JPH04191849A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain satisfactory color reproducibility even after the lapse of time as well as to improve color reproducibility with respect to every hue by incorporating a specified magenta coupler and a specified yellow coupler. CONSTITUTION:A magenta coupler represented by formula I is incorporated into one of silver halide emulsion layers and a yellow coupler represented by formula II into one of the remaining silver halide emulsion layers. In the formula I, R is H or a substituent, Z is a group of nonmetallic atoms required to form an N-contg. hetero ring and X is H or a group releasable by a reaction with the oxidized body of a color developing agent. In the formula II, each of RA and RB is alkyl, cycloalkyl, etc., XA is acylamino, etc., and ZA is a group releasable by a reaction with the oxidized body of a color developing agent and represented by formula III or IV. In the formulae III, IV, each of RC-RF is H or a substituent and each of Y and W is -O-, -S(O)P-, etc. Synthetically superior color reproducibility is ensured with respect to every hue and a dye image having superior light resistance can be formed.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic material that forms a dye image with good spectral absorption characteristics, excellent color reproducibility, and excellent light fastness. It is something.

[Background of the Invention] In /XX rosin silver photographic light-sensitive materials intended for direct viewing, especially color photographic paper, a combination of yellow coupler, magenta coupler and cyan coupler is usually used as a coupler to form a coloring dye. ing.

With the progress of silver halide photographic light-sensitive materials, requirements for the performance of couplers are becoming more and more stringent. By developing a coupler with a sharp color, it is possible to make the color tone of the dye itself clear.

As a result of much research and development into magenta couplers, significant improvements in color reproducibility have been observed with pyrazolotriazole couplers having specific substituents, as described in JP-A No. 83-30745. Ta.

On the other hand, although research and development is continuing on yellow couplers, it has not yet been possible to find a product that satisfies both color reproducibility from the perspective of sharpness of visible absorption spectrum waveforms and image preservation properties such as light resistance. However, even if the magenta coupler is used, sufficient color reproducibility cannot be obtained for hues such as red, green, and yellow.

As mentioned above, the reality is that a silver halide photographic material with comprehensively excellent color reproducibility for all hues has not yet been found.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic material that forms a dye image that has good spectral absorption characteristics, excellent color reproducibility, and excellent light fastness.

[Structure of the Invention] The object of the present invention is to provide blue light sensitivity on a support! - In a silver halide photographic light-sensitive material having photographic constituent layers including a silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, at least one of the silver halide emulsion layers , contains at least one magenta coupler represented by the following general formula [M-I], and at least one of the remaining silver halide emulsion layers contains a magenta coupler represented by the following general formula [Y-N]. This is achieved by a silver halide photographic material characterized by containing a yellow coupler.

General formula [M-11 [In the formula, R represents a hydrogen atom or a substituent, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z represents a substituent 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. ] General formula [Y-11 0Re [In the formula, RA and R represent an alkyl group, a cycloalkyl group, or an aryl group. XA represents an acylamino group or a sulfonylamino group.

ZA represents a group that is released by reaction with an oxidized product of a color developing agent represented by the general formulas [Y-II] and [Y-III].

General formula [Y-II]! [In the formula, RC and RD represent a hydrogen atom or a substituent, and Y represents -N-1-〇- or -S (0), -G (wherein, R represents a hydrogen atom or a substituent. , p
represents an integer from 0 to 2. ). general formula [Y-II
I] RF [In the formula, RE and RF represent a hydrogen atom or a substituent, and W represents -0- or -S (0) , -.

"represents an integer from 0 to 2.]] [Specific Structure of the Invention] The magenta coupler represented by the general formula CM-IE of the present invention will be explained.

In the magenta coupler represented by the general formula [M-1] 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. May have.

X represents a hydrogen atom or a group that is released upon reaction with an oxidized product of a color developing agent.

Further, k represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl, but in addition to these, halogen Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfonyl Also included are famoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as 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 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.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. .

Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; as the heterocyclic group, a 5- to 7-membered group is preferable; specifically, a 2-furyl group, a 2-thienyl 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-tetrahydrobilanyl-2-oxy group, 1
-phenyltetrazole-5-oxy group, etc.

The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as a 2-pyridylthio group, a 2-benzothia zolylthio group, or a 2,4-diphenoquine-1,3,5-triazole-6-thio group. etc.

Siloxy groups include trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxine, etc. Imide groups include succinimide, 3-heptadecylsuccinimide, phthalimide, glutarimide, etc.; spiro compound residues is spiro [3,3 hebutane-
1-il et al.

As a bridged hydrocarbon compound residue, bicyclo[2゜2.1
] heptan-1-yl, tricyclo[3゜3.1.13
-7codecan-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, etc. are mentioned.

Examples of the group that is released by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
Each group such as carboxyl, chiral (R1' is the same as the above R, Z' is the same as the above Z, and R2' and R3' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group). or preferably a halogen atom, especially a chlorine atom.

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

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

Below are the blanks General formula [M-II] General formula [M-III] General formula CM-rV General formula EM-V General formula [M-V [] General formula [M-■ General formula [M-n] ] ~ [M-■] R8-R6
and X have the same meanings as R and X above.

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

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

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

The most preferred substituents R2 and R3 on the heterocycle are those represented by the following general formula [M-IXI.

General formula [M-IXI 1o-C- In the formula, R,, Rlo and R1□ each have the same meaning as R above.

Moreover, two of the above R1, R1° and R11, for example, R1
and Rlo may be combined to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle), and R31 may be further combined to the ring to constitute a bridged hydrocarbon compound residue. Good too.

Among the general formula [M-■], R5-R1,
At least two of them are alkyl groups.

Further preferred among these is the case where two of R7-R1 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, the substituents that the ring formed by 2 in the general formula [M-IF and the ring formed by Z in the general formula [M-■] may have, as well as the substituents of the general formula [M-n] to [ M-
Ro and ~R6 in Vl] are represented by the following general formula [M-
[2] is preferable.

General formula [MXco-Rl 2- N HCO-Rs 3 In the formula, R12 represents an alkylene group, and R1 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R12 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 it is straight chain or branched.

The cycloalkyl group represented by R13 is preferably a 5- to 6-membered one.

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

Margin below-I CaH+ 7(1) CHs CaH+t(t)M-16 Csfbi 4H9 7H1s M-28 M-29 H3 H3 H3 (1) CaH+F I H3 Fb 0CaH,7 CI J CaH17(1) M-61 CHl I I2H2S x:y-50:50 M-73 x:y-50:50 In addition to the above typical examples of compounds according to the present invention, specific examples of compounds according to the present invention include JP-A-82- 1663
Among the compounds described on pages (18) to (32) of Specification No. 39, N11L1-4.6.8-17.19
~24.26~43.45~59.61~104.10
Compounds represented by 6-121°, 123-162, and 184-223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal or the Che
sicalSociety), Perk
in) I (1977), 2047-2052, U.S. Patent No. 8,725.087, JP-A-59-99437
No. 58-42045, No. 59-162548,
No. 59-171.956, No. 60-38552, No. 6 (No. 1-43659, No. 80-172982, No. 8)
No. 0-190779, No. 62-209457 and No. B
It can be synthesized with reference to No. 3-[7453 and the like.

The couplers of this invention are typically 1X per mole of silver halide.
It can be used in a range of 10 mol to 1 mol, preferably ix to" mol to 8 X 10" mol.

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

Next, the Y coupler represented by the general formula [Y-1] will be explained.

In the general formula [Y-I], the alkyl group represented by RA and R is a linear or branched alkyl group, such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-dodecyl group, and 1-hexylnonyl group. Further, examples of the cycloalkyl group represented by RA and R include a cyclopropyl group, a cyclohexyl group, and an adamantyl group. These R
The alkyl group and cycloalkyl group represented by A and R can further have a substituent, and examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an aryl group (for example, a phenyl group, pt-octylphenyl group, etc.), alkoxy groups (e.g., methoxy group, etc.), aryloxy groups (e.g., 214-di-t-amylphenoxy group, etc.), sulfonyl groups (e.g., methanesulfonyl group, etc.), acylamino groups (e.g., (acetyl group, benzoyl group, etc.), sulfonylamino group (for example, n-dodecanesulfonylamino group, etc.), and hydroxy group.

Examples of the aryl group represented by RA and R11 in the above general formula [Y-I] include a phenyl group and a naphthyl group. These aryl groups represented by RA and RB can further have a substituent, and examples of the substituent include a halogen atom (e.g., chlorine atom, bromine atom, etc.), a cyano group, a nitro group, an alkyl group (e.g., methyl group, trifluoromethyl group, isopropyl group, t-
butyl group, n-dodecyl group, etc.), aryl group (e.g., phenyl group, pt-octylphenyl group, etc.), alkoxy group (e.g., methoxy group, etc.), aryloxy group (e.g., 2,4-di-t- amylphenoxy group, etc.), sulfonyl group (e.g., alkylsulfonyl group such as methanesulfonyl group, trifluoromethanesulfonyl group, and arylsulfonyl group such as p-toluenesulfonyl group)
, acylamino groups (e.g. acetylamino groups, alkylcarbonylamino groups such as myristoylamino groups, arylcarbonylamino groups such as benzoylamino groups), sulfonylamino groups (e.g. methanesulfonylamino groups, heptafluoropropanesulfonylamino groups, n-hexafluoropropanesulfonylamino groups), Examples include an alkylsulfonylamino group such as a decylsulfonylamino group, a p-toluenesulfonyl group, an arylsulfonylamino group such as pentafluorobenzenesulfonylamino, and a hydroxy group.

RA is preferably an alkyl group, particularly preferably a branched alkyl group, and particularly preferably a t-butyl group.

RB is preferably an alkyl group, with a methyl group being particularly preferred.

In the above general formula [Y-I], XA is an acylamino group or a sulfonylamino group, more preferably a group represented by the following general formula [A1-[F].

Margin below General formula [A -N　S　O2RK ■ R.L. General formula [B] -N-C-R.

RL General formula [C] RL General formula CD] - N -C-L -S O2RK RL General formula [E] RL RN General formula [F] -N-C-0RK RL General formula [A] ~ [F] , RK represents an alkyl group, a cycloalkyl group or an aryl group, and RL and RN
independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. RM represents an unsubstituted alkyl group or cycloalkyl group.

As the alkyl group and cycloalkyl group represented by R*, RL s RM s and R, for example, the above R
Examples include the same groups as the alkyl group and cycloalkyl group represented by A and R. Of these, R.K.
The alkyl group and cycloalkyl group represented by N RL and RN can further have a substituent,
Examples of the substituent include the same substituents as those listed as substituents for the alkyl group and cycloalkyl group represented by RA and RB above.

Examples of the aryl group represented by Ry, % RL %, and RN include the same groups as the aryl groups represented by R^ and R, above. These R,,R
The aryl group represented by L s and Rs can further have a substituent, and examples of the substituent include the above R
As substituents for the aryl group represented by A and R6, the same substituents as those listed above can be mentioned.

RM is preferably an alkyl group, more preferably a branched alkyl group.

In the above general formulas [C] and [D], L represents a divalent linking group selected from an alkylene group and an arylene group. The alkylene group represented by includes a cycloalkylene group, such as methylene M, 1,2-ethylene group,
Straight chain alkylene groups such as 1,3-propylene group or 1,4-butylene group, 1.1-propylene group (ethylmethylene group), 2.3-propylene group (1-methyl-1,2- (ethylene group), a branched alkylene group such as a 2,2-propylene group (dimethylmethylene group), or a 1,2-cyclohekylene group. In addition, these alkylene groups may further have a substituent, and examples of the substituent include the same groups as those listed as substituents for the alkyl group and cycloalkyl group represented by RA and RB above. The following substituents can be mentioned.

The arylene group represented by L has 6 to 14 carbon atoms.
Examples of the arylene group include a 1°2-phenylene group, a 1,4-phenylene group, and a 1,4-naphthylene group. These arylene groups may further have a substituent, and examples of the substituent include the same substituents as the substituents for the aryl groups represented by RA and R3 above. I can do that.

L is preferably an alkylene group, and is a linear or branched alkylene group having 1 to 4 carbon atoms in the connecting portion (for example, 1,3-propylene group, 1,1-brobylene group, or 1,1-benzene group). etc.) are more preferred.

In the above general formula [C], B represents a group that can be substituted on the benzene ring, and includes, for example, an alkyl group, a cycloalkyl group, and an aryl group as defined for the groups represented by RA and R6 above. Also, chlorogen atoms (e.g. chlorine atom, bromine atom, etc.), cyano group, nitro group, hydroxy group, alkoxy group (e.g. methoxy group etc.), aryloxy group (e.g. 2,4-di-t-amylphenoxy group) etc)
, acyloxy group (e.g. methylcarbonyloxy group,
penzoyloquine group, etc.), alkylsulfonyl group (e.g., methanesulfonyl group, etc.), arylsulfonyl group (e.g., benzenesulfonyl group, p-toluenesulfonyl group, etc.), sulfamoyl group (e.g., N-propylsulfamoyl group, N-phenyl group, etc.) sulfamoyl group, etc.), acylamino group (e.g. acetyl group, benzoyl group, 3-(
2゜4-di-t-amylphenoxy)butyroyl group, etc.)
, an alkylsulfonylamino group (e.g., methanesulfonylamino group, dodecanesulfonylamino group, etc.), an arylsulfonylamino group (e.g., benzenesulfonylamino group, etc.), a carbamoyl group (e.g., N-methylcarbamoyl group, N-phenylcarbamoyl group, etc.), Also included are alkoxycarbonyl groups (eg, methoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl group, etc.), and imide groups (eg, succinimide group, etc.). n is 0
Represents an integer from ~3.

The group which can be substituted on the benzene ring represented by B is preferably an alkyl group or a hydroxy group, and the alkyl group is more preferably a branched alkyl group such as a t-amyl group or a t-octyl group.

Examples of the substituents represented by RC and R9 in the general formula [Y-II] include the same groups as the alkyl group, cycloalkyl group, and aryl group represented by RA and R8 above. The alkyl group, cycloalkyl group, and aryl group represented by Rc and RD may have a substituent, and examples of the substituent include the alkyl group, cycloalkyl group, and cycloalkyl group represented by RA and RB above. and the same substituents as the groups listed as substituents for the aryl group. Furthermore, the substituents represented by Rc and RD in the general formula [Y-II] include, for example, an alkoxy group,
Mention may also be made of substituents linked by heteroatoms such as aryloxy, alkylamino, anilino, alkylsulfonyl, and arylsulfonyl groups. The substituents connected through these heteroatoms can also have a substituent, and examples of the substituent include the above-mentioned RA.
and an alkyl group represented by RB, a cycloalkyl group,
and the same substituents as the groups listed as substituents for the aryl group.

Rc is preferably a substituted or unsubstituted alkyl group.

R9 is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms.

In the above general formula [Y-II], Y represents -N-1G -0-1 and -5(0), -, and is preferably 10-. p represents an integer from 0 to 2.

Examples of the substituent represented by Rc in the above general formula [Yn] include substituents as defined above for Rc and RD. Further, R6 can further have a substituent, and examples of the substituent include the above-mentioned RA and R
As substituents for the alkyl group, cycloalkyl group, and aryl group represented by B, the same substituents as those listed above can be mentioned.

R6 is preferably a hydrogen atom or an alkyl group, and R
, is an alkyl group, it may be bonded to RD to form a ring structure.

Examples of the substituents represented by RE and RF in the above general formula [Y-III] include substituents having the same meanings as Rc and RD in the above general formula [Y-R3]. Further, R and R6 can further have a substituent, and examples of the substituent include the above-mentioned RA and RB.
Examples of substituents for the alkyl group, cycloalkyl group, and aryl group represented by the following can be mentioned. RE and R2 may be the same or different, and further bond to each other,
A ring structure may be formed.

As RE and R1, aryl groups and alkyl groups are preferred, and alkyl groups are particularly preferred.

In the above general formula [Y-II[], W represents 10- and -S (0) , -, preferably 10-.

" represents an integer from 0 to 2.

The 2-equivalent yellow coupler represented by the above general formula [Y-IF may be bonded at any substituent to form a bis form.

The yellow coupler represented by the general formula [Y-1] according to the present invention can be synthesized by a conventionally known method.

Further, the yellow coupler represented by the general formula [Y-1] according to the present invention can be used alone or in combination of two or more, or can be used in combination with another type of yellow coupler.

Further, the yellow coupler according to the present invention can be used in a range of usually about IX10-3 mol to about 1 mol, preferably IX10-2 mol to 8 x 10-mol per mol of silver halide. .

Next, typical examples of the 2-equivalent yellow coupler represented by the general formula [Y-1] used in the present invention will be shown, but the present invention is not limited thereto.

Below margin ZA XA k RA RB ZA
XAH3 (3) “I・” -NHSO2
C1282%0CHzCHzOCJs ＼ NI RA R11ZAX＾ CHs CsLgoCJ
* 02GHz h RA till ZA
XA2H5 (14) = ” -NHCOCH
CToSOzCuHzsDrunkHi (15) 〃, = /1-NflSOzC
+5Htt(17) 〃 l/
”N
BCOCHNHCOCtJ2tH1 141RA Ra ZA
XA th th th LHzululbltNII
L RA R11ZA x
^6H13 The yellow coupler represented by the general formula [Y-1] of the present invention can be easily synthesized by a conventionally known method.

Typical synthesis examples of the present invention are shown below.

Synthesis Example; Synthesis of Exemplary Coupler (1) (A) C2H5 Exemplary Coupler (1) (1) Synthesis of 4-Equivalent Coupler (A) 132 g of α~pivaloyl-cetanilide was dissolved in 50 ml of ethyl acetate,
50 ml of water and 2.65 g of sodium carbonate were added and stirred vigorously. To this, 17.8 g of 2-(2.4-di-t-amylphenoxy)butyric acid chloride was added to 25 m of ethyl acetate.
A solution dissolved in 1 ml was added dropwise. After the addition was completed, the mixture was stirred at room temperature for 1 hour, and the organic layer was washed with a 5% aqueous potassium carbonate solution and diluted hydrochloric acid. After dehydration with magnesium sulfate, the solvent was removed under reduced pressure, and the residue was recrystallized from 100 ml of methanol to obtain the desired 4-equivalent coupler (A). Yield 24.
1 g (Yield 85%) (2) Synthesis of Exemplary Coupler (1) 24.1 g of the 4-equivalent coupler (A) obtained above was dissolved in 100 ml of chloroform, and 6.3 g of sulfuryl chloride was added dropwise to the solution while cooling with water. After the dropwise addition, the mixture was stirred for 1 hour, and the reaction solution was washed with water, dehydrated with magnesium sulfate, and the solvent was removed under reduced pressure.

The obtained residue was dissolved in 150 ml of acetone, and 13.0 g of 3-benzyl-4-ethoxyhydantoin was added thereto.
Then, 7.6 g of potassium carbonate was added and the mixture was heated under reflux for 3 hours. After filtering out insoluble matter, the mixture was washed with 5% aqueous potassium carbonate solution and diluted hydrochloric acid. After dehydration over magnesium sulfate, the solvent was removed under reduced pressure, and the residue was recrystallized from 100 ml of methanol to obtain the desired exemplary coupler (1). Yield 19.
1 g (yield 56%).

The structure of exemplary coupler (1) was confirmed by NMR, IR, and mass spectroscopy.

Exemplary couplers other than Exemplary Coupler (1) were also synthesized starting from their corresponding raw materials and according to the above synthesis example.

The magenta coupler and yellow coupler of the present invention can be added to a silver halide photographic material using various methods such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method.

For example, in the oil-in-water emulsion dispersion method, hydrophobic additives such as magenta coupler and yellow coupler are added to the boiling point of tricresyl phosphate, dibutyl phthalate, etc.
A low boiling point and/or water-soluble organic solvent such as ethyl acetate or butyl propionate is dissolved in the above high boiling point organic solvent as required, and a surfactant is used in a hydrophilic binder such as aqueous seratin solution. After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer.

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 applied to color photographic paper used for direct viewing. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, contains the magenta coupler of the present invention, the yellow coupler, and the known cyan coupler as photographic couplers in order to perform subtractive color reproduction. It has a structure in which green-sensitive, blue-sensitive, and red-sensitive silver halide emulsion layers and non-light-sensitive layers are laminated on a support in an appropriate number and layer order, but the number and layer order are important. It may be changed as appropriate depending on performance and purpose of use.

Examples of yellow couplers that can be used in combination with the yellow coupler of the general formula [Y-r] include penzoylacetanilide-based and pivaloylacetanilide-based compounds, and the magenta of the general formula [M-1] of the present invention Examples of the magenta coupler that can be used in combination with the coupler include pyrazolone compounds.

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).

) may be any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride.

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 dyes known as sensitizing dyes 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, a mordant, a development accelerator,
Development retardants, optical brighteners, matting agents, lubricants, antistatic agents, surfactants, and the like can be optionally used.

In the present invention, any treatment used in the art may be performed, such as color development treatment, bleaching, fixing, bleach-fixing, stabilization, washing with water, and stopping.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide emulsions) Three types of silver halide emulsions shown in Table 1 were prepared by a neutral method and a simultaneous mixing method.

Margin table below - 1 2 mg added per mole of silver halide 1'2 5XIO-' mole added per mole of silver halide 0.9 mmol added per mole of silver halide 64 added per mole of silver halide 0 Each silver halide emulsion with 0.2 mmol added per mole of silver halide contains 5TB as an emulsion stabilizer after chemical sensitization.
-1 was added in an amount of 5 x 10-' mol per mol of silver halide.

Margin below D-1 D-2 D-3 TB-1 H (Preparation of silver halide color photographic light-sensitive material sample) Next, the following layers 1 to 7 were sequentially coated on a paper support coated with polyethylene on both sides ( (simultaneous coating) to produce silver halide color photographic materials 1 to 30. (In the following examples, the amount added is shown per 1rTf of the photosensitive material.) Layer 1: Gelatin (1.2 g) and 0.29 g
(Silver equivalent.

1. A blue-sensitive silver halide emulsion (Em-1) (the same applies hereinafter); (A layer containing 159 moles of the yellow coupler shown in Table 2 and 0.3 g of dinonyl phthalate (DNP) in which 0.015. of 2,5-dioctylhydroquinone (HQ-1) was dissolved.

Layer 2...Gelatin (0.9g) and 0.04. of HQ-1 dissolved in 0.2 g of dioctyl phthalate (
DOP).

Layer 3: Gelatin (1,4r), 0.2 g of green-sensitive silver halide emulsion (Em-2), 0.9 mmol of magenta coupler shown in Table 2, 0.25. of light stabilizer (ST-1), 0.35 g of light stabilizer (ST-2)
) and 0.3 g of D in which 0.01 g of HQ-1 was dissolved.
Layer containing OP and 20 mg of the following filter dye (AI-1).

Layer 4... Gelatin (i, 2g) and [1,ll
1 g of ultraviolet absorber (UV-1) and 0.05 g of H
A layer containing 0.3 g of DNP in which Q-1 was dissolved.

Layer 5: Gelatin (1.4 g), 0.20 g of red-sensitive silver halide emulsion (Em-3), and 1.0 g of red-sensitive silver halide emulsion (Em-3).
mmol cyan coupler (C-1), 0.01st
of HQ-1 and 0.3g of ST-1 were dissolved.
, 3g K7) D OP.

Layer 6: Gelatin (1.1g) and 0.2g of U
A layer containing 0.2 t of DOP in which V-1 was dissolved and 20 g of the following filter dye (AI-2).

Layer 7... Gelatin (L, Og) and 0.05g
and 2,4-dichloro-6-hydroxytriazine sodium.

UV-I AI-1 AI-2 H NxOiSCHJ)I The following margins were obtained using a photosensitive needle KS-7 type (manufactured by Konica Corporation).
After wedge exposure with monochromatic light of blue, green, and red using
Light fastness was evaluated by determining the residual rate (%) of the dye image at an initial density of 1.0 for the blue-sensitive emulsion layer and the green-sensitive emulsion layer.

In addition, a color checker (manufactured by Macbeth Co., Ltd.) was photographed using a Konica Color G
After adjusting the tone of the gray part of the developed negative film, it was printed on the sample obtained above, and the color reproducibility in each hue was evaluated.

Thereafter, these samples were subjected to a 15-day fading test in the same manner as described above, and the color reproducibility of each hue was also evaluated.

The results are shown in Table-2.

[Processing process] Temperature Time color development 34.7 ± 0.3°C 45 seconds bleach fixing 34 ± 0.5°C 45 seconds stabilization 3
0~34℃ 90 seconds drying 60~
80°C 60 seconds [Color developer: Pure water 800ml 1 Triethanolamine 8g N,N-diethylhydroxyamine 5g Potassium chloride
2gN = ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30g potassium sulfite
Add 0.2 g of optical brightener (4,4'-diaminostilbendisulfonic acid derivative) and 1 g of pure water to bring the total amount to 1 g, and adjust the pH to 10.05.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100ml ammonium sulfite (
40% i11 liquid) Adjust the pH to 5.7 with 27.5 ml potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11
shall be.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make 1g, and adjust to pH 7.0 with sulfuric acid or potassium hydroxide. adjust.

The following margin comparison magenta coupler (MM-1) CJ CJ Comparison yellow coupler (YY-1) CJ As is clear from the results in Table 2, samples using yellow couplers and magenta couplers other than the present invention? For sample layer 2, in which only the magenta coupler was replaced with the coupler of the present invention, improvement in color reproducibility was observed for each hue of blue, red, and magenta. Sample Layer 3, which was changed to It is difficult to say that it is a photographic material with excellent color reproducibility.

On the other hand, samples Nα4 to 30, in which both magenta couplers and yellow couplers of the present invention were used, had excellent color reproducibility for all hues, indicating that the effects of the present invention are excellent. Recognize.

Furthermore, as is clear from Table 2, when the magenta coupler of the present invention and the yellow coupler of the present invention were used in combination, the color balance did not visually deteriorate significantly even after forced deterioration; , 1 to 3, color reproducibility also worsened due to forced deterioration, resulting in images with disrupted color balance.

Furthermore, as is clear from Table 2, Samples Nos. 4 to 30, which used a combination of the magenta coupler of the present invention and the yellow coupler of the present invention, used a magenta coupler other than the present invention and/or a yellow coupler of the present invention. 1 for comparison sample
It can be seen that the light resistance is also superior to that of Samples 3 to 3.

〔Effect of the invention〕

The silver halide photographic light-sensitive material of the present invention, which contains the magenta coupler of the present invention and the yellow coupler of the present invention, maintains practically sufficient light fastness and spectroscopy of the magenta dye and yellow dye formed. The absorption properties are improved, and as a result, color reproducibility for all hues can be greatly improved, and good color reproducibility can be maintained even after aging.

Applicant: Co., Ltd. Seikinsha

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. , at least one of the silver halide emulsion layers contains at least one magenta coupler represented by the following general formula [M-I], and at least one of the remaining silver halide emulsion layers contains the following magenta coupler: A silver halide photographic material containing a yellow coupler represented by the general formula [Y-I]. General formula [M-I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents a hydrogen atom or a substituent, and Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle , 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. ] General formula [Y-I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_A and R_B represent an alkyl group, a cycloalkyl group, or an aryl group. X_A represents an acylamino group or a sulfonylamino group. Z_A represents a group that can be separated by reaction with the oxidized product of the color developing agent represented by the general formulas [Y-II] and [Y-III]. General formula [Y-II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_C and R_D represent hydrogen atoms or substituents, and Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-
or represents -S(O)_p- (in the formula, R_G represents a hydrogen atom or a substituent, and p represents an integer from 0 to 2). ] General formula [Y-III] [In the formula, R_E and R_F represent a hydrogen atom or a substituent, and W represents -O- or -S(O)_r-. r represents an integer from 0 to 2. ]]