Source: http://www.google.com/patents/US4840886?dq=6702462
Timestamp: 2014-03-09 23:19:11
Document Index: 172151355

Matched Legal Cases: ['Application No. 42045', 'Application No. 24321', 'Application No. 99437', 'Application No. 99437', 'Application No. 2784', 'Application No. 48535']

Patent US4840886 - Silver halide color photographic material containing a 1h-pyrazole (3,2-C)-s ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA silver halide color photographic material having at least one silver halide emulsion layer on a support is disclosed. Said silver halide emulsion layer contains at least one of the 1H-pyrazolo [3,2-c]-S-triazole derived magenta couplers that have a substituent of the following formula at 3-position:...http://www.google.com/patents/US4840886?utm_source=gb-gplus-sharePatent US4840886 - Silver halide color photographic material containing a 1h-pyrazole (3,2-C)-s-triazole derived magenta couplerAdvanced Patent SearchPublication numberUS4840886 APublication typeGrantApplication numberUS 07/161,321Publication dateJun 20, 1989Filing dateFeb 26, 1988Priority dateSep 14, 1984Fee statusLapsedAlso published asDE3574787D1, EP0178789A1, EP0178789B1Publication number07161321, 161321, US 4840886 A, US 4840886A, US-A-4840886, US4840886 A, US4840886AInventorsKoichi Hatta, Yuji Hotta, Toshifumi Iijima, Hiroshi Kashiwagi, Katsunori Katoh, Satoshi Kawakatsu, Kenji Kumashiro, Noritaka Nakayama, Hiroko Ohya, Kaoru ShinozakiOriginal AssigneeKonishiroku Photo Industry Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (39), Non-Patent Citations (8), Referenced by (7), Classifications (16), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetSilver halide color photographic material containing a 1h-pyrazole (3,2-C)-s-triazole derived magenta couplerUS 4840886 AAbstract A silver halide color photographic material having at least one silver halide emulsion layer on a support is disclosed. Said silver halide emulsion layer contains at least one of the 1H-pyrazolo [3,2-c]-S-triazole derived magenta couplers that have a substituent of the following formula at 3-position:
--R.sub.1 --S(O).sub.n --R.sub.2
What is claimed is: 1. A silver halide color photographic material having at least one silver halide emulsion layer on a support, said silver halide emulsion layer containing at least one of the 1H-pyrazolo[3,2-c]-S-triazole derived magenta couplers that have a substituent of the following formula at 3-position: --R.sub.1 --S(O).sub.n --R.sub.2 wherein R.sub.1 is an alkylene group; R.sub.2 is an alkyl, cycloalkyl or aryl group; and n is 1 or 2. 2. A silver halide color photographic material according to claim 1, wherein said magenta coupler is one represented by the following formula: ##STR7## wherein R.sub.1 is an alkylene group;R.sub.2 is an alkyl, cycloalkyl or aryl group; X is a leaving group which leaves upon reaction with the oxidation product of a color developing agent; R is an alkyl, cycloalkyl, aryl or heterocyclic group; and N is 1 or 2. 3. A silver halide color photographic material according to claim 2, wherein the alkyl group represented by R is a tertiary alkyl group.
6. A silver halide color photographic material according to claim 2, wherein R in the formula for said magenta coupler is a secondary alkyl group, R.sub.1 is an alkylene group having 3 to 6 carbon atoms in the straight chain, n is 2 and R.sub.2 is an alkyl or cycloalkyl group.
This application is a continuation of application Ser. No. 086,188, filed Aug. 14, 1987, now abandoned which in turn is a continuation of application Ser. No. 775,685, filed Sept. 13, 1985 now abandoned.
FIELD OF THE INVENTION The present invention relates to a silver halide color photographic material that contains a magenta coupler capable of effective color formation and which forms a magenta dye image having improved keeping quality, particularly in terms of light fastness. More specifically, the invention relates to a silver halide color photographic material containing a novel 1H-pyrazolo[3,2-c]-S-triazole derived magenta coupler.
BACKGROUND OF THE INVENTION The formation of dye images in most silver halide color photographic materials depends on the reduction of exposed silver halide grains with an aromatic primary amine color developing agent and the subsequent coupling of the resultant oxidation product of the color developing agent with couplers that respectively form yellow, magenta and cyan dyes.
A variety of 1H-pyrazol[3,2-c]-S-triazole derived magenta couplers have been proposed to overcome these problems of the conventional pyrazolone type couplers. Reference should be had to U.S. Pat. No. 3,725,067, as well as British Pat. Nos. 1,252,418 and 1,334,515. The compounds disclosed in these patents avoid the problem of secondary absorption but the improvement is inadequate in terms of resistance to formalin gas and is insignificant in respect of the production of a light-fast magenta dye image. The compound disclosed in Research Disclosure No. 12443 has no commercial value because of its low color formation. The 1H-pyrazolo[3,2-c]-S-triazole type magenta coupler disclosed in Unexamined Published Japanese Patent Application No. 42045/1983 features significant improvements in formalin resistance and color formation but little improvement has been achieved in terms of the production of a light-fast image.
SUMMARY OF THE INVENTION One object, therefore, of the present invention is to provide a silver halide color photographic material that contains a magenta coupler capable of effective color formation and which forms a magenta dye image having improved light fastness and resistance to formalin gas.
These objects of the invention are achieved by a silver halide color photographic material that has at least one silver halide emulsion layer on a support, said silver halide emulsion layer containing at least one of the 1H-pyrazolo[3,2-c]-S-triazole derived magenta couplers that have a substituent of the following formula at 3-position:
--R.sub.1 --S(0).sub.N --R.sub.2
DETAILED DESCRIPTION OF THE INVENTION The inventors have found that compounds wherein a group represented by the above formula is substituted at 3-position of 1H-pyrazolo[3,2-c]-S-triazole will exhibit effective color formation and provide magenta dye images having improved light fastness and formalin resistance.
Further improvements in light fastness and color formation are achieved by introducing as a substituent a leaving group other than hydrogen at 7-position of 1H-pyrazolo[3,2-c]-S-triazole which is the site of coupling with the oxidation product of a color developing agent.
The alkylene group at R.sub.1 may be substituted by alkyl, aryl (e.g. phenyl), halogen, cyano, a group that is bonded by carbonyl (e.g. alkoxycarbonyl, acyl or carbamoyl), or a group that is bonded by a hetero atom (e.g. nitro, alkoxy, alkylthio or dialkylamino). The alkylene group at R.sub.1 preferably has 1 to 6 carbon atoms.
The alkyl group at R.sub.2 includes a primary alkyl, a branched alkyl (secondary or tertiary alkyl). The primary alkyl is an alkyl having two hydrogen atoms attached to the carbon atom directly coupled to the magenta coupler of the present invention; the secondary alkyl is an alkyl having one hydrogen atom attached to the carbon having a substituent; and the tertiary alkyl is an alkyl having no hydrogen atom attached to the carbon atom directly coupled to the magenta coupler of the present invention. The alkyl group as R.sub.2 may be linear or branched and preferably has 1-30 carbon atoms as illustrated by methyl, ethyl, propyl, i-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl and 2-hexyldecyl. An example of the cycloalkyl group as R.sub.2 is cyclohexyl. The alkyl or cycloalky group represented by R.sub.2 may have a substituent such as an aryl group, heterocyclic group, halogen atom or a cyano group; a substituent that is bonded by carbonyl as illustrated by alkoxycarbonyl, acyl or carbamoyl; or a substituent that is bonded by a hetero atom (e.g. O, N or S) as illustrated by nitro, alkoxy, alkylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arysulfinyl or dialkylamino. If two or more of these substituents are present, they may be the same or different. If the heterocyclic group is a 1H-pyrazolo[3,2-c]-S-triazole-3 -yl compound, a bis type 1H-pyrazolo[3,2-c]-S-triazole compound is formed and this is of course a magenta coupler included within the scope of the present invention.
Examples of the leaving group other than hydrogen that may be bonded to the 7-position coupling site include halogens and organic groups that are bonded to the coupling site by an oxygen, nitrogen or sulfur atom. Illustrative leaving groups that are bonded to the coupling site by an oxygen atom include alkoxy, aryloxy, acyloxy and heterocyclic oxy; exemplary leaving groups that are bonded to the coupling site by a nitrogen atom include acylamino, diacylamino, sulfonamido, and 5- or 6-membered heterocyclic groups containing that nitrogen atom; and illustrative leaving groups that are bonded to the coupling site by a sulfur atom include thiocyano, alkylthio, arylthio, heterocyclic thio, arylsulfonyl and alkylsulfonyl.
Compounds preferred for the purposes of the present invention are represented by the following formula: ##STR1## wherein R.sub.1, R.sub.2 and n are already defined above; X is a leaving group which leaves upon reaction with the oxidation product of a color developing agent and is also defined above.
The symbol R in the above formula represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. The alkyl group may be a primary alkyl or a branched secondary or tertiary alkyl. The alkyl may have a substituent as illustrated in connection with the definition of R.sub.2. If the alkyl as R is a secondary alkyl, it may preferably have the following formula: ##STR2## wherein R.sub.3 and R.sub.4 are each a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heterocyclic group, or an alkyl, aryl or heterocyclic group that is bonded by an oxygen, nitrogen or sulfur atom, or an alkyl, aryl or heterocyclic group that is bonded by an acylamino, carbamoyl, sulfonamido, sulfamoyl, carbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamido, sulfon or sulfonyloxy; R.sub.3 and R.sub.4 may combine together to form a carbon ring or a hetero ring.
Further description of R.sub.3 and R.sub.4 is given below. Examples of the halogen atom represented by R.sub.3 or R.sub.4 include Cl, Br and F. Examples of the alkyl group represented by R.sub.3 or R.sub.4 include straight-chained or branched alkyl groups having 1 to 20 carbon atoms (e.g. methyl, ethyl, propyl, i-propyl, sec-butyl, n-butyl, t-butyl, n-octyl, t-octyl, dodecyl and octadecyl). These groups may have substituents such as halogen atom, nitro, cyano, alkoxy, aryloxy, amino, acylamino, carbamoyl, sulfonamido, sulfamoyl, imido, alkylthio, arylthio, aryl, alkoxycarbonyl and acyl. Exemplary substituted alkyl groups include chloromethyl, bromomethyl, trichloromethyl, β-nitroethyl, δ-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl, benzoylamino, propyl, ethylcarbamoylethyl, methanesulfonamidoethyl, ethylthioethyl, p-methoxyphenylthiomethyl, p-chlorophenylmethyl, naphthylethyl, ethoxycarbonylethyl and acetylethyl.
Illustrative heterocyclic groups as R.sub.3 or R.sub.4 are 5- or 6-membered rings having at least one of nitrogen, oxygen and sulfur atoms and they may be aromatic or non-aromatic. Specific examples of the heterocyclic group include pyridyl, quinolyl, pyrrolyl, morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl and thiadiazolyl. These heterocyclic groups may have substituents as listed in connection with the description of the alkyl group.
Examples of the carbon ring formed by combination of R.sub.3 and R.sub.4 include cyclopropyl, cyclopentyl, cyclohexyl and cyclohexenyl. Examples of the hetero ring that may be formed by R.sub.3 as combined with R.sub.4 include piperidyl, pyrrolidyl, dioxanyl and morpholinyl.
The 1H-pyrazolo[3,2-c]-S-triazole derived magenta couplers in accordance with the present invention are illustrated by, but by no means limited to, the following compounds. Preferably, these couplers are non-diffusible and have molecular weights not exceeding 450. ##STR3##
The group R.sub.2 --SO.sub.2 --R.sub.1 -COOH is obtained by oxidizing the corresponding R.sub.2 --S--R.sub.1 -COOH with hydrogen peroxide in accordance with the method described in Unexamined Japanese Patent Application No. 24321/1972. The group R.sub.2 --SO--R.sub.1 --COOH is obtained by reacting equimolar amounts of R.sub.2 --S--R.sub.1 --COOH and hydrogen peroxide under cooling.
Synthesis of Magenta Coupler (1) The reaction scheme is shown below: ##STR4##
(1) Synthesis Compound (I) This compound was prepared by the method described in Journal of the Chemical Society, Perkin I, 1977, pp. 2047-2052.
(2) Synthesis of Compound (II) Ninety-two grams of (I) was dispersed in 1,000 ml of acetonitrile. To the dispersion, 60 g of triethylamine was added and acid chloride prepared by reacting 222 g of acid with thionyl chloride was added dropwise to the mixture under refluxing. The resulting mixture was refluxed for an additional 30 minutes. After cooling the mixture, the crystal was recovered by filtration, washed with water thoroughly and dried. The end compound was obtained in a yield of 80%.
(3) Synthesis of Compound (III) To 1,500 ml of toluene, 193 g of (II) and 53.5 g of phosphorus oxychloride were added and the mixture was refluxed for 5 hours. Thereafter, the toluene was distilled off and 1,500 ml of acetonitrile and 80 g of pyridine were added to the residue and the resulting mixture was refluxed for an additional 1.5 hours. After distilling off the acetonitrile, water was added to the residue and the resultant crystal was recovered by filtration. The crystal was washed with water, dried and recrystallized from acetonitrile to give the end compound (III).
(4) Synthesis of Compound (IV) One hundred and thirty grams of (III) was added to a mixture of glacial acetic acid (1,000 ml), concentrated sulfuric acid (100 ml) and water (20 ml) and the resultant mixture was refluxed for 10 hours. After leaving the mixture to cool down, an aqueous caustic soda solution consisting of 1,000 ml of water and 180 g of caustic soda was added under agitation. The resulting crystal was recovered by filtration, washed thoroughly with water, and dried to give the end compound (IV).
(5) Synthesis of Compound (1) Twenty grams of (IV) was dissolved in chloroform, and to the solution, an equivalent amount of N-chlorosuccinimide was added. The mixture was held at room temperature for 1 hour to perform reaction. The reaction mixture was washed with dilute alkali and subjected to further washing with water. The chloroform was distilled off and the residue was purified by column chromatography on silica gel using benzene-acetone as a solvent. The purified residue was identified as the end compound by NMR spectrum and mass spectrum.
Synthesis of Magenta Coupler (47) The synthesis scheme is shown below: ##STR5##
(1) Synthesis of Compound A A mixture of octadecylcaptan (28.6 g) and α-methyl-γ-butyrolactone (10 g) was dissolved in dimethylformamide (200 ml), and after addition of 28% aqueous sodium methylate (19.3 g), the mixture was heated at 80 under agitation. After the reaction, the mixture was poured into water and rendered acidic with hydrochloric acid.
(2) Synthesis of Compound B Compound A (38.6 g) was dissolved in acetic acid (200 ml) and to the solution, 25.4 g of 35% H.sub.2 O.sub.2 was slowly added dropwise at 60 the resulting crystal was recovered by filtration. After washing with 80% methanol, the crystal was recrystallized from methanol to obtain 26 g of compound B. m.p. 109
(3) Synthesis of Compound D In 200 ml of acetonitrile, 11.4 g of hydrazine compound (compound C) was dissolved and, to the solution, 6.1 g of triethylamine was added and the mixture was boiled under agitation. Acid chloride prepared from 25.8 g of the acid obtained in (2) was dissolved in a small amount of acetonitrile and the solution was added dropwise to the stirred solution.
Thereafter, the mixture was refluxed for 1 hour and cooled to cause crystallization. The crystal was recovered by filtration and washed with water. After drying, the crystal was recrystallized from methanol to obtain 27.6 g of compound D. m.p. 125
(4) Synthesis of Compound E Compound D (24.5 g) was dissolved in 150 ml of toluene and, to the solution, 6.2 g of phosphorus oxychloride was added and the resulting mixture was refluxed for 3 hours. Thereafter, the mixture was cooled to room temperature, and stirred for 10 minutes after addition of triethylamine (12 g). The stirred mixture was washed with warm water and the toluene was distilled off under vacuum. The residue was purified by column chromatography and recrystallized from methanol to obtain 15.0 g of compound E. m.p. 78
(5) Synthesis of Compound F Compound E (15.0 g) was added to a mixture of concentrated sulfuric acid (15 ml), glacial acetic acid (75 ml) and water (15 ml) and the resultant mixture was refluxed for 8 hours. After the reaction, the mixture was poured into iced water having 30 g of sodium hydroxide dissolved therein. The crystal was recovered by filtration and, after thorough washing with water, recrystallized from methanol to provide 10.2 g of compound F. m.p. 98
(6) Synthesis of Magenta Coupler (47) Compound F (10.0 g) was dissolved in 100 ml of chloroform and, to the solution, 2.6 g of N-chlorosuccinimide was added and the mixture was held at room temperature for 30 minutes. Thereafter, the reaction mixture was washed with water and the chloroform was distilled off. The residue was mixed with hexane and heated to cause crystallization. The crystal was recovered by filtration and recrystallized from methanol to provide 6.8 g of the end compound. m.p. 57
Synthesis of Magenta Couplers (2), (6) and (10) The 1H-pyrazolo[3,2-c]-S-triazole nucleus was prepared in accordance with Research Disclosure No. 12443, and respective leaving groups were introduced by the procedures described in U.S. Pat. No. 3,725,067 and Unexamined Published Japanese Patent Application No. 99437/1984.
The 1H-pyrazolo[3,2-c]-S-triazole nucleus in other magenta couplers was prepared as in the case of the synthesis of magenta coupler (1). Leaving groups were introduced in magenta couplers (5), (15), (17), (18) and (19) by referring to the disclosure in U.S. Pat. No. 3,725,067 and Unexamined Published Japanese Patent Application No. 99437/1984.
The magenta coupler of the present invention and the respective couplers associated thereto may be introduced into silver halide emulsion layers by any known method such as one described in U.S. Pat. No. 2,322,027. For example, the couplers are dispersed in hydrophilic colloids after being dissolved in high-boiling organic solvents or low-boiling organic solvents. Examples of the former type include alkyl esters of phthalic acid (e.g., dibutyl phthalate and dioctyl phthalate), phosphate esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and dioctylbutyl phosphate), citrate esters (e.g., tributyl acetylcitrate), benzoate esters (e.g., octyl benzoate), alkylamides (e.g., diethyl laurylamide), aliphatic acid esters (e.g. dibutoxyethyl succinate and dioctyl azelate) and trimesic acid esters (e.g. tributyl trimesate). The low-boiling organic solvents are those which boil at between about 30 (e.g. ethyl acetate and butyl acetate), ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate and methyl cellosolve acetate. The high-boiling organic solvents may be used in combination with the low-boiling organic solvents.
Illustrative anti-fading agents include hydroquinone derivatives of the type described in U.S. Pat. Nos. 2,360,290, 2,418,613, 2,673,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801 and 2,816,028, as well as British Pat. No. 1,363,921; gallic acid derivatives as described in U.S. Pat. Nos. 3,457,079 and 3,069,262; p-alkoxyphenols of the type described in U.S. Pat. Nos. 2,735,765 and 3,698,909, as well as Japanese Patent Publication No. 20977/1974 and 6623/1977; p-oxyphenol derivatives of the type described in U.S. Pat. Nos. 3,432,300, 3,573,050, 3,574,627 and 3,764,337, as well as Unexamined Published Japanese Patent Application Nos. 35633/1977, 147434/1977 and 152225/1977; and bisphenols as described in U.S. Pat. No. 3,700,455.
Exemplary ultraviolet absorbers include aryl-substituted benzotriazole compounds as described in U.S. Pat. No. 3,533,794, 4-thiazolidone compounds (as described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (as described in Unexamined Published Japanese Patent Application No. 2784/1971), connamic acid ester compounds (as described in U.S. Pat. Nos. 3,705,805 and 3,707,375), butadiene compounds (as described in U.S. Pat. No. 4,045,229), and benzoxidole compounds (as described in U.S. Pat. No. 3,700,455). Other compounds usable as UV absorbers are found in U.S. Pat. No. 3,499,762 and Unexamined Published Japanese Patent Application No. 48535/1979.
Particularly useful primary aromatic amino color developing agents are N,N'-dialkyl-p-phenylenediamine compounds wherein the alkyl or phenyl group may have a suitable substituent. Among these compounds, the following are particularly advantageous: N,N'-diethyl-p-phenylene-diamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, and 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluene sulfonate.
In addition to metal complex salts of these organic acids which are used as bleaching agents, the bleaching bath used in processing the color photographic material of the present invention may contain a variety of additives, and preferred additives are rehalogenating agents such as alkali or ammonium halides (e.g. potassium bromide, sodium bromide, sodium chloride and ammonium bromide), metal salts and chelating agents. Any other additives that are conventionally incorporated in bleaching baths may also be used and they include pH buffers (e.g. borate, oxalate, acetate, carbonate and phosphate salts), alkylamines and polyethylene oxides.
The fixing bath and bleach-fixing bath may also contain one or more pH buffers that are selected from among sulfites (e.g. ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite), and a variety of acids or salts (e.g. boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide).
EXAMPLE 1 One tenth of a mole, per mole of silver, of one of the magenta couplers listed in Table 1 (which follows) was mixed with an equal weight of tricresyl phosphate and three times the coupler's weight of ethyl acetate, and the mixture was heated to 60 The solution was then mixed with 1,200 ml of 5% aqueous gelatin solution containing 120 ml of a 5% aqueous solution of Alkanol B (trade name of du Pont for alkylnaphthalene sulfonate). The mixture was emulsified with an ultrasonic disperser and the dispersion obtained was added to 4 kg of a green-sensitive silver iodobromide emulsion (containing 6 mol% AgI). To the mixture, 120 ml of a 2% solution (water: methanol=1:1) of 1,2-bis-(vinylsulfonyl)ethane was added as a hardener, and the so prepared coating solution was applied to a subbed transparent polyester base, and the web was dried to provide a sample of color photographic material (with silver deposit of 20 mg/100 cm.sup.2). The other samples were prepared by the same procedure.
______________________________________Processing schemeSteps         Temperature,                       Time______________________________________Color development         38           3 min, 15 secBleaching     38           4 min, 20 secWashing       38           3 min, 15 secFixing        38           4 min, 20 secWashing       38           3 min, 15 secStabilizing   38           1 min, 30 secDrying        47 to 55     16 min, 30 sec______________________________________
______________________________________Color developerPotassium carbonate      30     gSodium hydrogencarbonate 2.5    gPotassium sulfite        5      gSodium bromide           1.3    gPotassium iodide         2      mgHydroxylamine sulfate    2.5    gSodium chloride          0.6    gDiethylenetriaminepentaacetic acid                    2.5    gsodium salt4-amino-3-methyl-N--ethyl-N--(&#946;-                    4.8    ghydroxyethyl)aniline sulfatePotassium hydroxide      1.2    gWater to make            1,000  mlpH adjusted to 10.06 by addition ofpotassium hydroxide or 20% H.sub.2 SO.sub.4.Bleaching bathEthylenediaminetetraacetic acid iron                    100    gammonium saltEthylenediaminetetraacetic acid                    10     gAmmonium bromide         150    gGlacial acetic acid      40     mlSodium bromate           10     gWater to make            1,000  mlpH adjusted to 3.5 by addition ofammonia water or glacial acetic acid.Fixing bathAmmonium thiosulfate     180    gAnhydrous sodium sulfite 12     gSodium metabisulfite     2.5    gEthylenediaminetetraacetic acid                    0.5    gdisodium saltSodium carbonate         10     gWater to make            1,000  mlStabilizing bathFormalin (37% aq. sol.)  2      mlKonidax (product of Konishiroku                    5      mlPhoto Industry Co., Ltd.)Water to make            1,000  ml______________________________________
TABLE 1______________________________________Sam-             Specific         Formalin                                    Lightple              sensi-   Maximum resis- fast-No.  Coupler used            tivity.sup.(1)                     density tance.sup.(2)                                    ness.sup.(3)______________________________________1-11 Comparative 100      2.64    92     25coupler 11-12 Comparative  96      2.58    91     27coupler 21-13 Comparative 103      2.70    93     23coupler 31-14 Comparative 102      2.71    94     24coupler 41-15 Coupler (11)            100      2.63    90     35of the invention1-16 Coupler (12)            101      2.65    92     34of the invention1-17 Coupler (1)  99      2.58    93     39of the invention1-18 Coupler (7) 102      2.75    91     40of the invention1-19 Coupler (3) 105      2.81    93     37of the invention1-20 Coupler (4) 110      2.92    90     35of the invention1-21 Coupler (19)            108      2.90    92     33of the invention______________________________________ acl Notes
(2) A sample was subjected to color development after it was held for 3 days in a sealed container of 0.9% aqueous formalin (6 ml) conditioned at 30 The formalin resistance of the first sample was calculated by the following formula: ##EQU1##
EXAMPLE 2 Sample Nos. 1-11 to 1-19 prepared in Example 1 were exposed through an optical wedge and subsequently processed by the following scheme. The results are shown in Table 2. The specific sensitivity and light fastness were measured by the same methods as used in Example 1.
______________________________________Processing scheme:______________________________________Color development          38                       3 min., 30 secBleach-fixing  33                       1 min., 30 secStabilizing or 25-30                       3 min.washingDrying         75-80                       ca. 2 min.______________________________________
______________________________________Color developerBenzyl alcohol             15     mlEthylene glycol            15     mlPotassium sulfite          2.0    gPotassium bromide          0.7    gSodium chloride            0.2    gPotassium carbonate        30.0   gHydroxylamine sulfate      3.0    gTripolyphosphoric acid (TPPS)                      2.5    g3-Methyl-4-amino-N--ethyl-N--(&#946;-methane-                      5.5    gsulfonamidoethyl)aniline sulfateBrightener (4,4'-diaminostilbenzosulfonic                      1.0    gacid derivative)Potassium hydroxide        2.0    gWater to make              1,000  mlpH adjusted to 10.20Bleachi-fixing bathEthylenediaminetetraacetic acid iron                      60     g(III) ammonium dihydrate saltEthylenediaminetetraacetic acid                      3      gAmmonium thiosulfate (70% aq. sol.)                      100    mlAmmonium sulfite (40% aq. sol.)                      27.5   mlpH adjusted to 7.1 by addition of potassiumcarbonate or glacial acetic acidWater to make              1,000  mlStabilizing bath5-Chloro-2-methyl-4-isothiazolin-3-one                      1.0    gEthylene glycol            10     g1-Hydroxyethylidene-1,1'-diphosphonic acid                      2.5    gBismuth chloride           0.2    gMagnesium chloride         0.1    gAmmonium hydroxide (28% aq. sol.)                      2.0    gSodium nitrilotriacetate   1.0    gWater to make              1,000  mlpH adjusted to 7.0 by addition ofammonium hydroxide or sulfuric acid.______________________________________
TABLE 2______________________________________Sample             Specific  Maximum  LightNo.   Coupler used sensitivity                        density  fastness______________________________________2-11  Comparative  100       2.41     24 coupler 12-12  Comparative  100       2.42     26 coupler 22-13  Comparative  105       2.51     23 coupler 32-14  Comparative  108       2.52     25 coupler 42-15  Coupler (11) of              101       2.42     37 the invention2-16  Coupler (12) of               99       2.39     38 the invention2-17  Coupler (1) of               77       2.39     36 the invention2-18  Coupler (7) of               98       2.38     40 the invention2-19  Coupler (3) of              102       2.43     37 the invention2-20  Coupler (4) of              105       2.50     38 the invention2-21  Coupler (19) of              104       2.48     34 the invention______________________________________
EXAMPLE 3 A sample of silver halide color photographic material was prepared by coating the following layers in sequence on a support made of polyethylene coated paper containing anatase type TiO.sub.2. The amounts of the additives incorporated in each of the layers described below are based on an area of 100 cm.sup.2.
(1) Layer containing 20 mg of gelatin, 5 mg in terms of silver of a blue-sensitive silver chlorobromide emulsion, and 3 mg of dioctyl phthalate coupler solvent having dissolved the resin 8 mg of Y-coupler* and 0.1 mg of 2,5-di-t-octylhydroquinone:
(5) Layer containing 16 mg of gelatin, 4 mg in terms of silver of a red-sensitive silver chlorobromide emulsion, and 2.0 mg of tricresyl phosphate coupler solvent having dissolved therein 3.5 mg of C-coupler* and 0.1 mg of 2,5-di-t-octyl-hydroquinone:
Eleven samples of multi-layered photographic material were prepared as above and each was processed as in Example 2. The specific types of the Y-coupler, M-coupler and C-coupler used, and the results of the photographic processing are shown in Table 3 below. Each of the samples was checked for its magenta density after exposure to white light. The specific sensitivity and light fastness were measured by the same methods as used in Example 1. The data in Table 3 show the improved light fastness of the dye images produced by using the magenta couplers prepared in accordance with the present invention. It was also clear that the light fastness of the images could be further improved by using UV absorbers in combination with the magenta couplers. ##STR6##
TABLE 3__________________________________________________________________________Sample    Layer (1)     Layer (3)             Layer (5)    Specific                                Maximum                                      LightNo. Y-coupler     M-coupler             C-coupler                   UV-absorber                          sensitivity                                density                                      fastness                                          Remarks__________________________________________________________________________3-31    Y-1   Comparative             C-1   --     100   2.30  22     coupler (1)3-32    Y-1   Comparative             C-1   UV-1   101   2.27  35  2 mg of UV     coupler (1)   UV-2                   absorber in                                          layer (5)3-33    Y-1   Coupler (12)             C-1   --      99   2.30  39     of the invention3-34    Y-1   Coupler (12)             C-1   UV-1   102   2.26  50     of the invention                   UV-23-35    Y-2   Coupler (12)             C-2   UV-1   102   2.35  49     of the invention                   UV-23-36    Y-2   Coupler (12)             C-2   UV-1   101   2.38  57  Another layer (2)     of the invention                   UV-2                   inserted between                                          layers (5) and (6)                                          in sample No. 353-37    Y-1   Coupler (12)             C-3   UV-1   103   2.39  48     of the invention                   UV-23-38    Y-1   Coupler (12)             C-3   UV-1    99   2.32  56  Same layer arrange-     of the invention                   UV-2                   ment as in Sample                                          No. 363-39    T-2   Coupler (12)             C-4   UV-1    97   2.32  47     of the invention                   UV-23-40    Y-2   Coupler (12)             C-1   UV-1   103   2.35  47     of the invention                   UV-23-41    Y-1   Coupler (11)             C-1   UV-1   102   2.37  51     of the invention                   UV-2__________________________________________________________________________
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2322027 *Dec 26, 1940Jun 15, 1943Eastman Kodak CoColor photographyUS2353754 *Nov 7, 1942Jul 18, 1944Eastman Kodak CoColor photography using metallic salt coupler compoundsUS3705896 *Jan 15, 1971Dec 12, 1972Eastman Kodak CoPyrazolo(3,2-c)-s-triazoles and process for the manufacture thereofUS3725067 *Jan 15, 1971Apr 3, 1973Eastman Kodak CoSilver halide emulsion containing 1-h-pyrazolo(3,2-c)-s-triazole color couplersUS3758309 *Jan 15, 1971Sep 11, 1973Eastman Kodak Co-pyrazolo(3,2-c)-s-triazole silver halide emulsions containing sensitizing dyes derived from a 1hUS4338393 *Feb 4, 1981Jul 6, 1982Eastman Kodak CompanyHeterocyclic magenta dye-forming couplersUS4456681 *May 27, 1983Jun 26, 1984Konishiroku Photo Industry Co., Ltd.Color photographic materialsUS4481268 *Sep 2, 1982Nov 6, 1984Eastman Kodak CompanyMethod of forming a photographic dye imageUS4500630 *Feb 15, 1984Feb 19, 1985Fuji Photo Film Co., Ltd.Method for forming magenta color imageUS4510234 *Sep 7, 1983Apr 9, 1985Konishiroku Photo Industry Co., Ltd.Silver halide photographic emulsionUS4529691 *Apr 4, 1984Jul 16, 1985Agfa-Gevaert AgColor photographic recording material containing color couplersUS4540654 *Mar 19, 1984Sep 10, 1985Fuji Photo Film Co., Ltd.Method of forming color image comprising heterocyclic magenta dye-forming couplerUS4548899 *Nov 1, 1984Oct 22, 1985Konishiroku Photo Industry Co., Ltd.Silver halide color photographic materialUS4562146 *Nov 16, 1984Dec 31, 1985Konishiroku Photo Industry Co., Ltd.Silver halide color photographic materialUS4576910 *Jun 11, 1984Mar 18, 1986Fuji Photo Film Co., Ltd.Silver halide color light-sensitive material containing magenta color image-forming polymer or copolymer coupler latexUS4581326 *Sep 6, 1984Apr 8, 1986Konishiroku Photo Industry Co., Ltd.Silver halide color photographic materialUS4585732 *Dec 27, 1984Apr 29, 1986Fuji Photo Film Co., Ltd.Silver halide photographic light-sensitive materialUS4590153 *Oct 29, 1984May 20, 1986Fuji Photo Film Co., Ltd.Silver halide color photographic materialsUS4600688 *Feb 8, 1985Jul 15, 1986Konishiroku Photo Industry Co., Ltd.Silver halide color photographic light-sensitive materialUS4607002 *Nov 14, 1985Aug 19, 1986Konishiroku Photo Industry Co., Ltd.Silver halide color photo-sensitive materialUS4623617 *Oct 8, 1985Nov 18, 1986Konishiroku Photo Industry Co., Ltd.Silver halide color photographic materialUS4639413 *Aug 14, 1985Jan 27, 1987Fuji Photo Film Co., Ltd.Silver halide color photographic materials containing magenta coupler and high boiling point organic solventUS4639415 *Sep 16, 1985Jan 27, 1987Konishiroku Photo Industry Co., Ltd.Silver halide color photographic material containing a magenta color image-forming couplerUS4655015 *Mar 11, 1986Apr 7, 1987Firma Pfeifer Seil-Und Hebetechnik Gmbh & Co.Anchor tie for carrying prefabricated concrete membersUS4659652 *Aug 23, 1985Apr 21, 1987Fuji Photo Film Co., Ltd.Silver halide color photographic materialUS4675280 *Oct 8, 1985Jun 23, 1987Konishiroku Photo Industry Co., Ltd.Silver halide color photographic material containing a 1H-pyrazolo [3,2-C]-SUS4695533 *Sep 12, 1985Sep 22, 1987Konishiroku Photo Industry Co., Ltd.Silver halide photographic light-sensitive materialDE1810464A1 *Nov 22, 1968Jul 24, 1969Eastman Kodak CoFarbphotographisches EntwicklungsverfahrenDE3339201A1 *Oct 28, 1983May 3, 1984Fuji Photo Film Co LtdFarbphotographisches lichtempfindliches silberhalogenidmaterialEP0073636A1 *Aug 24, 1982Mar 9, 1983EASTMAN KODAK COMPANY (a New Jersey corporation)Photographic elements containing ballasted couplersEP0143570A2 *Nov 2, 1984Jun 5, 1985Konica CorporationSilver halide color photographic materialEP0177765A1 *Sep 5, 1985Apr 16, 1986Fuji Photo Film Co., Ltd.Silver halide color photographic materialEP0178789A1 *Sep 16, 1985Apr 23, 1986Konica CorporationSilver halide color photograhic materialEP0723636A1 *Aug 25, 1995Jul 31, 1996ValeoAirflow-cooled torsion damperGB1247493A * Title not availableGB1252418A * Title not availableGB1334515A * Title not availableGB2132783A * Title not availableGB2135788A * Title not available* Cited by examinerNon-Patent CitationsReference1Bailey et al., "Synthesis of 1H-pyrazolo [3,2-C]-S-Triazoles and Derived Azamethine Dyes", J. Chem. Soc. Perkin I., 18, 1977, pp. 2047-2052.2 *Bailey et al., Synthesis of 1H pyrazolo 3,2 C S Triazoles and Derived Azamethine Dyes , J. Chem. Soc. Perkin I., 18, 1977, pp. 2047 2052.3 *Examiner s Report for EPO Pat. Appln. No. 85 306569.6, dated 4/9/87.4Examiner's Report for EPO Pat. Appln. No. 85 306569.6, dated 4/9/87.5 *Research Disclosure 12443, published Aug. 1974.6 *Research Disclosure 20525, published May 1981, p. 184.7 *Research Disclosure 20919, published Sept. 1981, pp. 345 346.8Research Disclosure 20919, published Sept. 1981, pp. 345-346.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5019489 *Jul 26, 1989May 28, 1991Eastman Kodak CompanyColor photographic element and processUS5032497 *Mar 10, 1989Jul 16, 1991Konishiroku Photo Industry Co., Ltd.Silver halide color photo-sensitive materialUS5298368 *Apr 23, 1991Mar 29, 1994Eastman Kodak CompanyPhotographic coupler compositions and methods for reducing continued couplingUS5534400 *Jan 5, 1995Jul 9, 1996Konica CorporationSilver halide color photographic light-sensitive materialUS5541045 *Oct 17, 1994Jul 30, 1996Fuji Photo Film Co., Ltd.Silver halide photographic materialUS6020114 *Aug 21, 1997Feb 1, 2000Agfa - Gevaert NvColor photographic recording materialUS6143485 *Dec 23, 1998Nov 7, 2000Eastman Kodak CompanyPyrazolotriazle dye-forming photographic coupler* Cited by examinerClassifications U.S. Classification430/558, 430/555, 430/505, 430/543, 430/386, 430/554, 430/502International ClassificationG03C7/38, G03C7/305, C07D487/04Cooperative ClassificationG03C7/3835, G03C7/30529, C07D487/04European ClassificationG03C7/38H2N4, G03C7/305B1M, C07D487/04Legal EventsDateCodeEventDescriptionSep 7, 1993FPExpired due to failure to pay maintenance feeEffective date: 19930620Jun 20, 1993LAPSLapse for failure to pay maintenance feesJan 19, 1993REMIMaintenance fee reminder mailedSep 22, 1989ASAssignmentOwner name: KONICA CORPORATION, JAPANFree format text: RELEASED BY SECURED PARTY;ASSIGNOR:KONISAIROKU PHOTO INDUSTRY CO., LTD.;REEL/FRAME:005159/0302Effective date: 19871021RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google