Silver halide color photographic light-sensitive material

FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic light-sensitive material, particularly relates to a silver halide color light-sensitive material having a high sensitivity and a high color forming efficiency.
BACKGROUND OF THE INVENTION
In a usual color photographic material, a substructive color reproduction system is used. Accordingly, a color image is formed by a combination of three dyes each derived from a yellow dye-forming coupler, magenta dye-forming coupler and cyan dye-forming coupler, respectively.
As the magenta dye-forming coupler, hereinafter simply referred as "magnet coupler", pyrazolone type, pyrazolinobenzimidazole type and indanone type couplers have been known. Among them, various 5-pyrazolone derivatives are widely used.
As a substituent to be bonded at 3-position of 5-pyrazolone ring of the 5-pyrazolone derivatives, for example, an alkyl group, an aryl group, an alkoxyl group described in U.S. Pat. No. 2,439,098, an acylamino group described in U.S. Pat. Nos. 2,369,489 and 2,600,788, and a ureido group described in No. 3,558,319 are used. However such couplers have some defects such as that the coupling activity with the oxidation product of a color developing agent is low and a magenta image having a high optical density is difficultly obtained, a magenta dye image obtained by color development has a strong secondary absorption at blue-light region and sharpness of cut-off of the main absorption of the dye at the long wavelength end thereof is insufficient.
3-anilino-5-pyrazolone type couplers described in U.S. Pat. Nos. 2,311,081, 13,677,764 and 3,684,514, BP Nos. 956,261 and 1,173,513 each has a high coupling activity and a high color forming efficiency and the dyes formed from the couplers have a small unnecessary adsorption in the red-light region. However, a color negative film is further demanded to have a higher sensitivity and a higher color forming efficiency than those of a light-sensitive material using the above 3-anilino-5-pyrazolone type couplers.
SUMMARY OF THE INVENTION
The first object of the invention is to provide a silver halide color photographic material having a high sensitivity and a high color forming efficiency.
The second object of the invention is to provide a silver halide color photographic light-sensitive material which have a layer reduced in the thickness and is excellent in the sharpness of image.
The above-mentioned objects of the invention is attained by a silver halide color photographic light-sensitive material comprising a support, provided thereon, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, in which the green-sensitive emulsion layer contains a coupler represented by the following Formula I; ##STR2## wherein R.sub.1 is a hydrogen atom or a group capable of being released upon reaction with the oxidation product of a color developing agent; R.sub.2 is a chlorine atom or an alkoxyl group; R.sub.3 and R.sub.4 are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an acyloxy group, a halogen atom, a hydroxyl group, an amino group, an alkylamino group, an acylamino group or a sulfonamido group, R.sub.3 and R.sub.4 may be linked with together to form a ring, provided that when R.sub.3 is a hydrogen atom, R.sub.4 is an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an acyloxy group, a halogen atom, a hydroxyl group, an amino group, an alkylamino group, an acylamino group or a sulfonamido group; R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are each a halogen atom.

DETAILED DESCRIPTION OF THE INVENTION
The coupler of the invention represented by Formula I is described below.
In Formula I, R.sub.1 is a hydrogen atom or a group capable of being released upon reaction with the oxidation product of a color developing agent. From the viewpoint of color forming efficiency, it is preferable that the group represented by R.sub.1 is a group capable of being released upon reaction with the oxidation product of a color developing agent. Examples of the group capable of being released upon reaction with the oxidation product of a color developing agent include a phenylthio group, a carboxy-propylthio group and a octylthio group. Among them, a phenylthio group, particularly a phenylthio group is preferable from the viewpoint of color forming efficiency. A phenylthio group having an acylamino group at the ortho-position with respect to the sulfur atom is particularly preferable for obtaining a high color forming efficiency.
R.sub.2 is a chlorine atom or an alkoxyl group such as a methoxy group, ethoxy group, iso-propyloxy group, t-butyloxy group or a hexyloxy group.
R.sub.3 and R.sub.4 are each independently a hydrogen atom or a substituent provided that when R.sub.3 is a hydrogen atom, R.sub.4 is a substituent. The substituent is an alkyl group such as a methyl group, ethyl group or iso-propyl group, an aryl group such as a phenyl group or p-methoxyphenyl group, an alkoxyl group such as a methoxy group, ethoxy group or t-butoxy group, an aryloxy group such as a phenoxy group of tolyloxy group, an acyloxy group, a halogen atom such as a fluorine atom, chlorine atom or bromine atom, a hydroxyl group, an amino group, an alkylamino group, an acylamino group or a sulfonamido group. The groups represented by R.sub.3 or R.sub.4 each may have a substituent. Groups each to be the substituent of R.sub.3 or R.sub.4 include the group the same as those described as the groups represented by R.sub.3 or R.sub.4. R.sub.3 and R.sub.4 may be linked with together to form a 3- to 6-member ring. It is preferable that at least one of R.sub.3 and R.sub.4 is a group represented by --OR.sub.10 or --OOCR.sub.11 in which R.sub.10 is a hydrogen atom, an alkyl group or an aryl group and R.sub.11 is an alkyl group or an aryl group.
R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are each independently a halogen atom such as a fluorine atom, chlorine atom or bromine atom. It is preferable that R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are each a chlorine atom by the reason of that a dye having a maximum spectral absorption at a preferable wavelength can be obtained from such coupler and a raw material of such coupler can be easily available with a low cost.
Typical examples of the coupler represented by Formula I described below.
__________________________________________________________________________Exemplified compound ##STR3##R.sub.1 R.sub.3 R.sub.4 R.sub.21__________________________________________________________________________ ##STR4## H CH.sub.2 CH.sub.3 ##STR5##2 " " CH.sub.3 "3 " " Cl "4 " " CH.sub.2 CHCH.sub.2 "5 " " CH.sub.2 CH.sub.2 CH.sub.3 "6 " " OCH.sub.2 CH.sub.3 "7 " " OC.sub.4 H.sub.9 "8 " " OOCCH.sub.3 "9 " " OOCC.sub.4 H.sub.9 (t) "10 " " OOCC.sub.9 H.sub.19 "11 " " ##STR6## "12 " " ##STR7## "13 " CH.sub.3 CH.sub.3 "14 " OCH.sub.3 OCH.sub.3 "15 " OOCC.sub.4 H.sub.9 OOCC.sub.4 H.sub.9 "16 ##STR8## Cl Cl ##STR9##17 H H CH.sub.2 CH.sub.3 "18 " " CH.sub.3 "19 " " OC.sub.4 H.sub.9 "20 " " OOCC.sub.4 H.sub.9 "21 " " ##STR10## "22 " " ##STR11## "23 " CH.sub.3 CH.sub.3 "24 " OOCC.sub.4 H.sub.9 OOCC.sub.4 H.sub.9 "25 ##STR12## H CH.sub.2 CH.sub.3 "26 " " OOCC.sub.4 H.sub.9 "27 ##STR13##28 ##STR14##__________________________________________________________________________
Examples of synthesis of the magenta couplers represented by Formula I of the invention are described below. However, the couplers of the invention can be synthesized referring usual synthesis method described in, for example, U.S. Pat. Nos. 2,369,489, 2,376,380, 2,472,581, 2,600,788, 2,933,391 and 3,615,506, BP Nos. 956,261 and 1,134,329 and JP No. 45-1970 and JP O.P.I. No. 2-39148/1990.
Synthesis example 1
Synthesis of exemplified compound 17 ##STR15##
To 1.85 g of 2,2-dimethyl-n-valeric acid, 3 ml of thionyl chloride is added, and the mixture is heated for 2 hours at -70.degree. C. Then thionyl chloride is removed under vacuum to obtain a pale yellow colored oil or Compound 2.
To 4.73 g of Compound 1, 27 ml of ethyl acetate, 10 ml of water and 2.46 g of sodium acetate anhydride were added and stirred. While stirring, Compound 2 was further added to the above mixture. After stirring for 30 minutes, 50 ml of hexane and precipitated matter was filtered. Colorless raw crystals were obtained by recrystalizing the filtered precipitation with 80 ml of acetonitoryl. The raw crystals were further recrystalized by making use of 80 ml of toluene. Thus 2.81 g of exemplified Compound 17 was obtained with a yield of 48.0%.
The chemical structure of above obtained compound 17 was confirmed with the NMR spectrum and mass spectrum thereof.
Synthesis example 2
Synthesis of exemplified compound 1 ##STR16##
To 2.34 g of exemplified Compound 17, 30 ml of N,N-dimethylformamide and 1.79 g of Compound 3 was added. The mixture was heated by 80.degree.-90.degree. C. and 0.32 g of bromine dissolved in 10 ml of N,N-dimethylformamide was further added to the mixture. The mixture was heated at 80.degree.-90.degree. C. for 3 hours and stood for cooling. After cooling, the mixture was poured into 150 ml of water. Thus white crystals were precipitated.
Then the precipitate was filtered. The filtered white crystals were purified by silica gel chromatography and recrystalized with 50 ml of acetontoryl. Thus 1.98 g of milky-white crystals of exemplified Compound 1 was obtained with a yield of 49.0%.
The chemical structure of above obtained compound 1 was confirmed with the NMR spectrum and mass spectrum thereof. The melting point of the compound was 155.degree.-156.degree. C.
In the color photographic light-sensitive material of the present invention, the magent coupler represented by Formula I is contained in a green-sensitive emulsion layer.
The magenta coupler of the invention is usually used in an amount of 1.times.10.sup.-3 to 8.times.10.sup.-1 moles, preferably 1.times.10.sup.-2 to 8.times.10.sup.-1 moles, per mol of silver contained in the emulsion layer in which the coupler to be contained.
The magenta coupler represented by Formula I may be used together with another kind of magenta coupler.
An usual method ca be used to contain the magenta coupler represented by Formula I in a silver halide photographic light-sensitive material. For example, a well known method by the following procedure can be applied. The coupler of Formula I is dissolved in a low-boiling solvent such as butyl acetate or ethyl acetate or a mixture of the low-boiling solvent and a high-boiling solvent such as dibutyl phthalate or tricresyl phosphate. Then the solution is mixed with an aqueous solution containing a surfactant and gelatin and dispersed and emulsified by a high-speed rotating mixer, a colloid mill or a ultrasonic dispersion apparatus. Thus obtained dispersion is directly added to a silver halide emulsion. In another way, the dispersion may be added to a silver halide emulsion after setting, cutting and washing.
Although the magenta coupler of Formula I may be dissolved in a low-boiling solvent and dispersed, it is more preferable to be dissolved in a mixture of a low-boiling solvent and a high-boiling solvent and dispersed in advance of addition to the emulsion.
The adding amount of the high-boiling solvent is preferably 0.01 g to 10 g, more preferably 0.1 to 3.0 g per gram of the coupler of Formula I.
In the light-sensitive martial of the invention, an usual silver halide photographic emulsion can be arbitrary used. The emulsion may be chemically sensitized by an usual method and may be spectrally sensitized for required wavelength region by an optical sensitizing dye.
An antifoggant and a stabilizer may be added to the silver halide emulsion. In the silver halide emulsion, gelatin is advantageously used.
A silver halide emulsion layer or another hydrophilic colloid layer of the light-sensitive material may be hardened, and a Plasticizer or a dispersion of a water-insoluble or hardly soluble synthesized polymer or latex may be contained in these layers. In emulsion layers of a color photographic light-sensitive material, various kinds of couplers can be contained.
Further, a colored coupler and competing coupler for color compensation, and a compound capable of releasing a photographically effective fragment such as a development accelerator, bleaching accelerator, developing agent, silver halide dissolving agent, toning agent, hardener, antifoggant, chemical sensitizer, optical sensitizer or desensitizer, upon coupling reaction with the oxidation product of a color developing agent.
As the support of the light-sensitive material, a paper laminated by a polyethylene layer, polyethylene-terephthalate film, baryta paper and cellulose triacetate film.
The light-sensitive material of the invention can be processed by an usual color photographic processing method after imagewise exposure to form a color image.
EXAMPLES
Example 1
In the followings, the amounts of compositions of light-sensitive material are described in grams per square meter, and the amounts of silver halide and colloidal silver are described in terms of silver. The amounts of sensitizing dyes are described in moles per mole of silver.
A side triacetyl cellulose film support was subbed. Backing layers each having the following compositions were coated on the surface of the support opposite to the subbed surface in the following order from the support.
______________________________________1st backing layerAlumina sol AS-100 (aluminum oxide 0.1 gproduced by Nissan Kagaku Kogyo Co.)Diacetyl cellulose 0.2 g2nd backing layerDiacetyl cellulose 100 mgStealic acid 10 mgFine silica particles 50 mg(average size: 0.2 .mu.m)______________________________________
Layers each having the following compositions were coated on the subbed surface of thus prepared support in the following order from the support to prepare Sample 1.
______________________________________1st layer: Antihalation layer (HC)Black colloidal silver 0.15UV absorbent (UV-1) 0.20Colored cyan coupler (CC-1) 0.02High-boiling solvent (Oil-1) 0.20High-boiling solvent (Oil-2) 0.20Gelatin 1.62nd layer: Interlayer (IL-1)Gelatin 1.33rd layer: Low-speed red-sensitiveemulsion layer (R-L)Silver iodobromide emulsion 0.4(average grain size: 0.3 .mu.m)(average iodide content: 2.0 mol %)Silver iodobromide emulsion 0.3(average grain size: 0.4 .mu.m)(average iodide content: 8.0 mol %)Sensitizing dye (S-1) 3.2 .times. 10.sup.-4Sensitizing dye (S-2) 3.2 .times. 10.sup.-4Sensitizing dye (S-3) 0.2 .times. 10.sup.-4Cyan coupler (C-1) 0.50Cyan coupler (C-2) 0.13Colored cyan coupler (CC-1) 0.07DIR compound (D-1) 0.006DIR compound (D-2) 0.01High-boiling solvent (Oil-1) 0.55Gelatin 1.04th layer: High speed red-sensitiveemulsion layer (R-H)Silver iodobromide emulsion 0.9(average grain size: 0.7 .mu.m)(average iodide content: 7.5 mol %)Sensitizing dye (S-1) 1.7 .times. 10.sup.-4Sensitizing dye (S-2) 1.6 .times. 10.sup.-4Sensitizing dye (S-3) 0.1 .times. 10.sup.-4Cyan coupler (C-2) 0.23Colored cyan coupler (CC-1) 0.03DIR compound (D-2) 0.02High-boiling solvent (Oil-1) 0.25Gelatin 1.05th layer: InterlayerGelatin 0.86th layer: Low speed green-sensitive emulsionlayer (G-L)Silver iodobromide emulsion 0.6(average grain size: 0.4 .mu.m)(average iodide content: 8.0 mol %)Silver iodobromide emulsion 0.2(average grain size: 0.3 .mu.m)(average iodide content: 2.0 mol %)Sensitizing dye (S-4) 6.7 .times. 10.sup.-4Sensitizing dye (S-5) 0.8 .times. 10.sup.-4Magenta coupler (M-a) 0.35Colored magenta coupler (CM-1) 0.05DIR compound (D-3) 0.02Additive 1 0.10High-boiling solvent (Oil-2) 0.7Gelatin 1.07th layer: High speed green-sensitive emulsionlayer (G-H)Silver iodobromide emulsion 0.9(average grain size: 0.7 .mu.m)(average iodide content: 7.5 mol %)Sensitizing dye (S-6) 1.1 .times. 10.sup.-4Sensitizing dye (S-7) 2.0 .times. 10.sup.-4Sensitizing dye (S-8) 0.3 .times. 10.sup.-4Magenta coupler (M-a) 0.20Colored magenta coupler (CM-1) 0.02DIR compound (D-3) 0.004High-boiling solvent (Oil-2) 0.35Additive 1 0.07Gelatin 1.08th layer: Yellow filter layer (YC)Yellow colloidal silver 0.1Additive (SC-1) 0.12High-boiling solvent (Oil-2) 0.15Gelatin 1.09th layer: Low speed blue-sensitiveemulsion layer (B-L)Silver iodobromide emulsion 0.25(average grain size: 0.3 .mu.m)(average iodide content: 2.0 mol %)Silver iodobromide emulsion 0.25(average grain size: 0.4 .mu.m)(average iodide content: 8.0 mol %)Sensitizing dye (S-9) 5.8 .times. 10.sup.-4Yellow coupler (Y-1) 0.6Yellow coupler (Y-2) 0.32DIR compound (D-1) 0.003DIR compound (D-2) 0.006High-boiling solvent (Oil-2) 0.18Gelatin 1.310th layer: High speed blue-senitiveemulsion layer (B-H)Silver iodobromide emulsion 0.5(average grain size: 0.8 .mu.m)(average iodide content: 8.5 mol %)Sensitizing dye (S-10) 3 .times. 10.sup.-4Sensitizing dye (S-11) 1.2 .times. 10.sup.-4Yellow coupler (Y-1) 0.18Yellow coupler (Y-2) 0.10High-boiling solvent (Oil-2) 0.05Gelatin 1.011th layer: 1st protective layer (PRO-1)Silver iodobromide emulsion 0.3(average grain size: 0.08 .mu.m)UV absorbent (UV-l) 0.07UV absorbent (UV-2) 0.10High-boiling solvent (Oil-1) 0.07High-boiling solvent (Oil-3) 0.07Gelatin 0.812th layer: 2nd protective layer (PRO-2)Compound A 0.04Compound B 0.004Polymethyl methacrylate 0.02(average particle size: 3 .mu.m)Copolymer of methyl methacrylate, ethyl 0.13methacrylate and mathacrylic acid,in the ratio of 3:3:4 by weight(average particle size: 3 .mu.m)Gelatin 0.5______________________________________
The above-mentioned Sample 1 further contains dispersing aid SU-1, coating aid SU-2, hardener H-1, Stabilizer ST-1, antimold agent DI-1, antifoggants AF-1 and AF-2, and dyes AI-1 and AI-2. ##STR17##
Samples 2 to 15 were prepared in the same manner as in Sample 1 except that the magenta coupler to be contained in 6th and 7th layer was changed as shown in Table 2.
In each of the samples, the molar amount of the coupler in the sample was the same as that of coupler M-a in Sample 1.
Samples 1 to 15 were each exposed to green light through an optical wedge and were processed under the following conditions.
______________________________________Processing Processing Processing Replenishingstep time temperature (.degree.C.) amount (ml)______________________________________Color Dev. 3' 15" 38 .+-. 0.3 780Bleaching 45" 38 .+-. 2.0 150Fixing 1' 30" 38 .+-. 2.0 830Stabilizing 60" 38 .+-. 5.0 830Drying 60" 55 .+-. 5.0 --______________________________________
In the above the replenishing is a volume per square meter of light-sensitive material.
The following color developer, bleaching solution, fixer and stabilizer and replenisher therefor were used in the processing.
______________________________________Color developer______________________________________Water 800 mlPotassium carbonate 30 gSodium hydrogen carbonate 2.5 gPotassium sulfite 3.0 gSodium bromide 1.3 gPotassium iodide 1.2 mgHydroxylamine sulfate 2.5 gSodium chloride 0.6 g4-amino-3-methyl-N-ethyl- 4.5 g(.beta.-hydroxyethyl)aniline sulfateDiethylenetriaminepentaacetic acid 3.0 gPotassium hydroxide 1.2 g______________________________________
Make to 1 liter with water and adjust pH value to 10.06 by sodium hydroxide or 20% sulfuric acid.
______________________________________Color developer replenisher______________________________________Water 800 mlPotassium carbonate 35 gSodium hydrogen carbonate 3 gPotassium sulfite 5 gSodium bromide 0.4 gHydroxylamine sulfate 3.1 g4-amino-3-methyl-N-ethyl- 6.3 g(.beta.-hydroxyethyl)aniline sulfateDiethylenetriaminepentaacetic acid 3.0 gPotassium hydroxide 2 g______________________________________
Make to 1 liter with water and adjust pH value to 10.18 by potassium hydroxide or 20% sulfuric acid.
______________________________________Bleaching solution______________________________________Water 700 mlFerric ammonium 1,3-diamino- 125 gpropanetetraaetateethylenediaminetetraacetic acid 2 gSodium nitrate 40 gAmmonium bromide 150 gGlacial acetic acid 40 g______________________________________
Make to 1 liter with water and adjust pH value to 4.4 by ammonia water or glacial acetic acid.
______________________________________Bleaching replenisher______________________________________Water 700 mlFerric ammonium 1,3-diamino- 175 gpropanetetraaetateethylenediaminetetraacetic acid 2 gSodium nitrate 50 gAmmonium bromide 200 gGlacial acetic acid 56 g______________________________________
Adjust pH value to 4.0 by ammonia water or glacial acetic acid and make to 1 liter with water.
______________________________________Fixer______________________________________Water 800 mlAmmonium thiocyanate 120 gAmmonium thiosulfate 150 gSodium sulfite 15 gEthylenediaminetetraacetic acid 2 g______________________________________
Adjust pH value to 6.2 by ammonia water or glacial acetic acid and make to 1 liter with water.
______________________________________Fixer replenisher______________________________________Water 800 mlAmmonium thiocyanate 150 gAmmonium thiosulfate 180 gSodium sulfite 20 gEthylenediaminetetraacetic acid 2 g______________________________________
Adjust pH value to 6.5 by ammonia water or glacial acetic acid and make to 1 liter with water.
______________________________________Stabilizer and stabilizer replenisher______________________________________Water 900 mlp-C.sub.8 H.sub.17 -C.sub.6 H.sub.4 -O-(CH.sub.2 CH.sub.2 O).sub.10 2.0 gDimethylolurea 0.5 gHexamethylenetetramine 0.2 g1,2-benzo-iso-thiazoline-3-one 0.1 gSiloxane (L-77 produced by UCC Co.) 0.1 gAmmonia water 0.5 ml______________________________________
Make to 1 liter with water and adjust pH value to 8.5 using ammonia water of 50% sulfuric acid
After processing the samples were subjected to densitometory with green light, and sensitometric characteristics of the samples were measured.
Sensitivity of the sample was determined as the reciprocal of exposure amount necessary to form a density of 0.3 on the fog density. Thus obtained results are listed in Table 2. In Table 2, the sensitivity of the sample is given as a relative value when the sensitivity of Sample 1 is set at 100.
TABLE 2______________________________________ Magenta couplerSample in 6th and 7th Sensi- MaximumNo. layers tivity density Note______________________________________1 M-a 101 1.26 Comparative2 M-b 107 1.40 Comparative3 Ex. Compound 1 200 2.22 Inventive4 Ex. Compound 2 202 2.21 Inventive5 Ex. Compound 3 198 2.18 Inventive6 Ex. Compound 7 201 2.15 Inventive7 Ex. Compound 8 201 2.31 Inventive8 Ex. Compound 9 200 2.34 Inventive9 Ex. Compound 11 210 1.93 Inventive10 Ex. Compound 12 205 1.89 Inventive11 Ex. Compound 15 209 2.36 Inventive12 Ex. Compound 25 200 2.18 Inventive13 Ex. Compound 26 199 2.28 Inventive14 Ex. Compound 27 200 2.28 Inventive15 Ex. Compound 28 200 2.10 Inventive______________________________________ Ex. Compound: Exemplified compound Mb (Comparative coupler) ##STR18##
As is obvious from Table 2, Samples 3 to 15, in which couplers of the invention are used, are each higher than those of Samples 1 and 2, in which the comparative couplers used. Accordingly, thickness of emulsion layer and amount of magenta coupler in a silver halide light-sensitive material can be reduced by making use of the coupler of the invention. As a result of that, sharpness of the light-sensitive material can be raised.

Number	Date	Country
0686872	Dec 1995	EPX
3628318	Feb 1988	DEX
150421	Jun 1993	JPX
1552701	Sep 1979	GBX

Silver halide color photographic light-sensitive material

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