image stabilizer of the present invention:
It is effective in stabilizing the dye image obtained from the magenta coupler of the present invention, and the effect becomes greater as the amount of m added is increased. Moreover, compared to sample 31, samples 32 to 40 showed extremely small discoloration of the dye images in the light emission test. moreover,
In the sample of the present invention, the discoloration and fading of the magenta dye are extremely small, and after the secondary light test, the overall color balance with the yellow and cyan couplers as a silver halide color photographic light-sensitive material is good, and the color reproducibility is extremely good. maintained its condition.

Claims (1)

[Scope of Claims] A silver halide photograph characterized by containing at least one magenta coupler represented by the following general formula [M-I] and at least one compound represented by the following general formula [A] photosensitive material. General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2 and R^3 are each a hydrogen atom,
It represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. However, the total number of carbon atoms in the groups represented by R^1, R^2 and R^3 is 8 or more. ]