JPS6394239A - Silver halide photographic sensitive material having improved stability of dye image - Google Patents

Abstract

PURPOSE:To obtain excellent color reproducibility of the titled material, and to improve remarkable lightfastness of a magenta dye image by incorporating a magenta coupler and a specific compd. to the titled material. CONSTITUTION:The titled material comprises at least one of the magenta coupler shown by formula I and at least one of the compd. selected from the compds. shown by formulas II, III and IV. In the formula I, Z is a non-metal atom group necessary for forming a nitrogen contg. heterocyclic group, X is hydrogen atom or a substituent capable of releasing by reacting with an oxidant of color developing agent, R is hydrogen atom or a substituent. In formulas II, III and IV, R<3> is hydrogen atom, alkyl or cycloalkyl group, etc., R<4> is a substituent, (m) is an integer of 0 or 1-6. Thus, the fastness of magenta dye image is improved, and decoloration descoloration against light are remarkably reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light and the generation of stain is prevented.

[Background of the invention]

The magenta dye formed from the IH-pyrazoloazole type coupler has a secondary absorption near the 430n ring at the 3rd position.
Compared to dyes formed from 5-pyrazolones having groups, it is significantly smaller and more favorable in terms of color reproduction, and furthermore, yellowing (Y-stain) of uncolored areas due to light, heat, and humidity is extremely small, which is a desirable advantage. It is something that you have.

However, the fastness of azomethine dyes formed from these couplers to light is rather low, and in addition, the dyes are easily discolored by light, which seriously impairs the performance of color photographic materials, especially printed color photographic materials. It is.

Furthermore, in JP-A No. 59-125732, an IH-pyrazolo(5°1-c)-1,2,4-triazole type magenta coupler can be used as a magenta dye by using a phenol compound or a phenyl ether compound in combination. Techniques have been proposed to improve the robustness of images to likelihood.

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.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned problems, and a first object of the present invention is to provide a photographic material with excellent color reproducibility and improved light fastness of magenta dye images. There is a particular thing.

A second object of the present invention is to provide a photographic material having a magenta dye image that is less discolored by light.

A third object of the present invention is to provide a color photographic material in which the occurrence of Y-stain in uncolored areas is prevented from occurring due to light, heat, and humidity.

[Structure of the invention]

The above object of the present invention is to combine at least one magenta coupler represented by the following general formula (H-1) and the following general formula (Ia
), (Ib) and (Ic).

General formula 04-1) 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 substituent which can be eliminated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

General formula (Ia) General formula (Ib) General formula (Ic) In the formula, 83 is a hydrogen atom, alkyl, cycloalkyl,
It represents each group of alkenyl, cycloalkenyl, alkynyl, heptadyl, heterocycle, acyl, sulfonyl, phosphonyl, carbamoyl, sulfamoyl, flukoxycarbonyl, and aryloxycarbonyl, and R4 represents a substituent.

The term represents O or an integer from 1 to 6. When l is 2 or more, a plurality of R4s may be the same or different.

Below 9 Next, the present invention will be specifically explained.

In the magenta coupler represented by the 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 formed by Z has a substituent. You may.

X represents a hydrogen atom or a group capable of forming a chemical compound by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, anilino, acylami/, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. Halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, Also included are sul7amoylamino/, alkoxycarbonylamino, aryloxycarbonylamino/, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, as well as spiro compound residues, organic 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 7 acyl amide groups represented by R include 7 alkyl carbonyl amide groups, 7 aryl carbonyl amide groups, and the like.

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

The arylthio group represented by R, the alkyl component in the arylthio group, and the aryl component include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and 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 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

As the sulfonyl group represented by R, alkylsulfonyl
/l, group, arylsulfonyl group, etc.; Sulfinyl group includes alkylsulfinyl group, arylsulfinyl group, etc.; phosphonyl group includes alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group; acyl group; Examples of the group include an alkylcarbonyl group, a monocarbonyl group, etc.; examples of the carbamoyl group include an alkylcarbamoyl group, an arylcarbamoyl group, etc.; examples of the sulfamoyl group include an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, 7lylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, aryl Ureido group, etc.; Examples of sulfamoyl 7 groups include 7 alkylsul 7 amoylamides, 7 lylsul 7 amoylamides, etc.; As heterocyclic groups, 5 to 7 mol groups are preferable, specifically 2-furyl groups, 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group ring; As the heterocyclic oxy group, one having 5 to 7 heterocycles is preferable, for example, 3,
4,5.6-tetrahydropyranyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group ring; As the heterocyclic thio group, a 5- to 7-shell heterocyclic thio group is preferable, such as 2-bilinorthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1 , 3,5-) lyazole-6 monothio group, etc.; as a siloxy group, a trimethylsiloxy group, a triethylsiloxy group, a trimethylbutylsiloxy group, etc.; as an imide group, a succinimide group, 3-heptadecylphuccinimide group, 7-thalimide group, glutarimide group, etc.; spiro compound residues include spiro [3,3] heptan-1-yl; and endogenous hydrocarbon compound residues include bicyclo [2゜2.
11 Hebutan-1-yl, tricyclo [3゜3.1,
1 piece? ]]Decan-1-yl7,7-tumethyl-bicyclo[2,2,11hebutan-1-yl and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy carbonyloxy, aryloxycarbonyl, flukyloxalyloxy, flukyloxalyloxy,
Alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with N atom, alkyloxycarbonyl 7mino, aryloxycarbonylamino, carporcyl, (R,″ is the same as the above R) Z'' has the same meaning as Z, and R2' and R5' each represent a hydrogen atom, an aryl group, a furkyl group, or a heterocyclic group, preferably a halogen atom, Especially the chlorine atom.

In addition, as the nitrogen-containing heterocycle formed by Z or Z',
Examples include a pyrazole ring, imidazole ring, triazole ring, and tetrazole ring, and examples of the substituents that the ring may have include those described for R above.

More specifically, what is represented by the general formula [M-1] is represented by, for example, the following general formulas [M-[1 to [M-■]].

General formula [M-u] General formula [M-I[1] General formula [M-IVI General formula [M-Vl General formula [M-Vll General formula [M-■]] Said general formula [M-Ill~[ M-■], R5 to R
, and X have the same meanings as R and X above.

Also, preferred among the general formulas [M-11] are those represented by the following general formula [M-1].

General formula [M-■] In the formula, R, , X and Zl are general formula [R in M-11,
It is synonymous with X and Z.

Among the magenta couplers represented by the general formulas [M-I11 to [M-■1], particularly preferred ones are those represented by the general formula [M-I
It is a magenta coupler represented by ll.

The most preferable substituents R and R7 on the heterocycle are represented by the following general formula [M-■] and are represented by the general formula [M-
ffl R9 R,, -C- R1+ where Rs = R,. and R11 each have the same meaning as R above.

Also, the above R,,R,. and two of R1+, for example R3
and R1° may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1 may be further combined with the ring to form a bridged hydrocarbon compound residue. You can.

Among the general formula [M-IXI, (i)
When at least two of R= ~R1+ are alkyl groups, (ii) one of Rs ~ R11, for example RI+, is a hydrogen atom, and the other two R3 and R1° are bonded to form a root carbon atom; When used together to form cycloalkyl.

Further preferred among (i) is the case where two of R to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, the ring formed by Z in general formula [M-IF, the substituent that the ring formed by Z in general formula M-1, and the general formula [M-Ill~[
R2 to R8 in M-Vl] are represented by the following general formula [
M −X ] is preferable.

General formula [M -X ] -R'-8Q2-R2 In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a dichlorofurkyl group, or a 7-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 it does not matter whether the straight chain has one branch or not.

The cycloalkyl group represented by R2 is preferably one having 5 to 6 shells.

Typical specific examples of the compounds according to the present invention are shown below.-1/ ― CH.

Hs ti3 CH.

CH.

In addition to the above representative examples of compounds according to the present invention, specific examples of compounds according to the present invention include Japanese Patent Application No. 61-9791.
No. 1-4.6-8-17-19-24.
26~43.45~59.61~104.106~12
Compounds represented by 1°123-162.164-223 can be mentioned.

Also, the coupler is a journal op the chemical.
Sosai7te< (Journal of the C
he+*1calsociety), t<-kin(
Perkin) I (197)).

2047-2052, U.S. Patent No. 3,725,067,
JP-A No. 59-99437, No. 58-42045, No. 59-162548, No. 59-171956, No. 6
No. 0-33552, No. 60-43659, No. 60-1
It can be synthesized by referring to No. 72982 and No. 60-190779.

The couplers of the invention typically contain 1Xl per mole of silver halide.
0-' mol-1 mol, preferably lXl0-2 mol-8
It can be used in an amount of X10-' moles.

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

The magenta dye image stabilizer represented by the general formula (Ia), (Ib) or (lef) used in conjunction with the magenta coupler of the present invention not only has the effect of preventing fading of the magenta dye image due to light, but also It is a tetrahydrobenzazepine compound that also has the effect of preventing discoloration caused by light.

General formula (Im) R general formula (Ib) general formula (Ic) In general formulas (Im), (Ib) and (Ic), the furkyl group represented by R3 is, for example, methyl,
Groups such as ethyl, t-butyl, octyl, dodecyl, and hexadecyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, alkenyl groups such as allyl, hexenyl, and oleyl, and cycloalkenyl groups include: For example, groups such as cyclohexenyl and cyclooctenyl; examples of alkynyl groups include propynyl, butynyl, and octenyl; examples of 71J-l groups include 7enyl, p-j-butylphenyl,
Groups such as naphthyl, heterocyclic groups include, for example, chenyl,
Groups such as tetrahydro7lyl and pyridyl; examples of acyl groups include groups such as acetyl, myristoyl, stearoyl, and benzoyl; examples of sulfonyl groups include groups such as methylsulfonyl and p-methoxy7enylsulfonyl;
Examples of the phosphonyl group include cuptylphosphonyl, diphenylphosphonyl, etc., and carbamoyl groups include,
For example, groups such as methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl; examples of sulfamoyl groups include groups such as ethylsul77moyl, trimethylsul77moyl, and phenylsulfamoyl; examples of phenoxycarbonyl groups include ethoxycarbonyl, octyloxycarbonyl, and dodecyloxy. Examples of groups such as carbonyl and 7lyloxycarbonyl groups include phenoxycarbonyl and pt-butylphenoxycarbonyl groups.

Compounds represented by general formulas (Ia) to (Ic) are 6.7
, 8.9-tetrahydrobenzo7zepine The substituent represented by 4 is not particularly limited, but typical examples include halogen atom, furkyl, cycloalkyl, alkenyl, cycloalkenyl, and alkynyl. ,
Aryl, bicyclic, 7-syl, sulfonyl, phosphonyl,
Carbamoyl, sul77moyl, cyano, hydroxyl, alkoxy, aryloxy, heterocyclicoxy, acyloxy, carbamoyloxy, amino, acylamino,
Sulfone 7 mido, imide, ureido, sulfone 7 amoyl 7
Examples include mino, furufkidicarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, and aryloxycarbonyl groups.

Among the compounds represented by general formulas (Ia) to (Ie),
R3 is an alkyl, dichlorofurkyl, aryl, or heterocyclic group; R4 is a halogen atom; Particularly preferred are compounds in which each of ureido, alkoxycarbonyl, and aryloxycarbonyl groups is 0 or an integer of 1 to 3.

Below, the above general formula [1a], (lb) or [
Typical specific examples of compounds represented by Ic] are shown below, but the present invention is not limited thereto. Synthesis methods for the magenta dye image stabilizers used in the present invention are known, for example, by Butsuma et al. It can be synthesized according to the methods described in Japanese Patent No. 1,535,085, US Patent No. 3,458,498, Japanese Patent Publication No. 45-21725, and the like.

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 the magenta coupler and magenta dye image stabilizer of the present invention are preferably used alternately in the same layer, the stabilizer may be used in a layer adjacent to the layer in which the coupler is present.

In order to introduce compounds such as the magenta coupler of the present invention and the madanta sub-all O dye image stabilizer of the present invention into the silver halide emulsion layer, for example, solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. Various methods can be used, and these methods can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or a high boiling point organic solvent. Or, by dissolving it in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic dispersion device. After emulsification, it may be added to the desired hydrophilic colloid layer.

In the photographic light-sensitive material of the present invention, the magenta dye image stabilizer according to the present invention further has the following general formula (II).
Other magenta dye image stabilizers shown in (1), ie, phenol compounds and phenyl ether compounds, can also be used in combination.

General formula (II) In the formula, R5 represents a hydrogen atom or an alkyl, alkenyl, aryl, or heterocyclic group, Ra, Ry, Rs, R+
.

each represents a hydrogen atom, a halogen atom, or a hydroxy, alkyl, alkenyl, aryl, alkoxy, or acylamino group, and R1 represents a furkyl, hydroxy, aryl, or alkoxy group. Furthermore, Bs and R6 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R'' represents a hydroxy or flukoxy group.
, R' and R6 may be ring-closed to form a methylenedioxy ring, and R7 and R1 may be ring-closed to form a 5-membered hydrocarbon ring, in which case Rs is an alkyl ,
For specific examples of these groups representing aryl or heterocyclic groups, except when R5 is a hydrogen atom and Ra is a hydroxy group, see JP-A-61-143754, No. 7 Shinshin, upper column. The same groups as those listed in the 3rd line to the 5th line in the lower right column are mentioned.

Among the compounds represented by the general formula (II), a particularly preferred compound is a tetraflukoxyvining compound, which can be represented by the following general formula (III).

General formula (III) In the formula, R14 represents an alkyl, alkenyl, 7-aryl or heterocyclic group, and V Rl2 each represents a hydrogen atom, a halogen atom, or an alkyl, alkenyl, or alkoxy group, ) represents a hydrogen atom or an alkyl, alkenyl, or aryl group.

Typical specific examples of the compound represented by the general formula (II) according to the present invention are shown below. -7 H-8 H-9 PH-10 In addition to the above-mentioned compounds, PH-
1.

4.5, 9, 11, 12, 14, 15, 1f, 18.2
0 to 23, 25 to 32, etc. can be used.

The compound represented by the general formula (If) can be used in an amount of preferably 200 mol % or less, more preferably 140 mol % or less, based on the magenta color 'is image stabilizer of the present invention.

The 7ヱ/-l M compound and the 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 71-nyl compound and the phenyl ether compound in the magenta dye image stabilizer of the present invention.

Generally, the magenta dye image obtained from the magenta coupler exhibits slight fading or 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 has the advantage that it prevents the magenta dye image obtained from the magenta coupler from fading and discoloration due to light. It has an effect that cannot be achieved with other magenta dye image stabilizers.

Therefore, when the conventional 7-functional alcohol compound and 7-functional ether compound are mixed and used in combination with the magenta dye image stabilizer of the present invention, the conventional 7-functional compound must be mixed with the magenta dye image stabilizer of the present invention to the extent that the discoloration due to light is not noticeable. The amount of magenta dye image stabilizer based on compounds and phenyl ethers must be selected.

When an appropriate amount of the compound represented by the general formula (11) is used in combination with the magenta dye image stabilizer of the present invention represented by the general formulas (Ia) to (Ic), a synergistic effect is observed due to the combination. In some cases.

The color photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but in particular, when color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effect is effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be for single color or multicolor.In the case of multicolor silver halide photographic material, it is usually for photographic use. It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers as couplers and a non-photosensitive layer are laminated on a support in an appropriate number and order of layers. The layer order may be changed as appropriate depending on the performance of heavy fish and the purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used.

The silver halide emulsion is chemically sensitized by conventional methods. *Also, it can be optically sensitized to a desired wavelength range.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known in the photographic industry as anti-capri agents or stabilizers can be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

In the color photographic light-sensitive material of the present invention, color anticaprilants, dye image stabilizers, ultraviolet edge inhibitors, antistatic agents, matting agents, surfactants, etc. which are commonly used in light-sensitive materials can be used.

An image can be formed on the color photographic material of the present invention by subjecting it to a color development process known in the art.

The color photographic material according to the present invention may contain a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath.

After color development, the color photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

〔Effect of the invention〕

According to the Force 2 photographic material of the present invention, which contains a magenta coupler represented by the general formula [base-■] and a magenta dye image stabilizer represented by the general formulas (Ia) to (Ic), The fastness of magenta dye images, which conventionally had low fastness to light, heat, and humidity, has been improved. Specifically, discoloration and fading due to light are suppressed, and Y in uncolored areas against light and heat is improved. - The occurrence of stains is well prevented.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A monochromatic color photosensitive material was prepared by sequentially coating the following layers from the support side onto a paper support laminated with polyethylene on both sides, and Sample 1 was obtained.

1st layer: emulsion layer Comparative magenta coupler a below: 4.5ig/100cm
", silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.5B7100 cm", butyl 7 tallate is 4
．． 5mg7100ci2 and gelatin at 12.0H/1
The coating was applied so that the coating amount was 00cz2.

2nd layer: Intermediate layer (ultraviolet, I@collection-containing layer 2-(2-hydroxy-3-sec-butyl-5
-t-butylphenyl)benzotriazole 4.01
9/l00CI”, 4.0mg/dibutyl 7tate
100CR2 and gelatin 10.019/100cm
The coating was applied so that the coating amount was ”.

3rd N: Protective layer Gelatin was coated to a coating amount of 8.0B7100cm'.

The above sample 1 contains the above P as a magenta dye image stabilizer.
Sample 2 was obtained in which Ii7 was added in the same molar amount as 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 24 of the present invention, respectively.

In the above Samples 3 and 7.11, the magenta dye image stabilizer PH-7 was added in equimolar amounts to the coupler to obtain Samples 4 and 8.12, respectively. Dye image stabilizers A-1 and A-3 were added in equimolar amounts to the coupler to prepare samples 5 and 5, respectively.
9,13 and 8,10,14 were obtained.

Comparative magenta coupler a rσ 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] Processing temperature Processing time Color development
Bleach fixing at 33℃ for 3 minutes and 30 seconds
Wash with water at 33℃ for 1 minute and 30 seconds
Dry at 33℃ for 3 minutes 50
~80°C for 2 minutes The components of each treatment solution are as follows.

[Color developer]

12 bottles of benzyl alcohol! Diethylene glycol 10aN Potassium carbonate 25g Sodium bromide
0.6g anhydrous sodium sulfite
2. OB hydroxylamine sulfate
2.58N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino 7-niline sulfate 4.5g Water was added to make 11, and the pH was adjusted to 10.2 with sodium hydroxide.

[Bleach-fix solution]

Ammonium 1,000 sulfate 120 g Sodium bisulfite 15 g Anhydrous sodium sulfite 3 g EDT 8 ferric hemmonium salt 65 g Add water to bring the pH to 11, and adjust the pH to 6.
．． Adjust to 7-6.8.

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

Add each of the above treated samples to xenon 7-ade megoo at 150 ml.
While examining the light fastness of the dye image and the Y-stin (y-s) of the uncolored area, each sample was heated at 60°C and 80% R.
The sample was left in a 1+ high temperature and high humidity atmosphere 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.

〔Survival rate〕

Initial concentration 1.01: Percentage of dye remaining after N exposure and humidity test.

[Y-Stin]

The value obtained by subtracting the concentration of Y-stin before the light and moisture resistance test from the concentration of Y-stin after the light and humidity resistance test.

[Degree of discoloration]

(Yellow density) after light emission test at initial density 1.0/
(magenta density) to (yellow density) before light test /
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish. -9, the following margins (t) As is clear from Table 1, sample 3,7.11 prepared using the coupler of the present invention is the conventional 4-equivalent type 3-
It can be seen that Y-stain is extremely less likely to occur in the light and moisture resistance tests compared to Sample 1, which was prepared using a 7nilino 5-pyrazolone type coupler. It can be seen that the color easily changes and fades when exposed to light. Samples 4, 8, and 12 were prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-7, and this certainly prevented the dye image from fading due to light. is significantly improved, but discoloration cannot be improved.

On the other hand, Samples 5, 6, 9.10, and 13°1 were prepared using the coupler of the present invention and the dye image stabilizer of the present invention.
In No. 4, the color change and fading of the dye image were small in the light, heat, and humidity resistance tests, and it was found that Y-staining in the uncolored areas was almost non-existent. This was not possible with the conventional combination of a 4-equivalent type 3-7 nylino-5-pyrazolone type coupler and the dye image stabilizer PH-7 (Sample 2).

Example 2 Four fabrics were prepared in exactly the same manner as in Example 1, using the combination of coupler and magenta dye image stabilizer shown in No. 2z, and Sample 15 was prepared.
~30 were created. Samples 15-30 were processed using the assembly method described in Fruit Example 1. Furthermore, these 1 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.

Note that the comparative magenta coupler b in the table has the following structure.

Comparative magenta coupler b p $ 2 As is clear from the table, the conventionally used
When the magenta dye image stabilizer of the present invention is used in combination with a 4-equivalent type 3-anilino-5-pyrazolone type coupler (Sample 15.16) and the magenta dye image stabilizer conventionally commonly used in the coupler of the present invention (Samples 19, 20, 21.22), it was not possible to improve all of the discoloration, fading, Y-stin in the uncolored area in the light fastness test, and Y-stin in the moisture resistance test, and this It can be seen that all of the above-mentioned improvements can only be achieved by using the coupler of the invention in combination with the magenta dye image stabilizer of the 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.

1st layer: blue-sensitive silver halide emulsion layer a-piparoyl-'-(2t4
-dioxo-1-pencylimidazolidin-3-yl)
6.8 mg of -2-chloro-5-[γ-(2,4-di-t-7milphenoxy)butyramide 1 acetanilide
/100cm'', blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.2g/100c2, dibutyl 7 tallate is 3.5g/100c2, and Gelatin was coated in an amount of 13.5B/100cm''.

2nd layer: middle layer 0.5 mg of 2.5-di-t-octylhydroquinone
/100cm2, Jib 1,000 7 tallate 0.5B/I
QOcm" and gelatin were coated in an amount of 9.0 mg 7100 cm".

Third layer: Green-sensitive silver halide emulsion layer The magenta coupler 1 was added at 3.5 g/100c theory 2;
Green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was converted into silver at a concentration of 2.5-g/100cm2, butyl 7 tallate was 3.0mg/100cm'', and gelatin was 12.0
The coating was applied so that the amount was 100 mg/100 cm.

4th layer: Intermediate layer UV absorber 2-(2-hydroquine-3-5ea-butyl-5-t-butylphenyl)benzotriazole 7.0-g/100c++*", di-butyl 7-talate 6 2,5-di-t-octylhydroquinone was coated at 5 mg/100 cm" and gelatin was coated at 12.0 mg/100 cm".

5th layer: red-sensitive silver halide emulsion layer 2-[α-(2,4-di-t-pentyl 7eth/xy)butanamide]-4,6-dichloro-5-2,000 phenol as cyanogen .2-g/100c theory 2,
3. Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver. O*g/100c+s", tricresyl phosphate at 3.5+*g/100cm" and gelatin at 11.5sg/100c+s".

6th layer: protective layer gelatin 8. OH/100cm".

In the above sample 31, the magenta dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3 to prepare multilayer samples 32 to 40, which were exposed and processed in the same manner as in Example 1. After that, a light emission test (a xenon fade meter was irradiated for 15 days) was conducted. The results are also shown in Table 3.

Table 3 below: From the results, the magenta dye image stabilizer of the present invention:
The magenta coupler of the present invention is effective in stabilizing dye images, and the effect becomes greater as the amount added increases. Further, in comparison with Sample 31, Samples 32 to 40 showed extremely small discoloration of the dye images in the light exposure test. Furthermore, in the sample of the present invention, the discoloration and fading of the magenta dye were extremely small, and the color balance with the yellow and cyan couplers was good as an overall color photographic material after the light exposure test, and the color reproducibility remained extremely good. .

Claims (1)

[Scope of Claims] At least one magenta coupler represented by the following general formula [M-1] and a compound selected from the following general formulas [I a], [I b] and [I c] A silver halide photographic material comprising at least one of: General formula [M-1] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula [I a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I c] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [ In the formula, R^3 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group,
It represents a phosphonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R^4 represents a substituent. m represents 0 or an integer of 1 to 6. When m is 2 or more, multiple R^4s may be the same or different. ]