US3926634A - Color silver halide photographic materials containing couplers having an oleophilic group - Google Patents

Color silver halide photographic materials containing couplers having an oleophilic group Download PDF

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US3926634A
US3926634A US455090A US45509074A US3926634A US 3926634 A US3926634 A US 3926634A US 455090 A US455090 A US 455090A US 45509074 A US45509074 A US 45509074A US 3926634 A US3926634 A US 3926634A
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group
coupler
residue
photographic material
color photographic
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Atsushi Sugizaki
Takeshi Hirose
Yukio Yokota
Akio Okumura
Yasushi Oishi
Atsuaki Arai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/28—Two oxygen or sulfur atoms
    • C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
    • C07D231/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/48—Oxygen atom in position 3 or 5 and nitrogen atom in position 4 with hydrocarbon radicals attached to said nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C07D233/78—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/44—Two oxygen atoms
    • 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
    • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific

Definitions

  • ABSTRACT A color photographic material comprising a support having thereon a silver halide emulsion layer containing a coupler which can form a dye by the coupling reaction with the oxidation product of an aromatic primary amino developing agent and which contains a alkoxycarbonylarylene group represented by the formula l -Ar-COO( CH ORa wherein R and R represent a hydrogen atom or an alkyl group, R represents an aryl group, Ar represents an arylene group, and n represents an integer of from 1 to 7.
  • the invention relates to a color photographic material having a silver halide emulsion layer containing a coupler having as an oleophilic group the alkoxycarbonylarylene group represented by the following general formula (I) wherein R and R represent a hydrogen atom or an alkyl group, R represents aryl group, Ar represents an arylene group, and n represents an integer of from 1 to 7, the alkoxycarbonylarylene group having from to 50 carbon atoms.
  • general formula (I) wherein R and R represent a hydrogen atom or an alkyl group, R represents aryl group, Ar represents an arylene group, and n represents an integer of from 1 to 7, the alkoxycarbonylarylene group having from to 50 carbon atoms.
  • a coupler having the straight chain alkyl group-containing alkoxycarbonylarylene group has a melting point of from about 60C to about 1 10C and may be quite soluble in organic solvents at comparatively high temperatures but the solubility of such a coupler depends greatly on the temperature and the coupler is difficult to dissolve in organic solvents.
  • a coupler having a branched chain alkyl groupcontaining alkoxycarbonylarylene group generally has a greatly improved solubility as compared to the straight chain alkyl type coupler due to the lower melting point and less temperature dependence of the solubility thereof.
  • the introduction of the alkoxyl group is accompanied by the disadvantages that the selectivity of the solvent is reduced and thus the purification of the coupler by recrystallization becomes quite difficult.
  • the introduction of an a-alkoxycarbonyl group as disclosed in the above-described patent is accompanied by such a disadvantage that the process of preparing the coupler having such a group is complicated and by the introduction of the group, the melting point and the temperature dependence of the solubility of the coupler are slightly'improved as compared with a coupler having a straight chain alkyl type alkoxycarbonylarylene group. That is to say, the improvement obtained by the introduction of an oz-alkoxycarbonyl group is insufficient.
  • a silver halide emulsion layer containing a coupler having an alkoxycarbonylarylene group has the feature that is exhibits a high development speed, provides a high maximum density, and gives color images having good light absorption characteristics in color development.
  • asilver halide emulsion layer containing a coupler having an alkoxycarbonylarylene group in particular a yellow dye-forming coupler of this type, has sufficiently high development speed and coupling density without the need for the use of a conventional high boiling solvent for coupler, such as dibutyl phthalate, tricresyl phosphate, etc.
  • a phenol type or naphthol type colored cyan coupler having at the coupling position an arylazo group having an alkoxycarbonyl group at the ortho-position to the azo group has good hue as a masking coupler.
  • a coupler having the straight chain alkylcontaining alkoxycarbonylarylene group and a coupler having the alkoxycarbonylarylene group which has an alkyl group substituted with an alkoxyl group or an a-alkoxycarbonyl group have a disadvantage, in addition to the above-described disadvantages in solubility and production difficulties, in that a photographic emulsion layer containing such a coupler has a low film strength.
  • such a coupler as described above has a low affinity for a high boiling solvent for a coupler and it sometimes happens that when a color photographic material having a silver halide emulsion layer containing such a coupler is placed under conditions in which the silver halide emulsions of the color photographic material are greatly deformed (for instance, the color photographic material is mechanically strained when the film is rolled up), the coupler diffuses from the silver halide emulsion to another silver halide emulsion to cause color mixing in the formation of color images on color development.
  • couplers having aryloxyalkylamide group are described in British Pat. No. 562,505, US. Pat. No. 2,589,004, US. Pat. No. 2,908,573, German Pat. No. 1,075,43l,and US. Pat. No. 3,558,700 and additional examples of couplers having an aryloxyalkylacylamide group are described in German Pat. Offenlegungsschrift Nos. 2,039,970, U.S. Pat. No. 3,761,274, US. Pat. No. 2,908,573, and U.S. Pat. No. 3,652,286. Furthermore, examples of couplers having an aryloxyalkoxycarbonylamino group are described in US. Pat. No. 3,677,764.
  • couplers have less temperature dependence of the solubility in organic solvents as compared with a coupler having a straight chain-alkyl group-containing alkoxycarbonylarylene group and a coupler having an alkoxycarbonyl group which has an alkyl group substituted with an alkoxyl group or an a-alkoxycarbonyl group. Also, it is known that a silver halide emulsion layer containing such a coupler has a high film strength and there is less movement of the coupler in a silver halide emulsion layer containing such a coupler.
  • R and R represents a hydrogen atom or an alkyl group
  • R represents an aryl group
  • Ar represents an arylene group such as a divalent aromatic group, e.g., a phenylene group and a naphthylene group
  • n is an integer of from 1 to 7, in which the aromatic ring Ar may have, further, as substituents at least one of an alkyl group, an alkoxyl group, an aryloxy group, an amino group, and a halogen atom has properties satisfying the above purposes and have succeeded in, based on this discovery, attaining the present invention.
  • the present invention provides a color photographic material comprising a support having thereon at least one silver halide emulsion layer containing a coupler represented by general formula I.
  • R and R represent a hydrogen atom or an alkyl group, e.g., having 1 to carbon atoms, for example an unsubstituted alkyl group such as a methyl,
  • a substituent such as an alkoxy, alkenyl, aryl, aryloxy, halogen, amino, acylamino, acylureido, alkylthio, arylthio, hydroxy, cyano, etc.
  • aryl groups for R include an unsubstituted aryl groups such as a phenyl, naphthyl, anthryl, pyridyl, quinolyl, etc.
  • substituents such as alkyl, alkoxy, aryl, aryloxy, halogen, amino, acylamino, acylureido, alkylthio, arylthio, hydroxy, cyano, alkyloxycarbonyl, etc. groups, e.g.
  • Suitable examples of arylene groups for Ar are anthrylene, phenanthrenediyl, pyridinediyl, both unsubstituted and substituted with the hereinbefore described substituents. Suitable examples of these substituents are alkoxy such as methoxy, ethoxy, hydroxyethoxy, methoxyethoxy, hexyloxy, octyloxy, dodecyloxy, allyloxy, benxyloxy, etc.
  • R and Ar are aromatic in nature and include carbocyclic aromatic groups and heterocyclic aromatic groups.
  • the couplers according to the present invention are characterized by having at least one alkoxycarbonylarylene group represented by the general formula (I) which is connected to a photographic color coupler nucleus, such as a S-pyrazolone coupler nucleus, a phenolic coupler nucleus, a naphtholic coupler nucleus and an open-chained ketomethylene coupler nucleus.
  • a photographic color coupler nucleus such as a S-pyrazolone coupler nucleus, a phenolic coupler nucleus, a naphtholic coupler nucleus and an open-chained ketomethylene coupler nucleus.
  • alkoxycarbonylarylene group represented by the general formula (I) are alkoxycarbonyarylene groups represented by the general formula (II) wherein R R and R are as previously defined with respect to the general formula (I) and Z represents a hydrogen atom, a halogen atom, an alkyl residue, an alkoxyl residue, an aryloxy residue, or an amino residue; or an alkoxycarbonylarylene group represented by the general formula (III) COOR3 1v coo (CH COR COCHCONH- l R (IV) wherein R R R and n have the same meaning as described with respect to the general formula (I), R represents an aliphatic residue, an aromatic residue or a heterocyclic residue, W represents a hydrogen atom or a residue capable of being released by the oxidative coupling with the oxidation product of an aromatic primary amino developing agent, and 2;, represents a hydrogen atom, an alkyl residue, an alkoxyl residue, an aryloxy residue,
  • R R R R W Z and n have the same meaning as described with respect to the general formula (VI), R and R each represents a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group.
  • alkyl residues for Z, to Z; in the above described formulas (II) to (VI) are alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, fi-butyl,
  • 2,4-Di-tert-amylphenoxy acetic acid chloride was dissolved in anhydrous diethyl ether and then the reaction was conducted using lithium aluminum hydride as a reducing agent. After adding acetic acid to the reaction system to stop the reaction, the reaction product was poured into water and then the organic layer formed was extracted with ethyl acetate. After distilling off the ethyl acetate from the mixture, under reduced pressure the high boiling residue thus formed was further distilled under reduced pressure, whereby the desired product was obtained. The boiling point thereof was l28-l30Cl 1.5 mm Hg.
  • n-hexane was added to the reaction system and the crystals thus precipitated were recovered by filtration. By recrystallizing the crystals using n-hexane, the desired'product was obtained. The amount thereof was 155 g and the melting point was 85.5-86.5C.
  • Example 3 The same procedure as described in Example 1 (l-c) was conducted except that ethyl-2-methylbenzoyl acetate g) was used instead of ethylbenzoyl acetate. By recrystallizing the crystals thus recovered using n-hexane, the desired product (Coupler 3) was obtained. The amount of the coupler was 41 g and the melting point was 80,.58 l .0C.
  • Example 1 By reducing B-2,4-di-tert-amylphenoxy butyric acid chloride with lithium aluminum hydride in anhydrous 10 diethyl ether as described in Example 1 (l-a), the desired product was obtained.
  • the melting point of the product was l25-l26C/O.5 mm Hg and the yield thereof was 77 percent.
  • Example 1 The same procedure as described in Example 1 (l-b) was conducted except that the B-ZA-di-tert-amylphenoxyl butanol (159 g) prepared in (3-a) was used instead of 2,4-di-tert-amylphenoxy ethanol. By recrystallizing the crystals recovered using n-hexane, the desired product was obtained. The amount thereof was 1 16 g and the melting point was 88-89C.
  • Example 1 The same procedure as described in Example 1 (l-c) was conducted except that the 5-[,8-(2,4-di-tert-amylphenoxy)-butoxycarbonyl]-2-chloroaniline (44 g) prepared in (3-b) was used instead of 5-[B-(2,4-di-tertamylphenoxy)ethoxycarbonyl]-2-chloroaniline. Then, by recrystallizing the crystals thus recovered using ethanol, the desired product (Coupler 9) was obtained, the amount thereof 40 g and the melting point was l32l33C.
  • Example 3(3-c) The same procedure as described in Example 3(3-c) was conducted using ethyl-3-methylbenzoyl acetate (25 g) instead of ethylbenzoyl acetate and by recrystallizing the crystals thus recovered using methanol, the desired coupler was contained. The amount thereof was 39 g and the melting point was ll0l lO.5C.
  • l-Hydroxy-Z-anphthoic acid phenyl ester (20 g) was caused to react with 3-amino-l-[B-(2,4-di-te'rt-amylphenoxy)-ethoxycarbonyl]-4-chlorobenzene (32 g) for about 1 hour at l50-l60C. Then, while maintaining the reaction system at reduced pressure at the same temperature and distilling off the phenol formed from the reaction system, the reaction was further continued for about 2 hours. Then, by recrystallizing the reaction product from ethyl acetate, the desired product was obtained. The amount thereof was 35 g and the melting point was l67l68C.
  • Example 6 The same procedure as described in Example 6 was conducted for about 2 hours using 5,5-dimethyl-2,4- oxazolidinedione (40 g) instead of 5,5-dimethylhydantoin.
  • the desired coupler was obtained. The amount thereof was 54 g and the melting point was l50-l5 l C.
  • the above-described excellent properties of a coupler having an alkoxycarbonylarylene group such as the excellent color development characteristics, good color image hue, and high resistance to formaldehyde are the general properties of the alkoxycarbonylarylene group and such excellent properties are not lost by the introduction of the alkoxyl group thereto.
  • the excellent properties of a coupler having an aryloxyalkylamide group or an aryloxyalkylacrylamide group such as the solubility, film strength, and reduced mobility in the silver halide emulsion layer are not the characteristics of an amide group or an acylamide group but are the characteristics of an aryloxyalkyl group.
  • a coupler having a straight chain alkyl group has a high fusion enthalpy and solution enthalpy and hence a high temperature dependence of solubility is shown. Therefore, a coupler having a straight chain alkyl group must have a low melting point if it is to have sufficient solubility.
  • a coupler having an aryloxyalkyl group has a comparatively high melting point but has a high solubility.
  • a coupler having a straight chain alkyl group has a same solubility as the coupler having an aryloxyalkyl group at a certain temperature (for instance at the temperature of dissolving the coupler), a coupler having a straight chain alkyl group shows a low solubility at low temperatures due to the high temperature dependence of solubility and hence tends to be precipitated at low temperatures as compared with a coupler having an aryloxyalkyl group.
  • a solution of a coupler having an aryloxyalkyl group in a high boiling oil or dispersion has a higher viscosity than that of a solution of the coupler having a straight chain alkyl group of the same concentration as above, which results in reducing the mobility of the coupler in the emulsion layer.
  • the coupler of this invention having an aryloxyalkoxycarbonylarylene group has less tendency to precipitate as compared with a coupler having a straight chain alkoxycarbonyl group, the property of the coupler having an alkoxycarbonylarylene group in which the reduction in the color development charac- 13 teristics is less when the amount of the high boiling oil for dispersion is reduced is more enhanced in the coupler of this invention.
  • a coupler having an alkoxycarbonylarylene group substituted with an a-alkoxycarbonyl group as described in U.S. Pat. No. 3,664,841 is positioned between a coupler having a straight chain alkoxycarbonyl group and a coupler having an aryloxycarbonylarylene group in solution characteristics but is, in fact, near the coupler having a straight chain alkoxycarbonyl arylene group and hence the improvement in the coupler in this respect is small as described above.
  • the coupler of this invention can be added to a photographic hydrophilic colloid using any known technique.
  • the coupler can be dissolved in a high boiling solvent (e.g., above 200C) such as dibutyl phthalate, tricresyl phosphate, and trihexyl phosphate as described in, e.g., US. Pat. No. 2,322,027 using, if desired, a subsidiary solvent such as ethyl acetate, tetrahydrofuran, acetophenone, isopropyl acetate, ethyl propionate, ,B-ethoxyethyl acetate, n-butylcarbitol acetate, etc., as described in US. Pat. Nos. 3,253,921 and 3,574,627 and then the solution is dispersed in a hydrophilic colloid.
  • a suitable coupler amount in the solvent ranges from about 0.01 to 100 percent by weight.
  • a coupler solution can be prepared using only the aforesaid subsidiary solvent without using the high boiling solvent and the solution can be dispersed in a hydrophilic colloid.
  • the coupler dispersion prepared in the manner as illustrated above is mixed with a silver halide emulsion such as a silver bromide emulsion, a silver iodobromide emulsion, a silver chloroiodobromide emulsion, a silver chloride emulsion, and a silver chlorobromide emulsion or a silver halide emulsion of the socalled conversion halide type as described in, e.g., US Pat. Nos. 2,592,250 and 3,622,318 and British Pat. No. 635,841 and then the mixture is applied to a support together with, if desired, a hydrophilic colloid can be added to the mixture before coating.
  • a silver halide emulsion such as a silver bromide emulsion, a silver iodobromide emulsion, a silver chloroiodobromide emulsion, a silver chloride emulsion, and
  • At least one known coupler which is not included within the scope of the couplers of this invention can constitute at least one photographic emulsion layer of a multilayer'silver halide color photographic material comprising a support having thereon a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green-sensitive emulsion layer containing a magenta dye-forming coupler, and a red-sensitive emulsion layer containing a cyan dye-forming coupler.
  • the silver halide emulsions for the multilayer type color photographic material the aforesaid silver halide emulsions can be appropriately used. Examples of these multilayer materials are disclosed in US. Pat. Nos.
  • a cellulose ester film such as cellulose nitrate film, a cellulose acetate film, etc.
  • a polyester film such as a polyethylene terephthalate film, etc., a polyvinyl chloride film, a polystyrene film, a polycarbonate film, a paper, a so called baryta-coated paper prepared by coating barium 14 sulfate on a paper support, a laminate film prepared by coating a cellulose ester, a polyester, a polyvinyl chloride, a polystyrene, or a polycarbonate on a paper or a baryta-coated paper, and a synthetic paper.
  • examples of the hydrophilic colloid which can be used for the coupler dispersion and the silver halide photographic emulsion are gelatin; a gelatin derivative such as acylated gelatin, graft gelatin, etc.; albumin, gum arabic; agar agar; a cellulose derivative such as acetyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc.; and a synthetic resin such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, etc.
  • the dispersion of the coupler in the aforesaid hydrophilic colloid or a mixture of the dispersion of the coupler and a silver halide emulsion can be subjected to a reduced pressure treatment or washed with water as described in US. Pat. Nos. 2,949,360 and 3,396,027 prior to coating as emulsion layers of the color photographic material for removing the subsidiary solvent used for dispersing the coupler.
  • the dissolution of the coupler can be promoted if desired, using heat or ultrasonic waves.
  • the aforesaid multilayer color photographic material of this invention having at least one silver halide emulsion layer containing the coupler of this invention can have, in addition to the above-described silver halide emulsion layers, other layers conventionally employed for constituting the color photographic material, such as, for instance, a protective layer, a filter layer, an intermediate layer, an anti-halation layer, a subbing layer, a backing layer, a layer containing an ultraviolet absorber, etc. Also, as the binders for these layers, the hydrophilic colloid used for the silver halide emulsion layers can be employed.
  • Each layer of the color photographic material of this invention can further contain a hardening agent for the hydrophilic colloid.
  • hardening agents are aldehyde type compounds such as formaldehyde, glyoxal, succinaldehyde, glutaraldehyde', 2,3-dihydroxy-1,4-dioxane, mucohloric acid, dimethylolurea, etc.; active vinylic compounds such as divinylsulfone, methylene bismaleimide, 5-acetyl-1,3-diacryloyll ,3 ,5-hexahydrotriazine, N,N', N-triacryloyl- 1,3,5-hexahydrotriazine, etc.; active halogen compounds such as 2,4-dichloro-6-oxytriazine sodium salt, 2,4-dichloro-6-methoxytriazine, sebacic acid bischloromethyl ester, N,N-bis(a-chloro
  • the silver halide emulsion containing the coupler of this invention can be chemically sensitized using active gelatin or a sulfur compound as described in US. Pat. Nos. 1,574,944, 1,623,499, 2,410,689, etc.
  • the emulsion can be sensitized using a salt of a noble metal such as palladium, gold, ruthenium, rhodium platinum, etc., as described in U.S. Pat. Nos. 2,448,060, 2,399,083, 2,642,361, etc.
  • the silver halide emulsion can be sensitized using a reducing agent such as a stannous salt, as described in U.S. Pat. No.
  • 2,487,850 and also can be sensitized using a polyalkylene oxide derivative.
  • the silver halide emulsion can be spectrally sensitized with a cyanine dye or a merocyanine dye, as disclosed in U.S. Pat. Nos. 2,519,001, 2,666,761, 2,734,900, 2,739,964, 3,481,742, etc.
  • the silver halide emulsion containing the coupler of this invention can further contain a stabilizer such as a mercury compound, an azaindene, etc., as described in U.S. Pat. Nos. 2,886,437, 2,444,605, 2,403,927, 3,266,877, 3,397,987, etc., a plasticizer such as glycerine as described in C. E. K. Mees and T. H. James The Theory of Photographic Process pages 5354, The Macmillan Co. New York. (1966), and U.S. Pat. Nos. 2,904,434, 2,940,854, etc., and a coating aid such as saponin, polyethylene glycol monolauryl ether, etc. as described in U.S. Pat. Nos. 3,415,649, 3,441,413,
  • the silver halide emulsion can contain an antistatic agent as described in U.S. Pat. Nos. 2,739,888, 3,428,456, 3,437,484, 3,457,076,
  • any couplers other than the coupler of this invention can also used.
  • a yellow dye-forming coupler there are open chained type ketomethylenic couplers and typical examples of such couplers are benzoylacetanilide couplers, acylacetanilide couplers, etc.
  • a magenta dyeforming coupler there are pyrazolone type couplers, indazolone type couplers, pyrazolobenzimidazole type couplers, cyanoacetyl type couplers, etc.
  • cyan dye-forming couplers there are illustrated phenol type couplers, naphthol type couplers, etc.
  • Each of these couplers can have at the active carbon of the coupling position a group capable of being released on oxidative coupling with an aromatic primary amine developing agent, such as a halogen, ether, thioether, acyloxy, phthalimide, hydantoin, thiocyano, sulfo, sulfino, saccharin, benzotriazole, etc. group, besides a hydrogen atom.
  • the coupler can be a socalled colored coupler having a chromophore such as a diazo group, a styryl group, etc., as a releasable group.
  • the coupler can have a so-called anti-diffusion group so that the coupler is prevented from diffusing in the emulsion layers.
  • the coupler can have a group such as a sulfo group, a carboxyl group, etc., for dispersing the coupler in a micellar state as an alkali metal salt or an alkaline earth metal salt thereof.
  • a dispersion assistant can be advantageously used and further in the case of coating the silver halide emulsions and other coating compositions for producing the color photographic material of this invention, a coating assistant can also be advantageously used.
  • coating assistants are an anionic active agent containing a sulfonic acid, a sulfuric acid, a phosphoric acid, a carboxylic acid group, or a salt thereof; a nonionicsurface active agent containing a hydroxyl group; a cationic surface active agent containing an ammonium, phosphonium, anilinium, pyridinium, etc. group; and an amphoteric surface active agent having an anionic group and a cationic group in the same molecule.
  • the color photographic material of this invention can be processed, after exposure, using known processingmethods.
  • the photographic material of this invention is a negative-positive type negative or positive color photographic material
  • the color photographic material can be processed using the following main steps:
  • a hardening step for hardening the emulsion layers and an alkaline bath pre-treatment step for removing a resin backing layer can be employed before the first step, or step 1 described above.
  • a hardening step can be employed between step 1 and step 2 or step 2 and step 3 or further after step 3.
  • a stabilization step for improving the stability of images formed can be employed.
  • washing steps can also be employed between each steps and after the last step.
  • the color photographic material is dried. That is to say, the color photographic material can be dried by natural drying by exposing to air, heating, hot-air drying, infrared radiation, electron rays, etc.
  • the color photographic material is processed using the following main steps:
  • step 2 can be omitted.
  • the reversal processing, a hardening step, an alkaline bath pre-treatment step, a stabilization step, and washing steps can be, if desired, employed before or after each step described above.
  • the color photographic material is also dried as described for the aforesaid negative-positive type treatment.
  • processing baths of known compositions can be used.
  • a useful color developer is an alkaline solution containing a color developing agent.
  • a color developing agent any known aromatic primary amine developing agents can be used as disclosed, for example, in U.S. Pat. Nos. 2,592,364, 2,193,015 and C. E. K. Mees, T. H. James, The Theory of the Photographic Process, page 294-295 Macmillan Co.
  • N,N- diethyl-p-phenylene diamine such as N,N- diethyl-p-phenylene diamine, N-ethyl-N-hydroxyethylp-phenylene diamine, N-ethyl-N-hydroxyethyl-Z-methyl-p-phenylene diamine, N-ethyl-N-fi-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N,N-diethyl- Z-methyl-p-phenylene diamine, and the sulfates, hydrochlorides, sulfites of these compounds.
  • the color developer used for developing the color photographic material of this invention can further contain conventional additives such as an alkali metal (e.g., sodium or potassium) sulfite, an alkali metal carbonate, an alkali metal bisulfate, an alkali metal bromide, an alkali metal iodide, benzyl alcohol, a water softener (such as sodium hexametaphosphate, an alkali metal hydroxide, hydroxylamine, a sulfate of hydroxylamine, and a hydrochloride of hydroxylamine), a competitive coupler (such as mono-sodium 1-amino-8- naphthol-3,6-disulfonate, citrazinic acid, etc.), and the like.
  • an alkali metal e.g., sodium or potassium
  • sulfite e.g., sodium or potassium
  • an alkali metal carbonate e.g., sodium or potassium
  • an alkali metal bisulfate
  • the stop solution used in the aforesaid processings can contain a known pH-reducing agent (such as acetic acid, phthalic acid, etc.).
  • a known pH-reducing agent such as acetic acid, phthalic acid, etc.
  • the fix solution can contain a known fixing agent such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, etc.
  • the bleach solution can contain a known bleaching agent such as a ferricyanide (e.g., potassium ferricyanide), a bichromate (e.g., potassium bichro'mate), a ferric salt of ethylenediamine tetraacetic acid, etc.
  • a ferricyanide e.g., potassium ferricyanide
  • a bichromate e.g., potassium bichro'mate
  • ferric salt of ethylenediamine tetraacetic acid etc.
  • a blix bath containing a known solvent for silver halide and a known silver oxidizing agent can be used.
  • a silver halide solvent examples include a thiosulfate (e.g., ammonium or potassium thiosulfate), a thiocyanate (e.g., ammonium or potassium thiocyanate), an organic diol containing an oxygen or sulfur atom (such as 3-thio-1,5-pentanediol, 3,6-dithio-1,8- octanediol, 9-oxa-3,6, 12, 1 S-tetrathia- 1 l7-heptadecanediol, etc.), a sulfur-containing organic dibasic acid or a salt thereof (such as ethylenebisthioglycolic acid, a sodium salt thereof, etc.), imidazolidinethione, and the like.
  • examples of the oxidizing agent for silver are a ferricyanide (e.g., potassium or ammonium ferricyanide), a quinone (e.g., quinone, p-benzoquinone, o-benz oquinone, p-toluquinone 1,2-naphthoquinone), a ferric salt (e'.g., a chloride or sulfate), a cupric salt (e.g., a chloride or sulfate), a cobaltic acid or salt e.
  • a ferricyanide e.g., potassium or ammonium ferricyanide
  • a quinone e.g., quinone, p-benzoquinone, o-benz oquinone, p-toluquinone 1,2-naphthoquinone
  • a ferric salt e'.g., a chloride or sulfate
  • a cupric salt
  • a chloride or sulfate a complex salt of an ammonium ion or alkali metal ion, a ferric ion, a cupric ion, or a cobalt ion, and an organic acid (such as malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, dithioglycolic acid, ethyliminopropionic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid, dithioglycolic acid, etc.), and a chelate compound of a ferric ion, a cupric ion, or a cobalt ion (examples of coordination compounds of these chelate compounds are ethylenediamine, diethylenetriamine triethylenetetramine, diaminopropane, diaminocycl
  • the couplers of this invention can be used, in addition to the aforesaid multilayer color photographic materials based on subtractive color process, for other silver halide photographic materials forming color images by color development using aromatic primary amino developing agents, such as color radiographic photographic materials, infrared photographic materials, photographic materials for radar images, color microphotographic materials, and the like.
  • the value of the AH fusion was measured using a Perkin-Elmer DSC-IB type differential scanning calorimeter.
  • the value of the AH solution was measured using a CM-204 type twin heat conductive calorimeter.
  • Coupler 3 of this invention was mixed with dibutyl phthalate in the ratio shown in Table 2 and using such a mixture, coated samples 1 to 12 were prepared in the folllowing manner.
  • the emulsion thus prepared in an amount corresponding to a coupler content of 0.0035 mol was mixed with g of a silver iodobromide emulsion (containing 0.029 mol 40 of silver) containing 1.2 mol percent iodine.
  • a hardening agent (4 ml of a 2 percent aqueous solution of 2,6-dichloro-4-oxyS-triayine sodium salt)
  • the mixture was coated (0.75 g/m as silver) on a transparent cellulose acetate film support and Processing Step 1. Color Development 14 minutes 2. Fix 4 minutes 3. Wash 4 minutes 4. Bleach 8 minutes 5. Wash 4 minutes 6. Fix 4 minutes 7. Wash 20 minutes
  • the compositions of the processing solutions used in 60 the steps were as follows:
  • Color Developer A (pH 105) Water 1000 ml 4Amino-3-methyl-N,N-
  • EXAMPLE 12 A mixture of 10 g of coupler (as shown in Table 3), 1 ml of dibutyl phthalate and 20 ml of ethyl acetate was heated to dissolve the coupler and then the solution was treated as described in Example 11 to form an emulsified dispersion. Then, the emulsified dispersion thus prepared in an amount corresponding a coupler content 0.0035 mol was mixed with 50 g of a silver iodobromide emulsion (containing 0.028 mol of silver) containing 6.0 mol percent iodine and the mixture was coated on a support as described in Example 1 1. Thus, coated samples 1 to 8 were prepared. The couplers used in samples 1 to 8 are shown in Table 3.
  • a color photographic material comprising a support having thereon at least one silver halide emulsion layer containing at least one coupler capable of forming a dye by an oxidative coupling reaction with the oxidation product of an aromatic primary amino developing agent, wherein said coupler is selected from the group consisting of couplers'represented by the general formulae (IV), (V), (Va), (VI) or (Vla) below:
  • R and R each represents a hydrogen atom or an alkyl group;
  • R represents an aryl group;
  • R represents an aliphatic residue, an aromatic residue, or a heterocyclic residue,
  • W represents a hydrogen atom or a coupling residue capable of being released by oxidative coupling with the oxidation 5 product of an aromatic primary amino developing agent, and
  • Z represents a hydrogen atom, an alkyl residue, an alkoxyl residue, an aryloxy residue, an amino residue, or a halogen atom, said alkoxycarbonyl group being at the -4- or 5-position of the anilide ring;
  • R R R and n have the same meaning as in general formula (IV);
  • R represents an aromatic resi due or a heterocyclic residue
  • W represents a hydrogen atom or a coupling residue capable of being released by oxidative coupling with the oxidation product of an aromatic primary amino developing agnet
  • Z represents a hydrogen atom, an alkyl residue, an alkoxyl residue, an aryloxy residue, or a halogen atom, the alkoxycarbonyl group being at the 4- or 5-position of the anilino ring;
  • R R R and n have the same meaning as in general formula (IV),
  • R represents a hydrogen atom or an alkyl group having less than 5 carbon atoms
  • W represents a hydrogen atom or a coupling residue capable of being released by oxidative coupling with the oxidation product of an aromatic primary amino developing agent
  • Z represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, and aryl group, an aryloxy group, an amino group, or an acylamino group; or
  • R R R R W Z and n have the same meaning as described with respect to general formula (VI), R and R each represents a hydrogen atom, a halogen atom, an alkyl group-or an alkoxy group; wherein the alkoxycarbonylarylene group of said couplers has from about to carbon atoms, said group being representable by the formula:
  • R represents a phenyl group substituted with l or 2 alkyl groups of alkoxyl groups.
  • alkoxylcarbonyl group represented by is selected from the group consisting of a ,B-(2,4-di-tert-butylphenoxy)ethoxycarbonyl group, a B-(2,4-di-tert-amylphenoxy)ethoxycarbonyl group, a 'y-(2,4-di-tert-amylphenoxy)propoxycarbonyl group,
  • W, W and W are selected from the group consisting of halogen atoms, aryloxy groups, acyloxy groups, alkylthio groups, arylthio groups, imido groups and azo groups.
  • W, W and W are selected from the group consisting of fluorine, chlorine, bromine, iodine, phenoxy, 4-chlorophenoxy, 4-carbophenoxy, 4-(4-hydroxy phenylsulfonyl) phenoxy, acetoxy, benzoxy, ethylthio, dodecylthio, phenylthio, 2-carbophenylthio, phthalimido, oxazoldinylimido, phenylazo, 2-ethoxycarbonylnaphthylazo and 3-methoxyphenylazo.

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  • Physics & Mathematics (AREA)
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  • 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)
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998642A (en) * 1975-07-11 1976-12-21 Eastman Kodak Company Silver halide emulsions with incorporated 4,6-difluorophenolic couplers
US4010035A (en) * 1974-05-29 1977-03-01 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic material and a process for developing thereof
US4138258A (en) * 1974-08-28 1979-02-06 Fuji Photo Film Co., Ltd. Multi-layered color photographic materials
US4189321A (en) * 1977-08-31 1980-02-19 Konishiroku Photo Industry Co., Ltd. Process for forming magenta dye images
US4220470A (en) * 1974-09-24 1980-09-02 Fuji Photo Film Co., Ltd. Silver halide material containing photographic magenta coupler
KR20010107331A (ko) * 2000-05-26 2001-12-07 오석중 전기투석공정에 의한 젖산회수 방법

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59116647A (ja) 1982-12-13 1984-07-05 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS59188641A (ja) 1983-04-11 1984-10-26 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
AU590563B2 (en) 1985-05-16 1989-11-09 Konishiroku Photo Industry Co., Ltd. Method for color-developing a silver halide color photographic light-sensitive material
CA1303412C (en) 1985-05-31 1992-06-16 Shigeharu Koboshi Method for forming direct positive color image
AU591540B2 (en) 1985-12-28 1989-12-07 Konishiroku Photo Industry Co., Ltd. Method of processing light-sensitive silver halide color photographic material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2808329A (en) * 1954-11-22 1957-10-01 Eastman Kodak Co Photographic color correction using colored and uncolored couplers
US3551155A (en) * 1966-01-21 1970-12-29 Fuji Photo Film Co Ltd Light sensitive silver halide materials containing yellow-forming couplers
US3658545A (en) * 1968-12-20 1972-04-25 Konishiroku Photo Ind Light-sensitive silver halide color photographic material containing cyan couplers
US3664841A (en) * 1969-11-28 1972-05-23 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion containing yellow-forming coupler

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2808329A (en) * 1954-11-22 1957-10-01 Eastman Kodak Co Photographic color correction using colored and uncolored couplers
US3551155A (en) * 1966-01-21 1970-12-29 Fuji Photo Film Co Ltd Light sensitive silver halide materials containing yellow-forming couplers
US3658545A (en) * 1968-12-20 1972-04-25 Konishiroku Photo Ind Light-sensitive silver halide color photographic material containing cyan couplers
US3664841A (en) * 1969-11-28 1972-05-23 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion containing yellow-forming coupler

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010035A (en) * 1974-05-29 1977-03-01 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic material and a process for developing thereof
US4138258A (en) * 1974-08-28 1979-02-06 Fuji Photo Film Co., Ltd. Multi-layered color photographic materials
US4220470A (en) * 1974-09-24 1980-09-02 Fuji Photo Film Co., Ltd. Silver halide material containing photographic magenta coupler
US3998642A (en) * 1975-07-11 1976-12-21 Eastman Kodak Company Silver halide emulsions with incorporated 4,6-difluorophenolic couplers
US4189321A (en) * 1977-08-31 1980-02-19 Konishiroku Photo Industry Co., Ltd. Process for forming magenta dye images
KR20010107331A (ko) * 2000-05-26 2001-12-07 오석중 전기투석공정에 의한 젖산회수 방법

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