JPH0869096A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide color photographic sensitive material containing a coupler giving a sufficiently high color development density. CONSTITUTION: The color photographic sensitive material contains the compound represented by the formula in which R<1> is an alkyl, aryl, alkoxy, or aryloxy group; X is a coupling-releasable group combined through an H, halogen, or 0 atom with the main ring; R<2> is a -OR<3> or -NR<3> R<4> group; and each of R<3> -R<5> is an alkyl or aryl group, R<4> and R<5> may be same or different and each may combine with each other to form an N-containing hetero ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material containing a novel magenta coupler and having improved color forming properties. .

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, a coupler which reacts with an oxidation product of an aromatic primary amine developing agent to form yellow, magenta and cyan couplers, is provided in the silver halide emulsion layer. Are generally contained in.

Among them, as magenta couplers, 1H-pyrazolo [3,2-c] -1,2,4-triazole described in US Pat. No. 3,725,067 and 4,540,654 are disclosed. In recent years, pyrazolotriazole couplers such as 1H-pyrazolo [1,5-b] -1,2,4-triazole described in U.S. Pat. These pyrazolotriazole couplers have been put to practical use in color papers and color negative photosensitive materials since 1980. However, under the conditions of recent rapid processing and low replenishment of the developing solution, the conventionally known pyrazolotriazole coupler has an insufficient color forming property. Further, various efforts have been made to put a pyrazolotriazole coupler into practical use in a color reversal light-sensitive material, but the color developability is still insufficient and improvement is desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a silver halide photographic light-sensitive material containing a coupler which gives a sufficiently high color density.

[0005]

The above-mentioned object has been achieved by a silver halide color photographic light-sensitive material characterized by containing a compound represented by the following general formula (I). General formula (I)

[0006]

Embedded image

In the formula, R ¹ represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group, X represents a coupling-off group bonded to the mother nucleus via a hydrogen atom, a halogen atom or an oxygen atom, and R ² is -OR ³ or-
NR ⁴ represents R ⁵ , R ³ , R ⁴ and R ⁵ represent an alkyl group or an aryl group, R ⁴ and R ⁵ may be the same or different, and R ⁴ and R ⁵ are bonded to each other to form a nitrogen-containing group. A heterocycle may be formed.

The present invention will be described in more detail below.

First, the compound represented by formula (I) will be described in detail below. In the formula (I), R ¹ is an alkyl group (a linear, branched, or cyclic alkyl group having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, s-butyl, t-butyl. , Dodecyl, neopentyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-
Adamantyl), aryl group (preferably having 6 to 3 carbon atoms)
2 aryl groups, such as phenyl, 1-naphthyl, 2
-Naphthyl), an alkoxy group (an alkoxy group having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropoxy, 1-butoxy, 2-butoxy, 2-ethylhexyloxy, t-butoxy, dodecyl. Oxy, cyclopentyloxy, cyclohexyloxy), an aryloxy group (an aryloxy group having 6 to 32 carbon atoms, preferably 6 to 10 carbon atoms, for example, phenoxy,
2-naphthoxy).

In formula (I), the group represented by R ¹ may further have a substituent, and a preferable substituent is an alkyl group (as defined in the description of R ¹ ), Alkenyl group (preferably an alkenyl group having 2 to 32 carbon atoms, such as vinyl or 1-propenyl), an aryl group (R
^{1 has} the same meaning as defined in the description of ¹ ), a heterocyclic group (preferably a 5- to 8-membered heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl). , 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxyl group, Carboxyl group, nitro group, alkoxy group (as defined in the description of R ¹ ), aryloxy group (as defined in the description of R ¹ ), heterocyclic oxy group (preferably having carbon atoms) 1-32 heterocyclic oxy groups,
For example, 1-phenyltetrazole-5-oxy, 2-
Tetrahydropyranyloxy, 2-furyloxy), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably carbon). An acyloxy group having a number of 2 to 32, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having a carbon number of 2 to 32, such as ethoxycarbonyloxy, t- Butoxycarbonyloxy, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, for example, phenoxycarbonyloxy). Carbamoyloxy group (preferably carbamoyloxy group having 1 to 32 carbon atoms, for example,
N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, for example, N, N-diethylsulfamoyloxy, N- Propylsulfamoyloxy), an alkanesulfonyloxy group (preferably an alkanecarbonyloxy group having 1 to 32 carbon atoms, for example, methanesulfonyloxy, hexadecanesulfonyloxy), arenesulfonyloxy (preferably an arene having 6 to 32 carbon atoms) A sulfonyloxy group, for example, benzenesulfonyloxy), an acyl group (preferably an acyl group having 1 to 32 carbon atoms, for example,
Formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), aryloxycarbonyl A group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, for example, phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 32 carbon atoms, for example, carbamoyl, N, N-dibutylcarbamoyl, N- Ethyl-N-
Octylcarbamoyl, N-propylcarbamoyl),
Amino group (preferably an amino group having 32 or less carbon atoms, for example, amino, methylamino, N, N-dioctylamino, tetradecylamino, octadecylamino), anilino group (preferably an anilino group having 6 to 32 carbon atoms) , For example, anilino, N-methylanilino), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, for example, 4-pyridylamino), a carbonamide group (preferably a carbonamide having 2 to 32 carbon atoms). On the basis of, for example,
Acetamide, benzamide, tetradecanamide),
Ureido group (preferably a ureido group having 1 to 32 carbon atoms, for example, ureido, N, N-dimethylureido, N
-Phenylureido), imide group (preferably having 1 carbon atom)
An imide group of 0 or less, for example, N-succinimide, N
-Phthalimide), an alkoxycarbonylamide group (preferably an alkoxycarbonylamide group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino), an aryloxycarbonylamino group. (Preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, for example, phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 32 carbon atoms, for example, methanesulfonamide, butanesulfonamide, Benzenesulfonamide, hexadecanesulfonamide), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 32 carbon atoms, for example, N, N-dipropylsulfamoylamino, N- Tyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, for example, phenylazo), an alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms, for example, ethylthio, Octylthio), an arylthio group (preferably an arylthio group having 6 to 32 carbon atoms, for example, phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, for example, 2-benzothiazolylthio group). Two
-Pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, for example, dodecanesulfinyl), and arenesulfinyl (preferably 6 to 3 carbon atoms).
2 arene sulfinyl groups such as benzenesulfinyl), alkanesulfonyl groups (preferably alkanesulfonyl groups having 1 to 32 carbon atoms such as methanesulfonyl and octanesulfonyl), arenesulfonyl groups (preferably 6 to 32 carbon atoms). Arenesulfonyl groups of, for example, benzenesulfonyl, 1-naphthalenesulfonyl), sulfamoyl groups (preferably sulfamoyl groups having 32 or less carbon atoms, for example, sulfamoyl,
N, N-dipropylsulfamoyl, N-ethyl-N-
Dodecylsulfamoyl), a sulfo group, and a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl).

R ¹ is preferably a primary or secondary alkyl group, an alkoxy group or an aryloxy group from the viewpoint of high color developability, and a tertiary alkyl group or aryloxy group from the viewpoint of fastness against color image light and heat. Is preferred. Preferred specific examples of the group represented by R ¹ include those shown below.

[0012]

[Chemical 3]

[0013]

[Chemical 4]

In the formula (I), X represents a coupling-off group bonded to the mother nucleus via a hydrogen atom, a halogen atom or an oxygen atom. More specifically, the coupling-off group represents an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, or the like. The preferred range and specific examples of these groups are the same as those described for the group represented by R ¹ and the group substitutable for R ¹ . When X represents a coupling-off group other than a halogen atom, X may further have a substituent, and preferred substituents are the same as those listed as the substitutable group for the group represented by R ^1. . X may be a photographically useful group such as a development accelerator, a development inhibitor, a desilvering accelerator or a leuco dye or a precursor thereof.

X is preferably a halogen atom, an aryloxy group or a carbamoyloxy group, and most preferably a chlorine atom or an aryloxy group. Preferred specific examples of the group represented by X include those shown below.

[0016]

[Chemical 5]

In the formula (I), R ² is --OR ³ or --NR
⁴ represents R ⁵ . Here, R ³ , R ⁴ and R ⁵ represent an alkyl group or an aryl group, and R ⁴ and R ⁵ may be the same or different. The detailed description of the alkyl group and aryl group represented by R ³ , R ⁴ and R ⁵ is the same as that defined in the description of R ¹ above, and each may have a substituent. Specific examples of the substituent include the substituents enumerated as the substituents which R ¹ may have.

R ⁴ and R ⁵ may combine with each other to form a nitrogen-containing heterocycle. In this case, the nitrogen-containing heterocycle may be a saturated or unsaturated, monocyclic or condensed ring having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, or substituted or unsubstituted. In addition to the nitrogen atom, an oxygen atom, a sulfur atom, etc. may be contained in the ring. The number of ring members is a 3-membered ring or more, preferably a 5- or 6-membered ring. Specifically, for example,
Morpholino, 1-imidazolidinyl, 1-pyrazolyl,
1-indolinyl, pyrrolidyl and piperidyl can be mentioned.

Preferred specific examples of the group represented by R ² include those shown below.

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

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The compounds represented by the general formula (I) are represented by R ¹ , R
^{In 2} and X, a dimer or a multimer which is bonded to each other through a divalent or divalent group may be formed. In this case, the number of carbon atoms may be out of the specified range for each substituent.

Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

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[0031]

[Chemical 15]

[0032]

Embedded image

[0033]

[Chemical 17]

[0034]

[Chemical 18]

Specific synthetic examples of the compound represented by formula (I) of the present invention are shown below. Synthesis of Exemplified Compound (4)

[0036]

[Chemical 19]

[0037]

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Synthesis of Intermediate (I-2) A solution of 70 g (0.5 mol) of Intermediate (I-1) in 300 ml of dimethylformamide was added to 1 part of potassium hydroxide.
41 g (2.5 mol) were added. Hydroxylamine-o-sulfonic acid 63 g (0.55
mol) was added little by little while being careful to keep the internal temperature below 30 ° C. After the addition was completed, stirring was continued at room temperature for 1 hour. Add 1 liter of water to the reaction mixture, and add ethyl acetate 50
Extraction operation was performed three times with 0 ml. The organic layer is saturated saline solution 3
After washing with 00 ml, it was dried with mirabilite. The solvent was distilled off, and the residue was purified by silica gel column chromatography to give 24.1 g of intermediate (I-2) (yield 31%).
Obtained.

Synthesis of Intermediate (I-3) A solution of 14 g (0.091 mol) of Intermediate (I-2) in 140 ml of acetonitrile was added to 9.5 g of acetic anhydride.
(0.093 mol) was added and the mixture was heated to reflux. After reacting for 1.5 hours, the solvent was distilled off, and the residue was purified by silica gel column chromatography. 13.6 g of intermediate (I-3)
(Yield 76%) was obtained.

Synthesis of Intermediate (I-4) To a solution of 13.6 g (0.069 mol) of Intermediate (I-3) in 50 ml of dimethylacetamide was added 11.1 g (0.071 mol) of phenyl chlorocarbonate at room temperature. Was dropped. After standing overnight at room temperature, the reaction solution was added to a mixed solvent of 200 ml of water and 400 ml of ethyl acetate for extraction. The organic layer was washed with saturated saline and then dried with mirabilite. The solvent was distilled off, and 21.5 g (yield 99%) of intermediate (I-4) was obtained as a crude product.
Obtained.

Synthesis of Intermediate (I-5) A solution of 21.5 g (0.068 mol) of Intermediate (I-4) in 50 ml of dimethylformamide was added to potassium-
7.63 g (0.068 mol) of t-butoxide was added and reacted at 40 ° C. for 3 hours. After adding 100 ml of dilute hydrochloric acid, the reaction mixture is extracted with 500 ml of ethyl acetate.
The organic layer was washed successively with 200 ml of water and 100 ml of saturated saline and then dried over sodium sulfate. The solvent was distilled off, 20 ml of ethyl acetate and 100 ml of hexane were added to the residue, and the precipitated crystals were collected by filtration. 10.5 g (70% yield) of intermediate (I-5)
I got

Synthesis of Intermediate (I-6) 2.6 g (0.012 mol) of Intermediate (I-5) was dissolved in 60 ml of tetrahydrofuran, and 1.9 g (0.017 mol) of potassium t-butoxide under ice cooling. Was added. After stirring for 30 minutes under ice cooling, 4.6 g of dodecyl triflate
(0.014 mol) was added. After stirring at room temperature for 20 minutes, diluted hydrochloric acid was added to the reaction solution. Extract with ethyl acetate,
The organic layer was washed with water and a saturated saline solution in that order, and dried over sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 2.8 g (yield 60%) of intermediate (I-6).

Synthesis of Intermediate (I-7) 0.1 g of potassium carbonate was added to a solution of 2.8 g (0.0072 mol) of Intermediate (I-6) in 60 ml of methanol, and the mixture was stirred at room temperature for 1 hour. Dilute hydrochloric acid was added to the reaction solution,
The precipitated crystals are collected by filtration to give the intermediate (I-7)
Was obtained in an amount of 2.2 g (yield 88%).

Synthesis of Exemplified Compound (4) To a solution of 2.2 g (0.0063 mol) of intermediate (I-7) in 40 ml of dichloromethane was added 0.86 g (0.0064 mol) of N-chlorosuccinimide, and the mixture was stirred at room temperature. Stirred overnight. Dichloromethane was added to the reaction solution, which was washed with water and a saturated saline solution in that order, and dried over sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to give 2.4 g of the exemplary compound (4) (yield 9
0%) was obtained. The structure was fixed by ¹ H NMR and mass spectrum.

The coupler represented by the general formula (I) of the present invention may be added to a silver halide color photographic light-sensitive material at any speed as long as it is a green-sensitive emulsion layer of the light-sensitive material. The addition amount is 3 × 10 ^{−5 to} 3 × 10 ⁻³ mol / m ² , preferably 3 × 10 ⁻⁴ to 2 × 10 ⁻³ mol / m ² , and 1 ×
More preferably, it is 10 ^{−4 to} 1.5 × 10 ⁻³ mol / m ² . If the addition amount is less than the above lower limit, the maximum color density will be insufficient, and if it is more than the above upper limit, the coupler will be used unnecessarily, which is wasteful in terms of cost.

Research Disclosure No. 308119 (19) generally describes various techniques and inorganic / organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same.
1989) can be used.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following parts of EP 436,938A2 and the patents cited below. There is.

Item This section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler No. Page 137, line 35 to page 146, line 33, page 149, line 21 to line 23 4) Magenta coupler, page 149, line 24 to line 28; EP 421,453A1 Page 3, line 5 to page 25, line 55 5) Cyan coupler page 149, line 29 to line 33; European Patent 432,804A2, page 3, line 28 to page 40, line 6) Polymer coupler, page 149, lines 34 to 38; EP 113, line 113, page 39 to page 123, line 37; 7) Colored coupler, page 53, line 42 to page 137, line 34. Page 149, lines 39-45 8) Other functionality Page 7, line 1 to page 53, line 41, page 149, line 46, coupler line to page 150, line 3; EP 435,334 4A2, page 3, line 1 -Page 29, line 50 9) Antiseptic / mildew agent page 150, lines 25-28 10) Formalin page 149, lines 15-17 17 Scavenger 11) Other additives, page 153, line 38 ~ Line 47; page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 of European Patent 421,453A1 12) Dispersion method page 150, line 4 ~ Line 24 13) Support page 150 line 32 to line 34 14) Film thickness and film physical properties page 150 line 35 to line 49 15) Color development step page 150 line 50 to page 151 47th line 16) Desilvering process, page 151, line 48 to page 152, line 53 17) Automatic processor, page 152, 54 Eyes - page 153, line 2 18) washing and stabilizing steps page 153, line 3 to 37 row

[0049]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto. Example 1 Preparation of Sample 101 A multilayer color light-sensitive material consisting of layers having the following compositions was prepared on a 127 μm-thick cellulose triacetate film support having an undercoat, to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.90 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 g Microcrystalline solid dispersion of Dye E-1 0.10 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling organic solvent Oil-3 0.10 g Dye D-4 0.80 mg

Third layer: intermediate layer Fine grained silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.050 g yellow colloidal silver amount 0.030 g Gelatin 0.40 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.30 g Emulsion B Silver amount 0.20 g Gelatin 0.80 g Coupler C-1 0.15 g Coupler C-2 0.050 g Coupler C-3 0.050 g Coupler C-4 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling point organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.20 g Emulsion C Silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling point organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.30 g Coupler C-2 0.10 g Coupler C-3 0.70 g Additive P-1 0.10 g

Layer 7: Intermediate layer Gelatin 0.60 g Additive P-2 0.30 g Color mixture inhibitor Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg High boiling organic solvent Oil -1 0.020 g

Eighth layer: intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.020 g Yellow colloidal silver Silver amount 0.020 g Gelatin 1.00 g Additive P-1 0.20 g Color mixture inhibitor Cpd-A 0.10 g Compound Cpd-C 0.10 g

Layer 9: Low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.10 g Emulsion F Silver amount 0.20 g Emulsion G Silver amount 0.20 g Gelatin 0.50 g Coupler M-1 0.25 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.020 g High boiling point organic solvent Oil-2 0.20 g

Layer 10: Medium sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.30 g Emulsion H Silver amount 0.10 g Gelatin 0.60 g Coupler M-1 0.20 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g Compound Cpd-L 0.050 g High boiling point organic solvent Oil-2 0.16 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.50 g Gelatin 1.00 g Coupler M-1 0.25 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg Compound Cpd-L 0.020 g High boiling point organic solvent Oil-1 0.020 g High boiling point organic solvent Oil-2 0.020 g

Twelfth layer: intermediate layer Gelatin 0.60 g Compound Cpd-L 0.050 g High boiling point organic solvent Oil-1 0.050 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.070 g Gelatin 1.10 g Color mixture inhibitor Cpd-A 0.010 g Compound Cpd-L 0.010 g High boiling point organic solvent Oil-1 0.010 g Fine crystals of dye E-2 Solid dispersion 0.050g

14th layer: Intermediate layer 0.60 g of gelatin

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.20 g Emulsion K Silver amount 0.30 g Gelatin 0.80 g Coupler Y-1 0.20 g Coupler Y-2 0.10 g Coupler Y-3 0.40 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.30 g Emulsion M Silver amount 0.30 g Gelatin 0.90 g Coupler Y-1 0.10 g Coupler Y-2 0.10 g Coupler Y-3 0.60 g

Layer 17: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20 g Emulsion O Silver amount 0.20 g Gelatin 1.20 g Coupler Y-1 0.10 g Coupler Y-2 0.10 g Coupler Y-3 0.60 g High boiling organic solvent Oil-2 0.10 g

Eighteenth layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g Formalin scavenger Cpd-H 0.40 g Dye D-1 0.15 g Dye D-2 0.050 g Dye D-3 0.10 g

19th layer: 2nd protective layer Colloidal silver Silver amount 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.10 g Gelatin 0.40 g

20th layer: Third protective layer Gelatin 0.40 g Polymethylmethacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methylmethacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.10 g Silicone oil 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Chemical 21]

[0075]

[Chemical formula 22]

[0076]

[Chemical formula 23]

[0077]

[Chemical formula 24]

[0078]

[Chemical 25]

[0079]

[Chemical formula 26]

[0080]

[Chemical 27]

[0081]

[Chemical 28]

[0082]

[Chemical 29]

[0083]

[Chemical 30]

[0084]

[Chemical 31]

[0085]

[Chemical 32]

[0086]

[Chemical 33]

[0087]

Embedded image

The couplers of the 9th, 10th and 11th layers are shown in the table.
Samples 102 to 108 were prepared in the same manner except that the changes were made as shown in 4. The coupler was coated so that the number of moles was the same as M-1.

After subjecting Samples 101 to 108 to wedge exposure with white light of 4800K, the following development processing was performed and the magenta density was measured. The results are shown in Table-5. It is clear from Table-5 that the coupler of the present invention has a high color forming property.

[0090]

[Table 4]

[0091]

[Table 5]

Treatment process time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 2 minutes 38 ° C. 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C. 4 liters 1100 ml / M ² Color development 6 minutes 38 ℃ 12 liters 2200 ml / m ² pre-bleaching 2 minutes 38 ℃ 4 liters 1100 ml / m ² bleaching 6 minutes 38 ℃ 12 liters 220 ml / m ² fixing 4 minutes 38 ℃ 8 liters 1100 ml / m ² Second washing 4 minutes 38 ℃ 8 liters 7500 ml / m ² Final rinse 1 minute 25 ℃ 2 liters 1100 ml / m ²

The composition of each processing liquid was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 1.5g 1.5g Diethylenetriaminepentaacetic acid pentasodium salt 2.0g 2.0g Sodium sulfite 30g 30g Hydroquinone・ Potassium monosulfonate 20g 20g Potassium carbonate 15g 20g Sodium bicarbonate 12g 15g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5g 2.0g Potassium bromide 2.5g 1.4g Potassium thiocyanate 1.2g 1.2g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 ml 1000 ml pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversing liquid] [Tank liquid] [Replenishing liquid] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank liquid Stannous chloride dihydrate 1.0 g p-amino Phenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with acetic acid or sodium hydroxide.

[Color developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0g 2.0g Sodium sulfite 7.0g 7.0g Trisodium phosphate dodecahydrate 36g 36g Potassium bromide 1.0g-Potassium iodide 90mg-Sodium hydroxide 3.0g 3.0g Citrazine acid 1.5g 1.5g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline 3/2 Sulfuric acid monohydrate 11g 11g 3,6-dithiaoctane-1,8-diol 1.0g 1.0g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid / sodium salt / dihydrate 8.0g 8.0g Sodium sulfite 6.0g 8.0g 1-Thioglycerol 0.4g 0.4g Formaldehyde sodium bisulfite adduct 30 g 35 g Water was added to 1000 ml 1000 ml pH 6.30 6.10 The pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid / sodium salt / dihydrate 2.0g 4.0g Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / dihydrate 120g 240g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenishing solution] Ammonium thiosulfate 80g The same sodium sulfite 5.0g 〃 Sodium bisulfite 5.0g 〃 Water is added to 1000 ml 〃 pH 6.60 pH is adjusted with acetic acid or ammonia water did.

[Stabilizing liquid] [Tank liquid] [Replenishing liquid] 1,2-benzisothiazolin-3-one 0.02 g 0.03 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 0.3 g polymalein Acid (average molecular weight 2,000) 0.1 g 0.15 g Add water 1000 ml 1000 ml pH 7.0 7.0

Example 2 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to prepare the following. A multilayer color photographic paper having the layer structure shown was produced and used as a sample 201. The coating liquid was prepared as follows.

Preparation of First Layer Coating Solution Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-7) 0.
To 7 g, 27.2 cc of ethyl acetate and 4.1 g of each of the solvents (Solv-3) and (Solv-7) were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate 8%.
Emulsified dispersion A was prepared by emulsifying and dispersing in 185 cc of 10% gelatin aqueous solution containing cc. On the other hand, silver chlorobromide emulsion A (cube, large size emulsion A having an average grain size of 0.88 μm and 0.70 μm
3: 7 mixture with small size emulsion A of m (silver molar ratio). Coefficients of variation of grain size distribution were 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of grain surface based on silver chloride in each size emulsion). In this emulsion, blue-sensitive sensitizing dyes A and B shown below were respectively added to the large-sized emulsion A per mol of silver at 2.0 × 10 ^−4.
2.5 for mol and small emulsion A
× 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, Cpd-10 and C are added to each layer.
The total amount of pd-11 is 25.0 mg / m ² and 50.0, respectively.
It was added to be mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0103]

Embedded image

(2.0 × 10 ^-4 mol each for large size emulsion A and 2.5 × 10 ^-4 mol each for small size emulsion A per mol of silver halide)

[0105]

Embedded image

(Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large size emulsion B and 5.6 × 10 ⁻⁴ mol for small size emulsion B), and

[0107]

Embedded image

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large size emulsion B and 1.0 × 10 ^-4 mol for small size emulsion B)

[0109]

[Chemical 38]

(0.9 × 10 ⁻⁴ mol for large size emulsion C and 1.1 × 10 ⁻⁴ mol for small size emulsion C per mol of silver halide)

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0112]

[Chemical Formula 39]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol, 2.5 x 10 per mol
^-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
-Tetrazaindene was added in an amount of 1 x 10 ^-4 mol and 2 x 10 ^-4 mol per mol of silver halide, respectively. Also,
The following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0114]

[Chemical 40]

(Layer Constitution) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion A 0.30 Gelatin 1.20 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Color image stabilizer (Cpd-7) 0.06 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18

Second Layer (Color Mixing Prevention Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm (Ag molar ratio) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is locally contained in a part of the grain surface based on silver chloride in each size emulsion.) 0.12 Gelatin 1.21 Magenta coupler ( M-2) 0.23 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-3) 0.16 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-9) 0.02 solvent (Solv-2 ) 0.40

Fourth Layer (UV Absorbing Layer) Gelatin 1.20 UV Absorbing Agent (UV-1) 0.47 Anti-Color Mixing Agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.58 μm and small size emulsion C of 0.45 μm (Ag molar ratio) The variation coefficient of grain size distribution is 0.09 and 0.11, and AgBr 0.6 mol% was locally contained in a part of the grain surface based on silver chloride in each size emulsion.) 0.23 Gelatin 1.03 Cyan coupler (ExC) 0.32 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-6) 0.18 color image stabilizer (Cpd-7) 0.40 color image stabilizer (Cpd-8) 0.05 solvent (Solv-6) 0.14

Sixth layer (UV absorbing layer) Gelatin 0.43 UV absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08

Seventh layer (protective layer) Gelatin 1.13 Polyvinyl alcohol acryl-modified copolymer 0.17 (Modification degree 17%) Liquid paraffin 0.03

[0124]

Embedded image

[0125]

Embedded image

[0126]

[Chemical 43]

[0127]

[Chemical 44]

[0128]

[Chemical formula 45]

[0129]

[Chemical formula 46]

The sample 201 prepared as described above was subjected to solid exposure with white light so that the area ratio was 30%.
Continuous processing (running) was carried out until double replenishment. Treatment process Temperature Time Replenisher ^* Color development 38.5 ° C 45 seconds 73 ml Bleach-fix 35 ° C 45 seconds 60 ml ^** Rinse (1) 35 ° C 30 seconds − Rinse (2) 35 ° C 30 seconds − Rinse (3) 35 ℃ 30 seconds 360 ml Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material ** In addition to the above 60 ml, 120 ml per 1 m ^{2 of} light-sensitive material was poured from the rinse (1). (Rinse was a three-tank counter-current system from (3) to (1))

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4 Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfona) Ethyl) hydroxylamine 5.0 g 10.0 g Sodium triisopropylnaphthalene (β) sulphonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaminoline 3/2 sulfuric acid Monohydrate 5.0 g 11.5 g Water was added to 1000 ml 1000 ml pH (25 ° C / hydroxylation Adjusted with potassium and sulfuric acid) 10.00 11.00

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 150 ml Ammonium thiosulfate (750 g / liter) 93 ml 230 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5 g 12.5 g Nitric acid (67%) 30 g 65 g Water added 1000 ml 1000 ml pH (25 ° C / adjusted with acetic acid and ammonia water) 5.8 5.6

[Rinse solution] (tank solution and replenisher are the same) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Samples 202 to 208 were prepared in the same manner except that the magenta coupler for the third layer was changed as shown in Table-6.
It was created. The coupler was coated so that the number of moles was the same as M-2.

[0135]

[Table 6]

Samples 201 to 208 each had a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature 3200 of light source).
K) was used for gradation exposure, the above-mentioned running liquid was used for treatment, and magenta in the maximum density part was measured (DM-1).
The magenta density was also measured when the same color developer was used and the development time was changed to 25 seconds (DM-2). The results are shown in Table-7. From Table 7, it is understood that the coupler of the present invention has a high color-forming property and gives a sufficient density, and gives a good image density even when the development processing time is shortened.

[0137]

[Table 7]

[0138]

According to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material which has good color developability and gives an image of sufficiently high density even in a short processing time.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (I). General formula (I) In the formula, R ¹ represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group, X represents a coupling-off group bonded to the mother nucleus via a hydrogen atom, a halogen atom or an oxygen atom, and R ² represents- R ³ or —NR ⁴ R ⁵ is represented, R ³ , R ⁴ and R ⁵ are alkyl groups or aryl groups, R ⁴ and R ⁵ may be the same or different, and
⁴ and R ⁵ may combine with each other to form a nitrogen-containing heterocycle.