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US3415652A - Silver halide color photographic elements utilizing alpha-sulfonyloxy substituted two-equivalent yellow-forming couplers - Google Patents

Silver halide color photographic elements utilizing alpha-sulfonyloxy substituted two-equivalent yellow-forming couplers Download PDF

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US3415652A
US3415652A US444822A US44482265A US3415652A US 3415652 A US3415652 A US 3415652A US 444822 A US444822 A US 444822A US 44482265 A US44482265 A US 44482265A US 3415652 A US3415652 A US 3415652A
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couplers
group
coupler
silver halide
forming
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US444822A
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Ralph F Porter
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to DE19661547672 priority patent/DE1547672A1/en
Priority to GB13184/66A priority patent/GB1092506A/en
Priority to FR55183A priority patent/FR1473553A/en
Priority to BE678578D priority patent/BE678578A/xx
Priority to US749896*A priority patent/US3542840A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
    • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds

Definitions

  • This invention rel-ates to color photography and more particularly to novel dye-forming coupler compounds for use in image forming systems and processes utilizing such compounds for the formation of images.
  • my invention relates to two-equivalent coupler compounds for forming yellow dye images in color photography.
  • the formation of colored photographic images by coupling the oxidation product of an aromatic amino developing agent with color-forming compounds is well known.
  • the subtractive color process is most frequently used, and the image dyes are of the primary colors cyan, magenta and yellow for the red, green and blue records respectively.
  • the couplers which form the cyan dyes are usually phenols or naphthols; those forming the magenta dyes are generally pyrazolones or cyanoacetyl compounds; and those forming the yellow dyes are open-chain compounds containing a methylene group having two carbonyl groups attached to it.
  • couplers which have been used in the previously described color processes are four-equivalent couplers, that is, they require 4 mols of silver halide for the formation of 1 mol. of dye.
  • certain of the prior art couplers which are two-equivalent couplers i.e., requiring only 2 mols of silver halide for the formation of 1 mol of dye, for example the couplers described in French Patent 991,453, British Patent 805,505, etc.
  • New two-equivalent couplers are desired that have improved characteristics for use in color photography.
  • Another object is to provide new two-equivalent couplers which have good reactivity even when incorporated in silver halide emulsion layers without any high boiling couplers solvents.
  • Another object is to provide new couplers which are valuable for use in any of the image forming systems (silver or non silver) where couplers are used to advantage, for example the coupler can be used to advantage in image 3,415,652 Patented Dec. 10, 1968 forming layers either alone or together with image forming compounds other than silver halide, such as, for example zinc oxide, cadmium sulfide, cadmium selenide, Zinc sulfide, nickel sulfide, etc., either with or without a binder.
  • My compounds retain the advantage of the prior art two-equivalent couplers while, at the same time avoid the disadvantage of color fog. Further, my couplers exhibit a high reactivity, unlike many of the previously described two-equivalent couplers. The sulfonyloxy group appears to be more readily eliminated from the coupler during the coupling reaction (i.e., with oxidized color developer) than does any one of a number of the prior art coupling-ofi groups. Consequently, my couplers exhibit a higher reactivity in the color-forming or coupling reaction.
  • My new couplers contain at least one open chain nucleus containing an active methylene group separating and joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, said active methine group having only one hydrogen atom substituted by a group wherein R, is a carbon-containing radical.
  • the said acyl and said amide radicals can be any of the acyl and amide radicals found in known coupler compounds since my couplers are derived to advantage from any of the known four-equivalent couplers.
  • the acyl radical can contain an organic radical that is open chain isocyclic, bicyclic, heterocyclic etc. in which each of these radicals can be saturated, unsaturated, sub stituted or unsubstituted.
  • the amide radical can contain an amino group or any of the substituted amino groups found in couplers.
  • My new class of couplers includes those represented by the following formula:
  • R represents an organic radical, e.g. open chain, isocyclic, bicyclic, heterocyclic, etc. in which the radicals can be saturated, unsaturated, substituted, or unsubstituted, for example, an alkyl group, especially those having from 1 to 22 carbon atoms, e.g., methyl, 3-pentadecylphenoxymethyl, ethyl, phenylethyl, n-propyl, isopropyl, u-(ZA-di-t-amylphenoXy)-propyl, d-sulfobutyl, sec-butyl, tert-buty1, docosyl, chloromethyl, trifluoromethyl, Z-hydroxymethyl, fi-carboxyethyLZ-(QA; 6 trichlorophenyl) ethyl, 2 aminoethyl, 01,01.
  • R represents an organic radical, e.g. open chain, isocyclic, bicyclic,
  • a terpenyl group especially groups, such as 7,7-dimethylnorbornyl, 2-alky1- 7,7-dimethylnorbornyl radicals in which the alkyl group has from 1 to 18 carbon atoms, such as methyl, butyl, octadecyl, etc., for example, Z-methyl-7,7-dimethylnorbornyl, 2-octadecyl-7,7-dimethylnorbornyl, etc., a 2-ary1
  • R and R each represent the same or dilferent member, e.g., hydrogen, an alkyl group (substituted or not) especially in which the alkyl group has from 1 to 22
  • Couplers such as Nos. 11 and 12 illustrate those that are incorporated as Fischer-type couplers.
  • the other couplers such as Nos. 1-6 and 13-20 are incorporated in emulsion layers by methods such as those described by US. Patent 2,304,939, issued Dec. 15, 1942, US. patent 2,322,027, issued June 15, 1943, etc., in which high boiling organic solvents are used to dissolve the coupler, and by methods described in US. Patent 2,801,170, and Patent 2,801,171, both issued July 30, 1957, US. Patent 2,949,360, issued Aug. 16, 1960, in which low boiling or water soluble solvents are used with or in place of the high boiling solvent.
  • Coupler No. 8 fonrns a diffusi-ble dye upon color development and can be used to advantage either in image transfer elements or in emulsion layers as a non-image-forzning competing coupler together with an image-forming competing coupler. Coupler No.
  • Coupler No. 21 contains a preformed dye attached to the coupler on the phenylsulfonyloxy group. This dye is eliminated on the coupling of the coupler with an oxidized color developer and diffuses out of the film.
  • This coupler can be used as a magenta-colored coupler for the purpose of correcting for the unwanted green absorption of yellow image dye, i.e., that formed from the coupler itself as well as that formed from other yellow couplers. Generally, such a coupler as this would be used in combination with another imageforming yellow coupler in the same layer.
  • any of the well known primary aromatic amino colorforming silver halide developing agents such as the phenylenediamines, e.g., diethyl-p-phenylenediamine hydro chloride, monomethyl-p-phenylenediamine hydrochloride dimethyl-pphenylenediamine hydrochloride, 2-amino-5- diethylaminotoluene hydrochloride, 2amino-5-(N-ethyl- N-lauryDtoluene, N-ethyl-B-methanesulfonamidoethyl-3- methyl-4-aminoaniline sulfate, N-ethyl-fi-methanesulfonamidoethyl-4-aminoaniline, 4-N-ethyl-N-B-hydroxyethvlaminoaniline, etc., the p-aminophenols and their substitution products where the amino group is unsubstituted may be used to
  • Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulrfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions.
  • My couplers are used in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type in the emulsion layer.
  • the emulsions may contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoidide, silver chlorobromoiodide, etc., as the light-sensitive material.
  • Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a snythetic resin, for instance, a polyvinyl compound.
  • Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in US. Patent 2,286,215, a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, as described in US. Patent 2,327,808, a water-soluble ethanolamine cellulose acetate as described in US.
  • Patent 2,322,085 a polyacrylamide having a combined acrylamide content of 60% and a specific viscosity of 025-15 or an imidized polyacrylamide of like acrylamide content and viscosity as described in 11.8.
  • the emulsions can be digested with naturally active gelatin, or sulfur compounds can be added.
  • the emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition.
  • the emulsions can also be chemically sensitized with gold salts, or stabilized with gold salts.
  • the emulsions can also be optically sensitized with dyes such as cyanine and merocyanine dyes.
  • the emulsions may also contain speed-increasing compounds of the quaternary ammonium type or of the polyethylene glycol type.
  • Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass and others.
  • my emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support.
  • the support is coated in succession with a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers.
  • the three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer.
  • these light-sensitive layers are arranged on the same side of the support.
  • Elements made for image transfer processing may use a separate reception sheet which is contacted with the light-sensitive layer during its development or the reception layer may be an integral part of the light-sensitive element. Any of the support materials mentioned previously may be used for a separate reception sheet.
  • the reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in US. Patent 2,882,156, granted Apr. 14, 1959.
  • Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in US. Patent 2,484,430, granted Oct. 11, 1949,
  • Strips of the above coatings were given -second exposure on a 1B intensity scale sensitometer and processed through the following process:
  • the resulting yellow dye images were observed with a spectrophotometer to determine the A max. values and examined with a densitometer to determine the D max. values.
  • the photo data are given for the above mentioned processed strips in Table I.
  • Couplers 3, 4 and 5 Single layer coatings similar to those described in Example 1 were prepared using Couplers 3, 4 and 5, respectively, except that in making these coatings no high boiling coupler solvent was used.
  • the couplers were dispersed using ethyl acetate as the only solvent. Typically, after such a dispersion is made it is chilled and the ethyl acetate solvent is removed by washing the chilled gelatin dispersion with cold water. This technique of dispersing couplers has been previously disclosed in the literature reference above. These coatings were processed in the same manner as those of Example 1. Photo data similar to that obtained in Example 1 were also obtained on these processed strips. This data is given in Table 11 below.
  • EXAMPLE 4 Single layer coatings similar in structure to those given in Example 1 above are prepared using compounds Nos. 7 and 8 respectively. Exposed strips of these coatings are processed by developing them for five minutes at 75 F. in contact with a mordant containing receiving sheet which had been presoaked in the following developer solution.
  • the films are removed from the mordant receiving sheets in which sheets are contained the transferred and mordanted yellow dye images, respectively.
  • couplers of my invention are used to advantage in color photography as illustrated previously with representative couplers.
  • the couplers of my invention are valuable as yellow image-forming couplers in multilayer photographic color films containing other classes of couplers in the other layers of said film.
  • Such other couplers are, for example, magneta-forming pyrazolones, cyanoacetyl coumarones, indazolones, etc., and cyan couplers such as naphthols and phenols.
  • coupler No. 4 The following preparation of coupler No. 4 will illustrate the syntheses of my yellow forming couplers:
  • Couplers 18 and 11-19 are prepared by similar reactions using the intermediates given in Table III below.
  • Coupler Coupler intermediate Silver salt of sulionio No. acid 1 a-Bromo-a-pivalyl-2-chloro-fi-[w- Methyl sulfonic acid.
  • Compound No. 9 is prepared by the catalytic (i.e., using palladium on charcoal as the catalyst) reduction of Compound No. 8.
  • Compound No. 10 is prepared by acylating Compound No. 9 using a-(3-pentadecylphenoxy) acetyl chloride in acetic acid containing sodium acetate as the condensing agent.
  • Compound No. is prepared by the catalytic (i.e., using palladium on charcoal as the catalyst) reduction of Compound No. 19.
  • Compound No. 21 is prepared by the diazotization of Compound No. 20 and the subsequent coupling of the diazo salt with acetyl H-acid disodium salt.
  • the two-equivalent image-forming couplers of m invention are distinguished from other two-equivalent couplers by having a sulfonyloXy group substituted on the coupling position of the coupler molecule.
  • My couplers are characterized by not producing color fog, a problem with certain prior art two-equivalent couplers, and by having very good coupling reactivity.
  • These couplers are dispersed readily in emulsion layers as a coupler solvent solution having a wide range of coupler to solvent ratios.
  • My couplers are not only valuable for the reasons cited, but because photographic emulsion layers color developed with them require only one-half the amount of silver halide required by four-equivalent couplers. Of particular value are certain of my nondilfusing couplers which have high coupling reactivity when dispersed in photographic emulsion layers without any high boiling solvent. These couplers are coated to advantage in particularly thin layers that produce good sharp images.
  • the couplers of my invention may be used in emulsion layers either alone or admixed with other couplers, either fouror two-equivalent couplers, competing couplers, and the like.
  • An image-forming layer containing a silver halide emulsion and a coupler which is capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent, said coupler containing from 1 to 2 open chain nuclei, each nucleus containing an active methylene group joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, so that when the said coupler contains one open chain nucleus its active methylene group is substituted by R S0 O- wherein R represents a group selected from the class consisting of an alkyl group and an aryl group, and when the said coupler has two nuclei the active methylene group of one open chain nucleus is connected to the active methylene group of the other open chain nucleus through a OSO R SO O group and R represents a group se'ected from the class consisting of an alkylene group and an arylene group.
  • n represents an integer of from 1 to 2;
  • R represents a group selected from the class consisting of an alkyl group, a terpenyl group, an aryl group, and a heterocyclic group;
  • R and R each represent a member selected from the class consisting of hydrogen, an alkyl group, an aryl group and a heterocyclic group;
  • R when n represents the integer 1, represents a group selected from the class consisting of an alkyl group and an aryl group, and, when n represents the integer 2, represents a group selected from the class consisting of an alkylene group and an arylene group.
  • a coupler which is capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent, said coupler containing from 1 to 2 open chain nuclei, each nucleus containing an active methylene group joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, so that when the said coupler contains one open chain nucleus its active methylene group is substituted by R SO O- wherein R represents a group selected from the class consisting of an alkyl group and an aryl group, and when the said coupler has two nuclei the active methylene group of one open chain nucleus is connected to the active methylene group of the other open chain nucleus through a OSO R SO O group and R represents a group selected from
  • n represents an integer of from 1 to 2;
  • R represents a group selected from the class consisting of an alkyl group, a terpenyl group, an aryl group, and a heterocyclic group;
  • R and R each represents a group selected from the class consisting of hydrogen, an alkyl group, an aryl group and a heterocyclic group;
  • R when n is the integer 1, represents a group selected from the class consisting of an alkyl group and an aryl group, and, when n is the integer 2, represents a group selected from the class consisting of an alkylene group and an arylene group.
  • an image-forming layer containing a silver halide emulsion comprising the use of a coupler which is capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent, said coupler containing from 1 to 2 open chain nuclei, each nucleus containing an active methylene group joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, so that when the said coupler contains one open chain nucleus its active methylene group is substituted by R SO O-- wherein R represents a group selected from the class consisting of an alkyl group and wherein n represents an integer of from 1 to 2; R represents a group selected from the class consisting of an alkyl group; a terpenyl group, an aryl group, and a heterocyclic group; R and R each represents a group selected from the class consisting of hydrogen, an alkyl group

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

United States Patent 0 3,415,652 SILVER HALIDE COLOR PHOTOGRAPHIC ELEMENTS UTILIZING ALPHA-SULFO- NYLOXY SUBSTITUTED TWO-EQUIVA- LENT YELLOW-FORMING COUPLERS Ralph F. Porter, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Apr. 1, 1965, Ser. No. 444,822
11 Claims. (CI. 96-100) ABSTRACT OF THE DISCLOSURE Alpha-sulfonyloxy substituted 2-equivalent yellow dyeforming couplers are used to advantage for forming yellow dye images in color photography, particularly because these couplers are characterized by not producing color fog and having very good coupling reactivity.
This invention rel-ates to color photography and more particularly to novel dye-forming coupler compounds for use in image forming systems and processes utilizing such compounds for the formation of images. In particular, my invention relates to two-equivalent coupler compounds for forming yellow dye images in color photography.
The formation of colored photographic images by coupling the oxidation product of an aromatic amino developing agent with color-forming compounds is well known. Presently, the subtractive color process is most frequently used, and the image dyes are of the primary colors cyan, magenta and yellow for the red, green and blue records respectively. The couplers which form the cyan dyes are usually phenols or naphthols; those forming the magenta dyes are generally pyrazolones or cyanoacetyl compounds; and those forming the yellow dyes are open-chain compounds containing a methylene group having two carbonyl groups attached to it.
Most of the above mentioned couplers which have been used in the previously described color processes are four-equivalent couplers, that is, they require 4 mols of silver halide for the formation of 1 mol. of dye. However, certain of the prior art couplers which are two-equivalent couplers, i.e., requiring only 2 mols of silver halide for the formation of 1 mol of dye, for example the couplers described in French Patent 991,453, British Patent 805,505, etc. New two-equivalent couplers are desired that have improved characteristics for use in color photography.
It is an object of my invention to provide novel improved couplers which are capable of forming yellow dye with the oxidation product of an aromatic amino color developing agent. It is a further object of my invention'to provide new and improved couplers capable of forming yellow dye with the oxidation product of an aromatic. amino developing agent and which couplers require less silver halide development to produce a given amount of dye than do the analogous prior art fourequivalent couplers. It is a further object of my invention to provide new and improved two-equivalent lowfogging yellow-forming couplers having good reactivity so that processing can be accomplished in a reasonable time and without prolonging development or without requirement for excessively high pH or high temperature processing conditions. Another object is to provide new two-equivalent couplers which have good reactivity even when incorporated in silver halide emulsion layers without any high boiling couplers solvents. Another object is to provide new couplers which are valuable for use in any of the image forming systems (silver or non silver) where couplers are used to advantage, for example the coupler can be used to advantage in image 3,415,652 Patented Dec. 10, 1968 forming layers either alone or together with image forming compounds other than silver halide, such as, for example zinc oxide, cadmium sulfide, cadmium selenide, Zinc sulfide, nickel sulfide, etc., either with or without a binder.
These and other objects which will appear from the following description of my invention are accomplished by the use of my oc-SLllfOnYlOXY substituted two-equivalent couplers.
My compounds retain the advantage of the prior art two-equivalent couplers while, at the same time avoid the disadvantage of color fog. Further, my couplers exhibit a high reactivity, unlike many of the previously described two-equivalent couplers. The sulfonyloxy group appears to be more readily eliminated from the coupler during the coupling reaction (i.e., with oxidized color developer) than does any one of a number of the prior art coupling-ofi groups. Consequently, my couplers exhibit a higher reactivity in the color-forming or coupling reaction.
My new couplers contain at least one open chain nucleus containing an active methylene group separating and joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, said active methine group having only one hydrogen atom substituted by a group wherein R, is a carbon-containing radical. The said acyl and said amide radicals can be any of the acyl and amide radicals found in known coupler compounds since my couplers are derived to advantage from any of the known four-equivalent couplers. For example, the acyl radical can contain an organic radical that is open chain isocyclic, bicyclic, heterocyclic etc. in which each of these radicals can be saturated, unsaturated, sub stituted or unsubstituted. The amide radical can contain an amino group or any of the substituted amino groups found in couplers.
My new class of couplers includes those represented by the following formula:
wherein n represents 1 or 2; R represents an organic radical, e.g. open chain, isocyclic, bicyclic, heterocyclic, etc. in which the radicals can be saturated, unsaturated, substituted, or unsubstituted, for example, an alkyl group, especially those having from 1 to 22 carbon atoms, e.g., methyl, 3-pentadecylphenoxymethyl, ethyl, phenylethyl, n-propyl, isopropyl, u-(ZA-di-t-amylphenoXy)-propyl, d-sulfobutyl, sec-butyl, tert-buty1, docosyl, chloromethyl, trifluoromethyl, Z-hydroxymethyl, fi-carboxyethyLZ-(QA; 6 trichlorophenyl) ethyl, 2 aminoethyl, 01,01. dimethylbutyl, a-methoxy-a-methyloctyl, a-propyl-u-octyldocosyl, a,a-dibutyl-docosyl, u,a-di-decylundecyl, 0:,a-di-t-bl1tYldodecyl, a,ot-di-secbutylpentadecyl, etc., a terpenyl group, especially groups, such as 7,7-dimethylnorbornyl, 2-alky1- 7,7-dimethylnorbornyl radicals in which the alkyl group has from 1 to 18 carbon atoms, such as methyl, butyl, octadecyl, etc., for example, Z-methyl-7,7-dimethylnorbornyl, 2-octadecyl-7,7-dimethylnorbornyl, etc., a 2-ary1- 7,7-dimethylnorbornyl radical, such as 2-phenyl-7,7- dimethylnorbornyl, 2-totyl-7,7-dimethylnorbornyl, etc., an aryl group including aryl groups, such as, phenyl, 3- (2-carboxybenzamido phenyl, 3- (,B-sulfopropionarnido phenyl, a-naphthyl, fl-naphthyl, 2,4,6-trichlorophenyl, 4-
ethoxyphenyl, 4-bromophenyl, 4-fluorophenyl, 3-[a-(2-4- di t amyl phenoxy)butyramido] phenyl, 3- ['y-(Z-4-ditamylphenoxy)butyramido]phenyl, etc., a heterocyclic radical including radicals such as, a benzofuranyl group, a furanyl group, a thiazolyl group, a benzothiazolyl group, anaphthothiazolyl group, an oxazolyl group, a benzoxazolyl group, an imidazolyl group, a benzirnidazolyl group, a quinolinyl group, etc., all of which are substituted or not; R and R each represent the same or dilferent member, e.g., hydrogen, an alkyl group (substituted or not) especially in which the alkyl group has from 1 to 22 carbon atoms (e.g., methyl, carbethoxyrnethyl, dodecyl, docosyl, 2-sulfoethyl, Z-chlorobutyl, 2-hydroxyethyl, 2-phenylethyl, etc.), an aryl group (e.g., phenyl, Z-methOXyphenyl, 4-methylphenyl, 4-[a-(2,4-di t amylphenoxy)butyramidolphenyl, 4 sulfamylphenyl-4-[5-(3-chlorosulfonylbenZamido)-2-(2,4 di t arnylphen0xy)benzamido]phenyl, 2,4,6-trichlorophenyl, 3,5-dibr0mophenyl, 3,5-dicarbomethoxyphenyl, 3,5-dicarboxyphenyl, naphthyl, 3-ethylnaphthyl, etc.), a heterocyclic group, such as a thiazolyl group (e.g., 4,5-dicarbethoxy-Z-thiazolyl, S-carbethoxy-Z- thiazolyl, thiazolyl, etc.), a benzothiazolyl group, a naphthothiazolyl group, an oxazolyl group, a benzoxazolyl group, a naphthoxazolyl group, an imidazolyl group, a benzimidazolyl group, a naphthimidazolyl group, a pyridyl group, a quinolyl group, etc.); R when n21, represents an alkyl groups substituted or not and especially those of from C to C e.g., methyl, ethyl, octadecyl, 2-carboxyethyl, 4-sulfobutyl, S-hydroxypentyl, 2-chloroethyl, t-butyl, 3-carbethoxypropyl, 4-mcthoxybutyl, etc., an aryl group substituted or not and especially a group such as phenyl, 3-aminophenyl, 4-methylphenyl, 3-carboXyphenyl, 4-sulfophenyl, 3-hydroxyphenyl, 4-cyanophenyl, 3-nitrophenyl, 2-chlorophenyl, 4-ethoxyphenyl, 3 octadecylcanbamylphenyl, 4 butyramidophenyl, 3- docosylphenyl, l-naphthyl, etc; R when n=2, represents a bivalent organic radical, such as, alkylene from C to C similar to alkyl above, e.g., ethylene, propylene, Z-carboxypropylene, 3-hydroxybutylene, etc., arylene, e.g., m-phenylene, 5-carbomethoXy-m-phenylene, 5-octadecyloxy-m-phenylene, 5-carbomethoxy-m-phenylene, S- octadecyloxy-m-phenylene, etc.
The following typical couplers will serve to illustrate but not limit my invention. (1) 0c Methylsulfonyloxy 0c pivalyl 2 chloro 5- ['y- 2,4-di-t-amylphenoxy) butyramido 1 acetanilide (CH3) aCCOCHC ONH NI1CO(CH2)3O S02 CH3 csHn-li (2) u Pivalyl a (p tolylsulfonyloxy) 2 chloro- 5-['y-(2,4 di-t-amylphenoxy)butyramido1acetanilide (3) oz Methylsulfonyloxy u pivalyl 2 chloro 4- N-methyl-N-octadecylsulfamyl) acetanilide (4) a Methylsulfonyloxy a pivalyl 4 (N methyl- N-octadecylsulfamyl) acetanilide (5) a Methylsulfonyloxy 0c pivalyl 2,5 dichloro- 4- N-methyl-N-octadecylsulfamyl acetanilide (6) a {3 [0L (2,4 di t amylphenoxy)butyramido] benzoyl}tat-methylsulfonyloxy-2-methoxyacetanilide (7) a (4 octadecyloxyphenylsulfonyloxy) 0L pivalyl- 4-sulfarnylacetanilide I SO:
orrmoootlnrrc oNrr- I COOH (11) a (2 methoxybenzoyl) a propylsulfonyloxy 4 [2 (2,4 di t amylphenoxy) 5 (3 sulfobenzamido) benzamido1acetanilide sodium salt (12) 0t (6 Carboxybutylsulfonyloxy) u 3 [a- (2,4 di 1t amylphenoxy) butyramido]benzoyl}-2- methoxyacetanilide (13) a (6 Carbomethoxybutylsulfonyloxy) a {3 [a (2,4 di t amylphenoxy)butyrarnidoqbenzoyl} Z-methoxyacetanilide (14) a Octadecylsulfonyloxy a pivalyl N,N bis- (carbethoxymethyl acetamide (15) a Benzoyl a docosylsulfonyloxy N (4,5 dicarbethoxy-Z-thiazolyl) acetamide I SIOz cur c OCI'ICONHC l (I) N-C-COOCzHs S 02 (16) a Furoyl on ('y hydroxypropylsulfonyloxy) 4 ['y- 3-pentadecylpl1enoxy butyramido] acetanilide I C 151131 S 02 (Clinton (17) a (7,7 dimethylnorbornyl 1 carbonyl) on (8-ethoxyoctylsulfonyloxy -3-palmitamido acetanilide (18) oz,oc' Ethylenedisulfonyloxybis{a benzoyl 4 [cc 2,4-di-t-amylphenoxy) acetamido] acetanilide} I laHn-t (19) u (4 nitrophenylsulfonyloxy) a pivalyl 3 [v- 2,4-di-t-amylphenoxy butyramido] acetanilide (20) a 4 aminophenylsulfonyloxy) oz pivalyl 3 ['y- 2,4-di-t-amylphenoxy butyramido] acetanilide (21) u [4 (8 acetamido 3,6 disulfo 1 hydroxy 2 naphthylazo)phenylsulfonyloxy] u pivalyl 3 ['y- 2,4-di-t-amylphenoxy butyramido acetanilide The couplers of my invention are nondilfusible and are used to advantage in photographic emulsion layers. Couplers such as Nos. 11 and 12 illustrate those that are incorporated as Fischer-type couplers. The other couplers such as Nos. 1-6 and 13-20 are incorporated in emulsion layers by methods such as those described by US. Patent 2,304,939, issued Dec. 15, 1942, US. patent 2,322,027, issued June 15, 1943, etc., in which high boiling organic solvents are used to dissolve the coupler, and by methods described in US. Patent 2,801,170, and Patent 2,801,171, both issued July 30, 1957, US. Patent 2,949,360, issued Aug. 16, 1960, in which low boiling or water soluble solvents are used with or in place of the high boiling solvent. Not only can emulsion layers containing my couplers be made thinner because they require only one-half the silver halide required by conventional couplers (i.e., four-equivalent couplers), but some of my couplers are sufficiently reactive so that they do not require any high boiling coupler solvent that is usually required by couplers. The thin image-forming layers are very desirable because they cause less light scattering and produce sharper images. Coupler No. 8 fonrns a diffusi-ble dye upon color development and can be used to advantage either in image transfer elements or in emulsion layers as a non-image-forzning competing coupler together with an image-forming competing coupler. Coupler No. 7 has a sulfamyl group on a non-coupling position which ionizes and forms a diffusible dye upon color development at a pH above 11 and a nondiffusi ble dye at a pH below 11. Coupler No. 21 contains a preformed dye attached to the coupler on the phenylsulfonyloxy group. This dye is eliminated on the coupling of the coupler with an oxidized color developer and diffuses out of the film. This coupler can be used as a magenta-colored coupler for the purpose of correcting for the unwanted green absorption of yellow image dye, i.e., that formed from the coupler itself as well as that formed from other yellow couplers. Generally, such a coupler as this would be used in combination with another imageforming yellow coupler in the same layer.
Any of the well known primary aromatic amino colorforming silver halide developing agents such as the phenylenediamines, e.g., diethyl-p-phenylenediamine hydro chloride, monomethyl-p-phenylenediamine hydrochloride dimethyl-pphenylenediamine hydrochloride, 2-amino-5- diethylaminotoluene hydrochloride, 2amino-5-(N-ethyl- N-lauryDtoluene, N-ethyl-B-methanesulfonamidoethyl-3- methyl-4-aminoaniline sulfate, N-ethyl-fi-methanesulfonamidoethyl-4-aminoaniline, 4-N-ethyl-N-B-hydroxyethvlaminoaniline, etc., the p-aminophenols and their substitution products where the amino group is unsubstituted may be used to develop photographic coatings containing my couplers. Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulrfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions.
My couplers are used in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type in the emulsion layer. The emulsions may contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoidide, silver chlorobromoiodide, etc., as the light-sensitive material.
Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a snythetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in US. Patent 2,286,215, a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, as described in US. Patent 2,327,808, a water-soluble ethanolamine cellulose acetate as described in US. Patent 2,322,085; a polyacrylamide having a combined acrylamide content of 60% and a specific viscosity of 025-15 or an imidized polyacrylamide of like acrylamide content and viscosity as described in 11.8. Patent 2,541,474, zein as described in US. Patent 2.563.791, a vinyl alcohol polymer containing urethane carboxvlic acid groups of the type described in US. Patent 2.768154. or containing cayano-acetyl groups, such as the vinyl alcohol-vinvl cyanoacetate copolymer as described in US. Patent 2,808,331, or a polymeric material which results from polymerizing a protein or a satusensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added. The emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition. The emulsions can also be chemically sensitized with gold salts, or stabilized with gold salts. The emulsions can also be optically sensitized with dyes such as cyanine and merocyanine dyes. The emulsions may also contain speed-increasing compounds of the quaternary ammonium type or of the polyethylene glycol type.
The above-described emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass and others.
Usually my emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers. The three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.
Elements made for image transfer processing may use a separate reception sheet which is contacted with the light-sensitive layer during its development or the reception layer may be an integral part of the light-sensitive element. Any of the support materials mentioned previously may be used for a separate reception sheet. The reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in US. Patent 2,882,156, granted Apr. 14, 1959. Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in US. Patent 2,484,430, granted Oct. 11, 1949,
, and cetyl trimethyl ammonium bromide, etc.
My invention is further illustrated by the following typical examples.
EXAMPLE 1 Single layer camera speed gelatin silver bromoiodide emulsions containing yellow-forming coupler and coupler solvent di-n-butyl phthalate were made for my couplers Nos. 3, 4 and 5 respectively. The coatings contained 10 parts of gelatin, 5 parts of silver halide, 2 parts of coupler and 1 part of coupler solvent by weight.
Strips of the above coatings were given -second exposure on a 1B intensity scale sensitometer and processed through the following process:
Time: Process steps 30" Water dip. 10 Development. 5' Stop bath. 5 Ferricyanide bleach. 5 Wash.
5 Fixing bath. l0" Wash. 30" Photo-Flo (wetting agent solution).
The following developer solutions were used:
Developer 1 G. Sodium sulfite (anhydrous) 2 2-amino-5-diethylaminotoluene HCl 2 Sodium carbonate monohydrate Potassium bromide 2 Water to 1 liter. pH 10.86.
Developer 2 Benzyl alcohol ml 4.00 Sodium sulfite (anhydrous) g 2.00 N-ethyl-B-methanesulfonamidoethyl 4 aminoanilinesulfate g 5.00 Sodium carbonate monohydrate g 50.00 Sodium bromide g 0.86 Sodium hydroxide (20% solution) ml 4.00 Sodium hexametaphosphate g 0.50 Water to 1.00 liter. pH 10.75.
The resulting yellow dye images were observed with a spectrophotometer to determine the A max. values and examined with a densitometer to determine the D max. values. The photo data are given for the above mentioned processed strips in Table I.
Single layer coatings similar to those described in Example 1 were prepared using Couplers 3, 4 and 5, respectively, except that in making these coatings no high boiling coupler solvent was used. In place of the di-n-butyl phthalate coupler solvent used in the coatings of Example 1, the couplers were dispersed using ethyl acetate as the only solvent. Typically, after such a dispersion is made it is chilled and the ethyl acetate solvent is removed by washing the chilled gelatin dispersion with cold water. This technique of dispersing couplers has been previously disclosed in the literature reference above. These coatings were processed in the same manner as those of Example 1. Photo data similar to that obtained in Example 1 were also obtained on these processed strips. This data is given in Table 11 below.
A comparison of the D max. values given for these dye images with those for the same couplers in the coatings of Example 1 shows clearly that the reactivity of the coupler remains essentially unchanged when coated with no coupler solvent.
8 EXAMPLE 3 Single layer coatings similar in structure to those given in Example 1 above were made containing Compound 1. The coating containing this coupler was exposed and processed similar to the process given in Example 1 above using Developer 1 of Example 1. The D max. of the image dye in the coating containing my coupler No. l was 3.14.
EXAMPLE 4 Single layer coatings similar in structure to those given in Example 1 above are prepared using compounds Nos. 7 and 8 respectively. Exposed strips of these coatings are processed by developing them for five minutes at 75 F. in contact with a mordant containing receiving sheet which had been presoaked in the following developer solution.
G. Sodium carbonate monohydrate 22 Ascorbic acid 0.24 Potassium bromide 0.8 Sodium sulfite (anhydrous) 2.0 4-amino-N-ethyl-N-,8-hydroxyethylaniline sulfate 11.0 Water to make 1.0 liter. pH adjusted to 12.5 using 20% sodium hydroxide solution.
After the development period, the films are removed from the mordant receiving sheets in which sheets are contained the transferred and mordanted yellow dye images, respectively.
Similarly, other couplers of my invention are used to advantage in color photography as illustrated previously with representative couplers. Further, the couplers of my invention are valuable as yellow image-forming couplers in multilayer photographic color films containing other classes of couplers in the other layers of said film. Such other couplers are, for example, magneta-forming pyrazolones, cyanoacetyl coumarones, indazolones, etc., and cyan couplers such as naphthols and phenols.
In general, my couplers are prepared from the parent coupler having the formula:
wherein R, R and R are as described previously, by reacting the parent coupler with the silver salt of a sulfonic acid, said salt having the formula [AgOSO R in which R and n are as defined previously. The above mentioned u-bromo couplers can be prepared by methods similar to those in, for example, McCrossen et al. US. Patent 2,728,658, issued Dec. 27, 1955, in which patent is described the preparation of a-chloro yellow couplers.
The following preparation of coupler No. 4 will illustrate the syntheses of my yellow forming couplers:
A mixture of 26 g. of a-brorno-a-pivalyl-4-(N-methyl- N-octadecylsulfamyl)acetanilide and 9 g. of methyl sulfonic acid silver salt in 400 ml. of acetonitrile was refluxed for 24 hours, after which time the silver bromide which precipitated was collected. The filtrate was concentrated in vacuo and the residue was dissolved in 500 ml. of ethyl acetate, which solution was filtered to remove a small amount of insoluble material. This filtrate was washed with water, twice with 250 ml. portions of 1% sodium bromide solution, and then dried over sodium sul-- fate. The dried solution was separated from the sodium sulfate and concentrated in vacuo. The solid residue was recrystallized twice from 300 ml. of acetonitrile, yielding 23 g. of product, M.P. 9496 C.
Couplers 18 and 11-19 are prepared by similar reactions using the intermediates given in Table III below.
TABLE III Coupler Coupler intermediate Silver salt of sulionio No. acid 1 a-Bromo-a-pivalyl-2-chloro-fi-[w- Methyl sulfonic acid.
(2,4-di-t-an1ylphcnoxy)butyramidolacetanilide. 2 Same as No. 1 above p-Toluenc snlfonic acid 3-.- a-Bromo-a-pivalyl-2-chloro-4- Methyl sullonic acid.
(N-mcthyl-N-octadeoylsultamyl} acctanilide.
4 u-Brmno-a-pivalylA-(N-metliyl- Do.
N-octadecylsullamyl)aoctanilide 1 5 a-Bromo-a-pivalyl-2. 5-dicliloro- Do.
4-(N-methyl-N-octadecylsultamyl; aectanilidc.
6...- wBromo-a-l3-[1-(2,4-di-t-amyl- Do.
phenoxy)butyramidolhcnzolyl-Z- metboxyacetanilide.
7 a-Brome-m-oivalvl- '.sulfan*-yl 4-Octadeeyloxyheuncctanilidc. zene sulionic acid 1.)
8 wBromo-n-pi alyl-ii. -dicarb- S-Nitmheuzene suloxyacctanilide. Ionic acid. I
11 a-Bromo-o-lZ-methorybenzoyb- Propyl-l-suliomc acid.
4-[r1-(2,4-di-t-amylphenoxy)-5- (3-snifobenzamido)benzaniidolacetanilidc sodium salt.
-0 arbo .rybutvl-l- Compound No. 9 is prepared by the catalytic (i.e., using palladium on charcoal as the catalyst) reduction of Compound No. 8. Compound No. 10 is prepared by acylating Compound No. 9 using a-(3-pentadecylphenoxy) acetyl chloride in acetic acid containing sodium acetate as the condensing agent. Compound No. is prepared by the catalytic (i.e., using palladium on charcoal as the catalyst) reduction of Compound No. 19. Compound No. 21 is prepared by the diazotization of Compound No. 20 and the subsequent coupling of the diazo salt with acetyl H-acid disodium salt.
The two-equivalent image-forming couplers of m invention are distinguished from other two-equivalent couplers by having a sulfonyloXy group substituted on the coupling position of the coupler molecule. My couplers are characterized by not producing color fog, a problem with certain prior art two-equivalent couplers, and by having very good coupling reactivity. These couplers are dispersed readily in emulsion layers as a coupler solvent solution having a wide range of coupler to solvent ratios.
My couplers are not only valuable for the reasons cited, but because photographic emulsion layers color developed with them require only one-half the amount of silver halide required by four-equivalent couplers. Of particular value are certain of my nondilfusing couplers which have high coupling reactivity when dispersed in photographic emulsion layers without any high boiling solvent. These couplers are coated to advantage in particularly thin layers that produce good sharp images. The couplers of my invention may be used in emulsion layers either alone or admixed with other couplers, either fouror two-equivalent couplers, competing couplers, and the like.
The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be eifected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
I claim:
1. An image-forming layer containing a silver halide emulsion and a coupler which is capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent, said coupler containing from 1 to 2 open chain nuclei, each nucleus containing an active methylene group joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, so that when the said coupler contains one open chain nucleus its active methylene group is substituted by R S0 O- wherein R represents a group selected from the class consisting of an alkyl group and an aryl group, and when the said coupler has two nuclei the active methylene group of one open chain nucleus is connected to the active methylene group of the other open chain nucleus through a OSO R SO O group and R represents a group se'ected from the class consisting of an alkylene group and an arylene group.
2. An image-forming layer containing a silver halide emulsion and a two-equivalent yellow dye-forming coupler of the formula:
wherein n represents an integer of from 1 to 2; R represents a group selected from the class consisting of an alkyl group, a terpenyl group, an aryl group, and a heterocyclic group; R and R each represent a member selected from the class consisting of hydrogen, an alkyl group, an aryl group and a heterocyclic group; R when n represents the integer 1, represents a group selected from the class consisting of an alkyl group and an aryl group, and, when n represents the integer 2, represents a group selected from the class consisting of an alkylene group and an arylene group.
3. A light-sensitive hydrophi ic colloid silver halide emu'sion layer containing a-methylsulfonyloXy-a-pivalyl- 2-chloro-4- (N-methyl-N-octadecylsulfamyl) acetanilide.
4. A light-sensitive hydrophilic colloid silver halide emulsion layer containing ot-methylsulfonyloXy-a-pivalyl- 4-(N-methyl-N-octadecylsulfamyl)acetanilide.
5. A light-sensitive hydrophilic colloid silver halide emulsion layer containing a-methylsulfonyl0Xy-a-pivalyl 2,5-dichloro-4-(N-methyl-N octadecylsulfamyl)acetanilide.
6. A light-sensitive hydrophilic colloid silver halide emulsion layer containing u-{S-[a-(3-pentadecylphenoxy) acetamido]phenylsulfonyloxy}-u-pivalyl-3,5 dicarboxyacetanilide.
7. A light-sensitive hydrophilic colloid silver halide emulsion layer containing c d-ethylenedisulfonyloxybis(abenzoyl 4 [oz-(2,4 di t amylphenoxy)acetamido] acetanilide.
8. In a multilayer, multicolor element containing a silver halide emulsion and incorporated color-forming couplers, the improvement comprising the incorporation of a coupler which is capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent, said coupler containing from 1 to 2 open chain nuclei, each nucleus containing an active methylene group joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, so that when the said coupler contains one open chain nucleus its active methylene group is substituted by R SO O- wherein R represents a group selected from the class consisting of an alkyl group and an aryl group, and when the said coupler has two nuclei the active methylene group of one open chain nucleus is connected to the active methylene group of the other open chain nucleus through a OSO R SO O group and R represents a group selected from the class consisting of an alkylene group and an arylene group.
9. In a multilayer multicolor element containing a silver halide emulsion and incorporated color-forming couplers, the improvement comprising the incorporation of a coupler having the formula:
wherein n represents an integer of from 1 to 2; R represents a group selected from the class consisting of an alkyl group, a terpenyl group, an aryl group, and a heterocyclic group; R and R each represents a group selected from the class consisting of hydrogen, an alkyl group, an aryl group and a heterocyclic group; R when n is the integer 1, represents a group selected from the class consisting of an alkyl group and an aryl group, and, when n is the integer 2, represents a group selected from the class consisting of an alkylene group and an arylene group.
10. In an image-forming layer containing a silver halide emulsion, the improvement comprising the use of a coupler which is capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent, said coupler containing from 1 to 2 open chain nuclei, each nucleus containing an active methylene group joined directly to the carbon atoms of two carbonyl groups, one of said carbonyl groups being part of an acyl radical and the other of the carbonyl groups being part of an amide radical, so that when the said coupler contains one open chain nucleus its active methylene group is substituted by R SO O-- wherein R represents a group selected from the class consisting of an alkyl group and wherein n represents an integer of from 1 to 2; R represents a group selected from the class consisting of an alkyl group; a terpenyl group, an aryl group, and a heterocyclic group; R and R each represents a group selected from the class consisting of hydrogen, an alkyl group, an aryl group and a heterocyclic group; R when n is the integer 1, represents a group selected from the class consisting of an alkyl group and an aryl group, and, when n is the integer 2, represents a group selected from the class consisting of an alkylene group and an arylene group.
References Cited UNITED STATES PATENTS 2,289,804 7/1942 Peterson 9656.6 3,311,476 3/1967 Loria 96100 FOREIGN PATENTS 648,907 1/ 1951 Great Britain.
1. TRAVIS BROWN, Primary Examiner.
U.S. Cl. X.R. 9674
US444822A 1965-04-01 1965-04-01 Silver halide color photographic elements utilizing alpha-sulfonyloxy substituted two-equivalent yellow-forming couplers Expired - Lifetime US3415652A (en)

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GB13184/66A GB1092506A (en) 1965-04-01 1966-03-25 Colour photography employing colour couplers and sulphonyloxy-substituted amido derivatives suitable therefor
FR55183A FR1473553A (en) 1965-04-01 1966-03-28 New yellow dye-forming couplers and photographic emulsions containing couplers
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DE2163812A1 (en) * 1970-12-26 1972-11-30 Konishiroku Photo Ind Process for the production of yellow images
DE2213461A1 (en) * 1971-03-20 1972-11-30 Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa (Japan) Yellow color photographic photosensitive coupler-containing element and process for the formation of yellow photographic images
US3930861A (en) * 1973-04-06 1976-01-06 Agfa-Gevaert N.V. Silver halide emulsions containing 3-anilino-2-pyrazolin-5-one color couplers
US4036643A (en) * 1973-06-11 1977-07-19 Gaf Corporation Diffusion transfer color process using lactone or sultone ring containing lipophilic non-diffusing color formers which yield diffusing dyes
US4046573A (en) * 1975-03-24 1977-09-06 Fuji Photo Film Co., Ltd. Color photographic materials
US4126462A (en) * 1975-02-25 1978-11-21 Konishiroku Photo Industry Co., Ltd. Process for forming a photographic magenta dye image
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0317983A2 (en) 1987-11-27 1989-05-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5118599A (en) * 1991-02-07 1992-06-02 Eastman Kodak Company Yellow couplers for photographic elements and processes
US5190848A (en) * 1989-05-09 1993-03-02 Eastman Kodak Company Photographic β-ketoamide and photographic elements containing them
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CH627562A5 (en) 1977-04-29 1982-01-15 Ciba Geigy Ag COLOR PHOTOGRAPHIC MATERIAL.

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US2289804A (en) * 1940-01-03 1942-07-14 Eastman Kodak Co Sulphonic ester coupler
GB648907A (en) * 1947-12-24 1951-01-17 Gevaert Photo Prod Nv Improvements in and relating to the production of colour photographic images
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2289804A (en) * 1940-01-03 1942-07-14 Eastman Kodak Co Sulphonic ester coupler
GB648907A (en) * 1947-12-24 1951-01-17 Gevaert Photo Prod Nv Improvements in and relating to the production of colour photographic images
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2163812A1 (en) * 1970-12-26 1972-11-30 Konishiroku Photo Ind Process for the production of yellow images
DE2213461A1 (en) * 1971-03-20 1972-11-30 Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa (Japan) Yellow color photographic photosensitive coupler-containing element and process for the formation of yellow photographic images
US3930861A (en) * 1973-04-06 1976-01-06 Agfa-Gevaert N.V. Silver halide emulsions containing 3-anilino-2-pyrazolin-5-one color couplers
US4036643A (en) * 1973-06-11 1977-07-19 Gaf Corporation Diffusion transfer color process using lactone or sultone ring containing lipophilic non-diffusing color formers which yield diffusing dyes
US4126462A (en) * 1975-02-25 1978-11-21 Konishiroku Photo Industry Co., Ltd. Process for forming a photographic magenta dye image
US4046573A (en) * 1975-03-24 1977-09-06 Fuji Photo Film Co., Ltd. Color photographic materials
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0317983A2 (en) 1987-11-27 1989-05-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5190848A (en) * 1989-05-09 1993-03-02 Eastman Kodak Company Photographic β-ketoamide and photographic elements containing them
US5118599A (en) * 1991-02-07 1992-06-02 Eastman Kodak Company Yellow couplers for photographic elements and processes
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes

Also Published As

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DE1547672A1 (en) 1970-02-05
GB1092506A (en) 1967-11-29
BE678578A (en) 1966-09-01

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