Classifications

• • 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
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
• • 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
  • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
• • 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
  • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group

Definitions

• the present invention relates to a multiple-layered silver halide color photographic light-sensitive material, more specifically to a multiple-layered silver halide color photographic light-sensitive material which offers excellent gradation.
• the effect thus obtained is unsatisfactory.
• the light-sensitive material becomes more susceptible to the developing inhibitor released from the diffusible DIR coupler or the like in the developing solution.
• the object of the invention is accomplished by a multiple-layered silver halide color photographic light-sensitive material having at least one coupler-containing layer on the support, wherein at least one coupler-containing layer is substantially free from high boiling solvent and at least one coupler-containing layer and/or at least one of the layers other than the coupler-containing layers contains a compound which upon reaction with the oxidation product of a developing agent releases a development inhibitor capable of changing to a less inhibitory compound, or a precursor thereof.
• a coupler is defined to be capable of coupling with the oxidation product of a color developing agent at its active site.
• the couplers for the present invention include those having a photographically useful group such as a developing inhibitor, antifogging agent, dye, desilvering agent, developing accelerator, fogging agent or brightening agent or a precursor thereof at the active site.
• Low molecular, hydrophobic couplers are preferably used in the dispersion method for the present invention.
• “being low molecular” means that the molecular weight is not more than 2000, preferably not more than 1500, and still more preferably not more than 1000.
• “being hydrophobic” means that the solubility in 100 g of distilled water at 25 ° C is not more than 0.1 g, preferably not more than 0.01 g, and still more preferably not more than 0.001 g, with the coupler molecule containing no sulfonic acid group, carboxylic acid group or phosphoric acid group.
• Yellow dye forming couplers which are preferably used are known acyl acetanilide couplers, of which benzoyl acetanilide and pivaloyl acetanilide compounds are advantageous.
• Examples of usable yellow dye forming couplers are given in British Patent No. 1,077,874, Japanese Patent Examined Publication No. 40757/1970, Japanese Patent O.P.I. Publication Nos. 1031/1972, 26133/1972, 94432/1973, 87650/1975, 3631/1976, 115219/1977, 99433/1979, 133329/1979 and 30127/1981, US Patent Nos.
• magenta dye forming couplers there can be preferably used 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers and chain-opened acyl acetonitrile couplers.
• magenta dye forming couplers which can be advantageously used are given in Japanese Patent Application Nos. 164882/1983, 167326/1983, 206321/1983, 214863/1983, 217339/1983 and 24653/1984, Japanese Patent Examined Publication Nos. 6031/1965, 6035/1965, 40757/1970, 27411/1972 and 37854/1974, Japanese Patent O.P.I. Publication Nos.
• cyan dye forming couplers there can be preferably used naphthol couplers and phenol couplers.
• cyan dye forming couplers which can be advantageously used are given in British Patent Nos. 1,038,331 and 1,543,040, Japanese Patent Examined Publication No. 36894/1973, Japanese Patent O.P.I. Publication Nos. 59838/1973, 137137/1975, 146828/1976, 105226/1978, 115230/1979, 29235/1981, 104333/1981, 126833/1981, 133650/1982, 155538/1982, 204545/1982, 118643/1983, 31953/1984, 31954/1984, 59656/1984, 124321/1984 and 166956/1984 and US Patent Nos.
• “being substantially free from high boiling solvent” means that the content of high boiling solvent is not more than 0.5% by weight of the total weight of coupler(s) contained in a particular layer.
• a dispersed coupler containing substantially no high boiling solvent for the present invention can be obtained by precipitation or mechanical pulverization as described below.
• Methods based on precipitation include the method in which a coupler, provided that it is a base- soluble coupler, is dissolved in basic water and added to an acidic liquid to yield a dispersion, the method in which a coupler, provided that it is soluble in organic solvent, is dissolved in a water-miscible organic solvent and added to water to yield a dispersion, and the method in which a coupler is dissolved in a water-immiscible low boiling organic solvent to yield an oil-in-water dispersion, after which the solvent is evaporated off.
• such methods include 1) the method in which a coupler is dissolved in a basic solution of hydrophilic colloid containing a dispersing agent and acid is gradually added to yield a dispersion, 2) the method in which a coupler is dissolved in a basic aqueous solution and gradually added to a neutral or acidic solution of hydrophilic colloid containing a dispersing agent to yield a dispersion, 3) the uniform precipitation method of H. H. Willard, L. Gordon et al.
• US Patent No. 3,658,546 discloses a method in which a coupler is dissolved in ethyl acetate and added to an aqueous solution of surfactant to yield a dispersion.
• US Patent No. 2,870,012 discloses a method in which a coupler having a carboxylic acid group or carboxylate group is dissolved in a water-miscible organic solvent and mixed with an aqueous solution of surfactant to yield a coupler dispersion.
• British Patent No. 1,193,349 and Research Disclosure No. 16,468 disclose a method in which a photographic hydrophobic compound is dissolved in alkali-containing methanol and mixed with an aqueous solution of gelatin, followed by neutralization to yield a dispersion.
• US Patent No. 4,388,403 disclose a method in which a photographic hydrophobic compound is dissolved in a water-miscible organic solvent and mixed with an aqueous solution of a hydrophilic polymer having a nonionic group and ionic group to yield a dispersion.
• Japanese Patent O.P.I. Publication No. 120848/1990 discloses a method in which a photographic hydrophobic compound having an alkali-hydrolyzable group is dissolved in a water-miscible organic solvent and added to water to yield a dispersion.
• European Patent No. 374,837 discloses a method in which a photographic hydrophobic compound is dissolved in a water-miscible organic solvent containing alkali and added to water containing an anionic surfactant and nonionic polymer to yield a dispersion.
• International Application No. 90/08345 discloses dispersion processes for this method.
• the hydrophilic colloid described above may be gelatin.
• the gelatin may be limed gelatin or may be acid-treated gelatin, enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan No. 16, p. 30 (1966) gelatin. Hydrolyzates and enzyme decomposition products of gelatin can also be used.
• Gelatins having a low calcium content are preferably used for dispersion for the present invention.
• a low calcium gelatin can easily be prepared by treating ordinary gelatin with ion exchange resin.
• the calcium content of low calcium gelatin for the present invention is normally not more than 1000 ppm, preferably not more than 800 ppm, and still more preferably not more than 600 ppm.
• the water-miscible organic solvent is not subject to limitation, as long as it is capable of dissolving photographic reagents without decomposing them and is miscible with water.
• Typical examples of such water-miscible organic solvents include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, diacetone alcohol and ethylene glycol monobutyl ether, glycols such as ethylene glycol, diethylene glycol and propylene glycol, cyclic ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile, amides such as dimethylformamide and N-methyl-2-pyrrolidone, with preference given to n-propyl alcohol from the viewpoint of dispersion stability.
• alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, diacetone alcohol and ethylene glycol monobutyl ether
• glycols such as ethylene glycol, diethylene glycol and propylene glycol
• cyclic ethers such as dioxane and tetrahydrofur
• Examples of basic solutions for the present invention include solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium citrate, lithium citrate, sodium acetate, potassium acetate and ammonia.
• alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium citrate, lithium citrate, sodium acetate, potassium acetate and ammonia.
• anionic surfactants for the present invention include the surfactants S-1 through S-12 shown below.
• the nonionic water-soluble polymer for the present invention may be any nonionic water-soluble polymer, as long as it comprises a polar group and a non-polar group and is attracted to the head group of the surfactant used and acts in cooperation with the surfactant to prevent the increase in the grain size of the coupler dispersed during storage.
• Typical examples of such polymers are polypropylene oxide, polyvinyl alcohol and methyl cellulose.
• Appropriate polymers are polyethylene oxide and polyvinyl pyrrolidone.
• Methods based on mechanical pulverization include the method in which a coupler is finely powdered using high energy of, for example, ultrasonic waves, after which it is added to a solution of hydrophilic colloid to yield a dispersion, and the method in which an additive is added to water or bad solvent and a coupler is finely dispersed at high temperature using a mill with a medium of narrow grain size distribution in the presence of a dispersing agent and/or a hydrophilic colloid.
• Japanese Patent O.P.I. Publication Nos. 172826/1989 and 110547/1990 disclose a method in which a photographic hydrophobic compound is mechanically milled and dispersed using a ball mill or sand mill in the presence of a surfactant and hydrophilic colloid.
• fine solid grain dispersion can be achieved using a ball mill, roll mill, sand mill and other apparatuses, with preference given to a sand mill.
• Various commercially available sand mills can be used.
• Examples of the medium substance for the present invention include glass, alumina, zirconia, agate, stainless steel and nylon, with preference given to glass, zirconia and alumina.
• glass When using glass, its silicon dioxide content is preferably over 60% by weight.
• the medium is preferably spherical. Although grain size is not limited, the medium is normally 0.1 to 20 mm0 in diameter, preferably 0.2 to 10 mm0, and still more preferably 0.5 to 5 mm0.
• Glass media include Bright Glass Beads, produced by Bright Hyoshiki Kogyo K.K..
• Couplers for the present invention may be used in combination with so-called oil-protected coupler.
• the DIR compound which releases a development inhibitor capable of changing to a less inhibitory compound or a precursor thereof (hereinafter referred to as the DIR compound for the present invention) releases the developing inhibitor or precursor thereof as a result of a reaction, such as coupling reaction or redox reaction, with the oxidation product of a developing agent immediately after the reaction or after an intramolecular nucleophilic substitution reaction and other reactions.
• the developing inhibitor or precursor thereof thus released changes to a less inhibitory compound upon hydrolysis and other reactions.
• a precursor When a precursor is released, it once becomes a development inhibitor and then changes to a less inhibitory compound.
• This conversion may take place in the light-sensitive material or in a processing solution such as a developer.
• the DIR compound for the present invention is preferably a compound in which the development inhibitor formed changes to a less inhibitory compound upon hydrolysis, more preferably represented by the following formula DIR-1.
• Cp represents a coupler residue
• T represents a bonding group whose bond with Z is broken after Cp-T bond has been broken upon reaction with the oxidation product of a developing agent, which preferably binds to the coupling site of the coupler.
• Z represents a development inhibitor residue
• L represents a bonding group having a chemical bond which is cleaved by a component of the developer after the compound having Z has exhibited its development inhibitory action.
• Y represents a substituent; m represents 0, 1 or 2, preferably 0 or 1; n represents 1 or 2; when n is 2, L and Y may be identical or not.
• the coupler residue represented by Cp is a yellow dye forming coupler residue, magenta dye forming coupler residue, cyan dye forming coupler residue, coupler residue which forms substantially no image forming dyes, or the like.
• the yellow dye forming coupler residue represented by Cp is preferably a coupler residue of the acyl acetanilide type (e.g., pivaloyl acetanilide type, benzoyl acetanilide type), malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolyl acetamide type, malon ester monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolyl acetamide type or benzimidazolyl acetate type, or a coupler residue derived from the heterocyclic substituted acetamide or heterocyclic substituted acetate included in US Patent No.
• the acyl acetanilide type e.g., pivaloyl acetanilide type, benzoyl acetanilide type
• malondiester type malondiamide
• the magenta dye forming coupler residue represented by Cp is preferably a coupler residue having a 5-oxo-2-pyrazoline nucleus or pyrazoloazole nucleus such as a pyrazolotriazole nucleus or a coupler residue of the cyanoacetophenone type.
• the cyan dye forming coupler residue represented by Cp is preferably a coupler residue having a phenol nucleus or a-naphthol nucleus.
• the coupler forms substantially no image forming dyes after releasing a developing inhibitor upon coupling with the oxidation product of a developing agent, it has an equivalent DIR coupler effect.
• coupler residues represented by Cp include the coupler residues described in US Patent Nos. 4,052,213, 4,088,491, 3,632,345, 3,958,993 and 3,961,959, specifically coupler residues which form no dyes, so-called oozing dye forming coupler residues, characterized by oozing of the dye from the light-sensitive material into a processing solution and so-called bleacheable dye forming coupler residues, which are bleached upon reaction with a component of a processing solution.
• coupler residues for Cp include yellow dye forming coupler residues of the pivaloyl acetanilide type or benzoyl acetanilide type, magenta dye forming coupler residues having a 5-oxo-2-pyrazoline nucleus, cyan dye forming coupler residues having an a-naphthol nucleus and oozing dye forming coupler residues having an a-naphthol nucleus substituted by a hydrophilic group.
• Example of the group represented by T include 1) groups which cause a cleavage reaction based on an electron transfer reaction along a conjugation system, 2) groups which cause a cleavage reaction based on an intramolecular nucleophilic substitution reaction, 3) groups utilizing a hemiacetal cleavage reaction, 4) groups utilizing an iminoketal cleavage reaction and 5) groups utilizing a hydrolytic cleavage reaction of ester.
• T its bond with Z may be broken upon reaction with the oxidation product of a developing agent after the Cp-T bond has been broken.
• Examples of such forms of T include coupler components which couple with the oxidation product of a developing agent, and redox components involved in redox reaction with the oxidation product of a developing agent.
• T is a coupler component
• it is exemplified by the coupler residues exemplified for Cp.
• T is a redox component
• hydroquinones catechols, pyrogallols, aminophenols such as p-aminophenol and o-aminophenol, naphthalenediols such as 1,2-naphthalenediol, 1,4-naphthalenediol and 2,6-naphthalenediol and aminonaphthols such as 1,2-aminonaphthol, 1,4-aminonaphthol and 2,6-aminonaphthol.
• groups represented by T those represented by the following formulas are preferable.
• * 1 denotes the Cp-binding site
• * 2 denotes the Z-binding site.
• Examples of the substituent represented by R 1 include halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, anilino groups, acylamino groups, ureido groups, cyano groups, nitro groups, sulfonamide groups, sulfamoyl groups, carbamoyl groups, aryl groups, carboxyl groups, sulfo groups, cycloalkyl groups, alkanesulfonyl groups, arylsulfonyl groups and acyl groups, all of which may have an additional substituent.
• Examples of the substituent represented by R 2 or R 3 include alkyl groups, alkenyl groups, cycloalkyl groups and aryl groups, all of which may have an additional substituent.
• L in Formula DIR-I is a divalent bonding group having a chemical bond which is cleaved by a component of the developer such as a nucleophilic reagent such as hydroxy ion or hydroxylamine.
• the mediating divalent group may have an ether bond, amide bond, carbonyl group, thioether bond, sulfo group, sulfonamide bond or urea bond.
• W 3 represents a hydrogen atom or substituent.
• the substituent is a halogen atom, nitro group, alkoxy group or alkyl group.
• the bonding group represented by L preferably has one of the following structures.
• * 3 denotes the Z-bonding site;
• * 4 denotes the Y-bonding site.
• Wi, W 2 and W 3 ' independently represent a hydrogen atom or substituent; d represents an integer of 0 to 10, preferably 0 to 5.
• the substituent represented by W 1 is selected from halogen atoms, alkyl groups having 1 to 10, preferably 1 to 5 carbon atoms, alkanamide groups, alkoxy groups, alkoxycarbonyl groups, alkanesul- fonamide groups, alkylcarbamoyl groups, aryloxycarbonyl groups, aryl groups, carbamoyl groups, nitro groups, cyano groups, arylsulfonamide groups, sulfamoyl groups, imide groups and other groups.
• Examples of the substituent represented by W 2 include alkyl groups, aryl groups and alkenyl groups; W 3 ' has the same definition as W 3 and is exemplified by the same substituents as with W 3 ; q represents an integer of 0 to 6.
• examples of the substituent represented by Y include alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups and heterocyclic groups, all of which may have an additional substituent.
• the alkyl group, cycloalkyl group or alkenyl group represented by Y is specifically a linear or branched alkyl group, alkenyl group or cycloalkyl group having 1 to 10, preferably 1 to 5 carbon atoms. It preferably has a substituent.
• substituents examples include halogen atoms, nitro groups, alkoxy groups having 1 to 4 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, alkanesulfonyl groups having 1 to 4 carbon atoms, alkanamide groups having 2 to 5 carbon atoms, anilino groups, benzamide groups, alkylcarbamoyl groups having 2 to 6 carbon atoms, carbamoyl groups, arylcarbamoyl groups having 7 to 10 carbon atoms, alkylsulfonamide groups having 1 to 4 carbon atoms, arylsulfonamide groups having 6 to 10 carbon atoms, alkylthio groups having 1 to 4 carbon atoms, arylthio groups having 6 to 10 carbon atoms, phthalimide groups, succinimide groups, imidazolyl groups, 1,2,4-triazolyl groups, pyrazolyl groups, benzotriazolyl groups, furyl groups, benzothiazolyl groups, al
• the aryl group represented by Y is a phenyl group, naphthyl group or the like, which may have an additional substituent.
• substituents include the substituents mentioned as examples for the substituent for the alkyl group or alkenyl group above, and alkyl groups having 1 to 4 carbon atoms.
• the heterocyclic group represented by Y is selected from diazolyl groups such as 2-imidazolyl group and 4-pyrazolyl group, triazolyl groups such as 1,2,4-triazol-3-yl group, thiazolyl groups such as 2-benzothiazolyl group, oxazolyl groups such as 1,3-oxazol-2-yl group, pyrrolyl groups, pyridyl groups, diazinyl groups such as 1,4-diazin-2-yl group, triazinyl groups such as 1,2,4-triazin-5-yl group, furyl groups, diazolinyl groups such as imidazolin-2-yl group, pyrrolinyl groups and thienyl groups.
• diazolyl groups such as 2-imidazolyl group and 4-pyrazolyl group
• triazolyl groups such as 1,2,4-triazol-3-yl group
• thiazolyl groups such as 2-benzothiazolyl group
• Z in Formula DIR-I is exemplified by a divalent nitrogen-containing heterocyclic group and nitrogen-containing heterocyclic thio group.
• heterocyclic thio group examples include tetrazolylthio group, benzothiazolylthio group, benzimidazolylthio group, triazolylthio group and imidazolylthio group.
• * 5 denotes the site of bonding with * 6 denotes the site of bonding with ( ⁇ (L-Y) n .
• X represents a hydrogen atom or substituent, and is located in the Z moiety in Formula DIR-I.
• substituent include halogen atoms, alkyl groups, alkenyl groups, alkanamide groups, alkenamide groups, alkoxy groups, sulfonamide groups and aryl groups.
• the alkyl group or alkenyl group represented by X has the same definition as the alkyl group or alkenyl group represented by Y in Formula DIR-I.
• the alkanamide group, cycloalkanamide group or alkenamide group represented by X is specifically a linear or branched alkanamide group, cycloalkanamide group or alkenamide group having 2 to 10, preferably 2 to 5 carbon atoms.
• the alkoxy group or cycloalkoxy group represented by X is specifically a linear or branched alkoxy group or cycloalkoxy group having 1 to 10, preferably 1 to 5 carbon atoms, which includes those having the same substituent as in the alkyl group or alkenyl group represented by Y in Formula DIR-I.
• DIR couplers for the present invention represented by Formula DIR-I, the following are preferred.
• R 1 ', R 2 ' and R 3 ' have the same definitions as R i , R 2 and R 3 , respectively;
• l' has the same definition as l;
• X' has the same definition as X.
• Cp and -L-Y- have the same definitions as Cp and -L-Y in Formula DIR-I.
• DIR compound for the present invention examples are given below, but these examples are not to be construed as limitative.
• the development inhibitor for the DIR coupler for the present invention must has a particular value for decomposition rate constant Specifically, the half-life of the developing inhibitor at pH 10.0 is not longer than 4 hours, preferably not longer than 2 hours, and still more preferably not longer than 1 hour.
• the half-life of a developing inhibitor can easily be determined as follows.
• the developing inhibitor is added to a developer with the following composition to reach a final concentration of 1 x 10- 4 mol/R. While keeping the solution at 38 °C, residual developing inhibitor concentration is determined by liquid chromatography.
• the DIR coupler for the present invention is a known compound, which can easily be synthesized in accordance with the methods described in Japanese Patent Publication O.P.I. Publication Nos. 151944/1982, 205150/1983, 218644/1985, 221750/1985, 233650/1985 and 11743/1986.
• DIR couplers may be added to a light-sensitive emulsion layer or non-light-sensitive emulsion layer.
• the amount of their addition is preferably 1 x 10- 4 to 1 x 10- 1 mol% of the total amount of silver coated.
• the compound for the present invention represented by Formula DIR-I
• a light-sensitive material it may be added to any one or more of an anti-halation layer, interlayer (such as between different color-sensitive layers, between the same kind of color-sensitive layers, between a light-sensitive layer and a non-light-sensitive layer), light-sensitive silver halide emulsion layer, non-light-sensitive silver halide emulsion layer, yellow filter layer and protective layer.
• These compounds may be added to light-sensitive material in combination of two or more kinds.
• the total amount of their addition is 0.01 to 50 mol%, preferably 0.1 to 5 mol% per mol of silver halide for an emulsion layer, and preferably 10- 7 to 10- 3 mol/m 2 , more preferably 10- 6 to 10- 4 mol/m 2 as of amount of coating for a non-light-sensitive hydrophilic colloid layer.
• the silver halide emulsion for the present invention can be chemically sensitized by a conventional method. Specifically, sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization using gold or another noble metal and other sensitizing methods can be used singly or in combination.
• the silver halide emulsion for the present invention can be sensitized by using the chemical sensitizers and sensitizing methods described in British Patent Nos. 618,061, 1,315,755 and 1,396,696, Japanese Patent Examined Publication No. 15748/1969, US Patent Nos.
• the silver halide emulsion for the present invention can be spectrally sensitized in the desired wavelength band using a dye which is known as a sensitizing dye in the photographic industry.
• a dye which is known as a sensitizing dye in the photographic industry In addition to sensitizing dyes, a compound which has no spectral sensitizing action per se or which absorbs substantially no visible light and which acts as a supersensitizer to enhance the sensitizing action of a sensitizing dye may be added to the emulsion.
• Sensitizing dyes for the present invention are cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.
• cyanine dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• These dyes can have any nucleus which is generally used for cyanine dyes as a basic heterocyclic nucleus.
• nuclei include pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus and nuclei resulting from fusion of these nuclei with an alicyclic hydrocarbon ring, nuclei resulting from fusion of these nuclei with an aromatic hydrocarbon ring such as indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucle
• the merocyanine dye or complex merocyanine dye may have a 5- or 6-membered heterocyclic nucleus such as such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,4-dione nucleus, thiazolidine-2,4,-dione nucleus, rhodanine nucleus or thiobarbituric acid nucleus as a nucleus having a ketomethylene structure.
• a 5- or 6-membered heterocyclic nucleus such as such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,4-dione nucleus, thiazolidine-2,4,-dione nucleus, rhodanine nucleus or thiobarbituric acid nucleus as a nucleus having a ketomethylene structure.
• Useful sensitizing dyes for blue-sensitive silver halide emulsion include those described in West German Patent No. 929,080, US Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572, British Patent No. 1,242,588 and Japanese Patent Examined Publication Nos. 14030/1969 and 24844/1977.
• Typical examples of useful sensitizing dyes for green-sensitive silver halide emulsion include the cyanine dyes, merocyanine dyes and complex cyanine dyes described in US Patent Nos. 1,939,201, 2,072,908 and 2,945,763 and British Patent No. 505,979.
• Typical examples of useful sensitizing dyes for red-sensitive silver halide emulsion include the cyanine dyes, merocyanine dyes and complex cyanine dyes described in US Patent Nos. 2,269,234, 2,270,378, 2,442,710, 2,454,629 and 2,776,280. Also, the cyanine dyes and complex cyanine dyes described in US Patent Nos. 2,213,995, 2,493,748 and 2,519,001 and West German Patent No. 929,080 can be advantageously used for green-sensitive or red-sensitive silver halide emulsion.
• sensitizing dyes may be used singly or in combination. Sensitizing dyes are often used in combination for the purpose of supersensitization. Typical examples of such combinations are given in Japanese Patent Examined Publication Nos. 4932/1968, 4933/1968, 4936/1968, 32753/1969, 25831/1970, 26474/1970, 11627/1971, 18107/1971, 8741/1972, 11114/1972, 25379/1972, 37443/1972, 28293/1973, 38406/1973, 38407/1973, 38408/1973, 41203/1973, 41204/1973, 6207/1974, 40662/1975, 12375/1978, 34535/1979 and 1569/1980, Japanese Patent O.P.I.
• one or more monomethine cyanine dyes it is preferable to use one or more monomethine cyanine dyes, one or more trimethine cyanine dyes or a combination of a monomethine cyanine dye and a trimethine cyanine dye.
• sensitizing dyes added is not limited, it is preferable to use sensitizing dyes at 2 x 10- 6 to 1 x 10- 2 mol, more preferably 5 x 10- 6 to 5 x 10- 3 mol per mol of silver halide.
• Sensitizing dyes can be added to emulsion by various methods which are obvious to those skilled in the art.
• these sensitizing dyes may be dispersed directly in emulsion, or in the form of solution in a soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide or mixture thereof or in dilution or solution in water.
• Ultrasonic vibration can also be used during dissolution.
• Dyes can be added to emulsion by the method described in US Patent No. 3,469,987 and other publications, in which a dye is dissolved in a volatile organic solvent, the resulting solution is dispersed in hydrophilic colloid and the resulting dispersion is added to the emulsion, and by the method described in Japanese Patent Examined Publication No. 24185/1971 and other publications, in which a water-insoluble dye is not dissolved but milled in a solid form and dispersed in an aqueous solvent and the resulting dispersion is added to the emulsion.
• Dyes can also be added to emulsion in the form of dispersion as prepared by the acid dissolution dispersion method.
• Other methods which can be used to add sensitizing dyes to emulsion include those described in US Patent Nos. 2,912,345, 3,342,605, 2,996,287 and 3,425,835.
• the sensitizing dyes for the present invention can be added to emulsion at any time during the processing process from formation of silver halide grains to their coating on the support.
• the sensitizing dyes can be added at any time selected from the period before formation of silver halide grains, during formation of silver halide grains, between completion of formation of silver halide grains and initiation of chemical sensitization, at initiation of chemical sensitization, during chemical sensitization, at completion of chemical sensitization and between completion of chemical sensitization and coating. Separate addition in several stages is acceptable.
• the sensitizing dyes may be added after dissolving each dye in the same solvent or different solvents and mixing the resulting solutions before adding to emulsion.
• the solutions may be separately added to emulsion. However, it is more preferable to mix the dye solutions before adding to emulsion.
• gelatin as a binder (or protective colloid) for the silver halide emulsion for the present invention
• gelatin derivatives, graft polymers of gelatin and another polymer and other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic polymer substances in the form of homo- or copolymer.
• gelatin as described above can be used.
• gelatin derivatives which can be used include those prepared by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimides, polyalkylene oxides and epoxy compounds. Specific examples are given in US Patent Nos. 2,614,928, 3,132,945, 3,186,846 and 3,312,553, British Patent Nos. 861,414, 1,033,189 and 1,005,784 and Japanese Patent Examined Publication No. 26845/1967.
• Preferable proteins are albumin and casein; preferable cellulose derivatives are hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate; preferable sugar derivatives are sodium alginate and starch derivatives.
• graft polymers of gelatin and another polymer there can be used those prepared by grafting gelatin with a homopolymer or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, ester or amide derivative thereof, acrylonitrile or styrene.
• graft polymers of gelatin with a polymer which is somewhat compatible with gelatin such as acrylic acid, acrylamide, methacrylamide or hydroxyalkyl methacrylate. Examples thereof are given in US Patent Nos. 2,763,625, 2,831,767 and 2,956,884.
• Typical synthetic hydrophilic polymer substances include homopolymers and copolymers of polyvinyl alcohol, partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole and polyvinyl pyrazole, specifically those described in West German OLS Patent Application No. 2,312,708, US Patent Nos. 3,620,751 and 3,879,205 and Japanese Patent Examined Publication No. 7561/1968.
• the photographic emulsion layer and other hydrophilic colloid layers of a light-sensitive material incorporating the silver halide emulsion of the present invention may be hardened by crosslinking molecules of binder (or protective colloid) and using one or more hardeners to increase film strength.
• the hardener can be added in such amounts that it is unnecessary to add a hardener to processing solution, it can also be added to processing solution.
• hardeners examples include aldehyde hardeners, aziridine hardeners such as those described in PB Report No. 19921, US Patent Nos. 2,950,197, 2,964,404, 2,983,311 and 3,271,175, Japanese Patent Examined Publication No. 40898/1971 and Japanese Patent O.P.I. Publication No. 91315/1975, isoxazole hardeners such as those described in US Patent No. 331,609, epoxy hardeners such as those described in US Patent No. 3,047,394, West German Patent No. 1,085,663, British Patent No. 1,033,518 and Japanese Patent Examined Publication No. 35495/1973, vinyl sulfone hardeners such as those described in PB Report No.
• triazine hardeners such as those described in West German Patent Nos. 2,410,973 and 2,553,915, US Patent No. 3,325,287 and Japanese Patent O.P.I. Publication No. 12722/1977
• polymeric hardeners such as those described in British Patent No. 822,061, US Patent Nos. 3,623,878, 3,396,029 and 3,226,234 and Japanese Patent Examined Publication Nos. 18578/1972, 18579/1972 and 48896/1972
• maleimide hardeners acetylene hardeners, methanesulfonate hardeners and N-methylol hardeners.
• the effect of the present invention is enhanced by the use of a vinyl sulfone hardener.
• a vinyl sulfone hardener is defined as a compound having a vinyl group bound to a sulfonyl group or a group capable of forming a vinyl group, preferably having at least two vinyl groups each bound to a sulfonyl group or at least two groups each capable of forming a vinyl group.
• the compound represented by the following formula VS-I is preferably used for the present invention.
• L represents an m-valent bonding group
• Y represents a group which can be eliminated in the form of HY by the action of base, such as a halogen atom, sulfonyloxy group, sulfoxy group (including its salt) or tertiary amine residue
• m represents an integer of 2 to 10; when m is 2 or more, the -S0 2 -X groups may be identical or not.
• the m-valent bonding group L is an m-valent group formed with one or more of aliphatic hydrocarbon groups such as alkylene, alkylidene, alkylidine and groups formed thereby, aromatic hydrocarbon groups such as arylene and groups formed thereby, and the bonds represented by -O-, -NR'- (R' represents a hydrogen atom or an alkyl group having preferably 1 to 15 carbon atoms), -S-, -CO, -SO-, -S0 2 - or -S0 3 -. When there are two or more -NR'- groups, the R' groups may bind to form a ring.
• the bonding group L also includes those having a substituent such as a hydroxyl group, alkoxy group, carbamoyl group, sulfamoyl group, alkyl group or aryl group.
• the vinyl sulfone hardeners for the present invention include the aromatic compounds described in German Patent No. 1,100,942 and US Patent No. 3,490,911, the alkyl compounds bond with hetero atoms described in Japanese Patent Examined Publication Nos. 29622/1969, 25373/1972 and 24259/1972, the sulfonamides and ester compounds described in Japanese Patent Examined Publication No. 8736/1972, the 1,3,5-tris[ ⁇ -(vinylsulfonyl)propionyl]-hexahydro-s-triazine described in Japanese Patent O.P.I. Publication No. 24435/1974, the alkyl compounds described in Japanese Patent Examined Publication No. 35807/1975 and Japanese Patent O.P.I. Publication No. 44164/1976 and the compounds described in Japanese Patent O.P.I. Publication No. 18944/1984.
• vinyl sulfone hardeners are used in solution in water or organic solvent and used at 0.005 to 20% by weight, preferably 0.02 to 10% by weight of binder (e.g., gelatin).
• binder e.g., gelatin
• the photographic emulsion layers and/or other hydrophilic colloid layers of a light-sensitive material incorporating the silver halide emulsion of the present invention may contain various surfactants for the purpose of improvement in coatability, antistatic, improvement in sliding property, emulsion dispersion, prevention of adhesion, improvement in photographic properties such as development acceleration, hardening and sensitization.
• anionic surfactants are those containing an acidic group such as a carboxyl group, sulfo group, phospho group, sulfate group or phosphate group.
• anionic surfactants include alkylcarboxylates, alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylphosphates, N-acyl-N-alkyltaurins, sulfosuccinates, sulfoalkylpolyoxyethylenealkylphenyl ethers and polyox- yethylenealkylphosphates.
• amphoteric surfactants include amino acids, aminoalkylsulfonic acids, aminoal- kylsulfates, aminoalkylphosphates, alkylbetaines and amine oxides.
• cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring.
• preferable nonionic surfactants include saponin (steroid), alkylene oxide derivatives such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides and polyethylene oxide adducts of silicon, glycidol derivatives such as alkenylsuccinic polyglyceride and alkylphenol polyglyceride, aliphatic esters of polyhydric alcohol and alkyl esters of sugar.
• saponin steroid
• alkylene oxide derivatives such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl
• anionic surfactants are preferred, with more preference given to those represented by the above formulas S-1 through S-12.
• a thickener may be added upon coating the photographic light-sensitive material incorporating the silver halide emulsion of the present invention.
• the light-sensitive material incorporating the silver halide emulsion of the present invention may be provided with an auxiliary layer such as a filter layer, anti-halation layer and/or anti-irradiation layer.
• auxiliary layer such as a filter layer, anti-halation layer and/or anti-irradiation layer.
• These layers and/or emulsion layers may contain a dye which oozes out or bleached from the light-sensitive material during the developing process.
• the filter dyes, anti-irradiation dyes and other dyes used for various purposes include oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes and azo dyes, of which oxanol dyes, hemioxanol dyes and merocyanine dyes are particularly useful.
• polymer latices for improving the film properties of the light-sensitive material binder, improving the adhesive properties and dimensional stability of the film and improving developability.
• Aqueous dispersion polymer latices synthesized by emulsification polymerization are preferred.
• the polymer latex may be a homopolymer comprising a single monomer compound, but it is preferable to use a copolymer, which comprises two or more different monomer compounds, because polymer latex properties are easier to control according to the combination.
• the monomer compound constituting the polymer latex for the present invention is preferably an ethylenic monomer compound.
• these monomer compounds include acrylates such as methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, phenyl acrylate and 2-hydroxyethyl acrylate, methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate and 2-ethoxyethyl methacrylate, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzo
• acrylic acid methacrylic acid, itaconic acid and maleic acid. These acids may be used in the form of a salts of an alkali metal such as sodium or potassium or in the form of ammonium ion.
• Other usable monomer compounds include the crosslinkable monomers described in US Patent Nos. 3,459,790, 3,438,708, 3,554,987, 4,215,195 and 4,247,673 and Japanese Patent O.P.I. Publication No. 205735/1982. Specifically, these crosslinkable monomers are exemplified by N-(2-acetoacetoxyethyl)acrylamide and N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide.
• acrylates Of these monomer compounds are preferred acrylates, methacrylates, vinyl esters, styrenes and olefins.
• the average grain size of the latex for the present invention is normally 0.005 to 2.0 am, particularly preferably 0.01 to 0.8 am.
• the molecular weight is normally 1,000 to 1,000,000, preferably 2,000 to 500,000.
• Glass transition temperature is normally - 40 to 150 C, preferably -40 to 20 C.
• the latex for the present invention can be added to photographic structural layers as such or in dispersion in water.
• the latex content is preferably 5 to 60% by weight of the binder in photographic structural layer.
• the latex may be added to any layer, whether it is a light-sensitive layer or non-light-sensitive layer, a light-sensitive layer is preferred as a site of addition.
• the high boiling solvent for the present invention is defined to have a boiling point of over 150°C, preferably 200 to 400 ° C.
• Examples of the high boiling solvent for the present invention include the esters of inorganic acid, esters of organic acid, esters of polyhydric alcohol and epoxidated oils described in detail below.
• esters of inorganic acid include phosphates, specifically triethyl phosphate, tributyl phosphate, tri-n-octyl phosphate, diphenyl-n-octyl phosphate, butyl-2-xylenyl phosphate, triphenyl phosphate, tricresyl phosphate and 2-ethylhexyldiphenyl phosphate.
• esters of organic acid include esters of lower fatty acid such as citrates, specifically tributyl citrate, acetyltributyl citrate, triethyl citrate, acetyltriethyl citrate, tricyclohexyl citrate, acetyltrioctyl citrate and acetyloctyldecyl citrate.
• esters of higher fatty acid examples include butyl stearate, methoxyethyl oleate, methylacetyl ricinoleate, ethylacetyl ricinoleate and methoxyethylacetyl ricinoleate.
• the esters of organic acid for the present invention also include diesters of aliphatic or aromatic organic acid.
• diesters of aliphatic organic acid examples include dibutyl adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-octyl sebacate, dibutyl sebacate, di-2-ethylhexyl azelate and di-i-decyl adipate.
• diesters of aromatic organic acid include phthalates, specifically dimethyl phthalate, di-i-isopropyl phthalate, diethyl phthalate, dibutyl phthalate, dibutyl terephthalate, butylbenzyl phthalate, dibutoxyethyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl isophthalate, di-n-nonyl phthalate, di-n-nonyl isophthalate, butylcyclohexyl phthalate, dibutyl tetrachlorophthalate, dibutyl isophthalate, dicapryl phthalate, di-2-methoxyethyl phthalate and di
• esters of polyhydric alcohol examples include glycol esters, specifically ethylphthalylethyl glycolate, butylphthalylbutyl glycolate, methylphthalylethyl glycolate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate and sucrose benzoate.
• epoxidated oils include epoxidated soybean oil, glycidyl oleate, aryl 9,10-epoxystearate, 2-ethylhexyl 9,10-epoxystearate, epoxidated tolu oil fatty acid 2-ethylhexyl and epoxidated tolu oil alkyls.
• one or more high boiling solvents may be added to a non-light sensitive layer after being mixed and then dispersed or after being separately dispersed and then mixed.
• the high boiling solvent for the present invention is added to at least one of the non-light-sensitive layers described above, it is preferable to add it as an oil-in-water dispersion like ordinary silver halide color photographic light-sensitive materials.
• a solution of hydrophilic colloid such as an aqueous solution of gelatin and a high boiling solvent are mixed in the presence of surfactant and dispersed using an ultrasonic homogenizer, homomixer, pressure sprayer and another means to yield a dispersion.
• the amount of high boiling solvent added to the light-sensitive material is preferably 0.05 to 5.0 g/m 2 , more preferably 0.2 to 2.0 g/m 2 .
• the non-light-sensitive layer containing a high boiling solvent may contain a UV absorbent, antistatic agent, antistaining agent, anti-irradiation dye, hardener and other additives as necessary.
• the hydrophilic colloid layers for the present invention such as the protective layer and interlayer may contain a UV absorbent for the purpose of preventing fogging due to electric discharge as a result of charging the light-sensitive material by friction etc. and for preventing image deterioration by UV light.
• UV absorbents examples include benzophenone compounds such as those described in Japanese Patent O.P.I. Publication No. 2784/1971 and US Patent Nos. 3,215,530 and 3,698,907, butadiene compounds such as those described in US Patent No. 4,045,229, 4-thiazolidone compounds such as those described in US Patent Nos. 3,314,794 and 3,352,681, aryl-substituted benzotriazole compounds such as those described in Japanese Patent Examined Publication Nos. 10466/1961, 1687/1966, 26187/1967, 29620/1969 and 41572/1973, Japanese Patent O.P.I. Publication Nos. 95233/1979 and 142975/1982, US Patent Nos.
• UV absorbing couplers such as a-naphthol cyan dye forming couplers and UV absorbing polymers such as those described in Japanese Patent O.P.I. Publication Nos. 111942/1983, 178351/1983, 181041/1983, 19945/1984 and 23344/1984 can be used.
• UV absorbents may be used in combination with mordant in a particular layer.
• a combination with a benzotriazole compound is preferred.
• colored couplers which can be used include those described in British Patent Nos. 937,621, 1,035,959 and 1,255,111, Japanese Patent O.P.I. Publication Nos. 22028/1973 and 42121/1977, Japanese Patent Examined Publication Nos. 22335/1963, 2016/1969 and 15754/1969 and US Patent Nos.
• the light-sensitive material incorporating the silver halide emulsion of the present invention may contain an image stabilizer for the purpose of preventing dye image deterioration.
• preferable image stabilizers include hydroquinone derivatives, gallic acid derivatives, phenol derivatives, bisphenol derivatives, hydroxycumarane and spirohydroxycumarane, hydroxychroman and spirohydroxychroman, piperidine derivatives, aromatic amine compounds, benzodioxane derivatives, benzdioxol derivatives, silicon atom containing compounds and thioether compounds. Specific examples thereof are given in US Patent No. 1,410,846, Japanese Patent O.P.I. Publication Nos.
• Hydroquinone derivatives are particularly preferable.
• the colloid layer formed on the top face of the silver halide emulsion layer formed farthermost from the support contains fine silver halide grains which have substantially no light sensitivity.
• This colloid layer is usually formed as a protective layer for photographic structural layers.
• silver halide grains which have substantially no light sensitivity are defined to undergo substantially no development in the developer. Although any such silver halide grains can be used, it is more preferable that they undergo substantially no development or dissolution in the developer.
• Fine grains are defined to have a grain size which minimized light scattering. It is preferable that the fine grains have an average grain size of not more than 0.3 am, more preferably 0.01 to 0.2 I .Lm, and still more preferably 0.02 to 0.15 am. Although grain size distribution is not subject to limitation, whether wide or narrow, a narrow distribution is preferred.
• Any silver halide grains can be used as substantially non-light-sensitive silver halide fine grains, such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. These silver halides may be used singly or in combination.
• the silver halide grains preferably comprise a silver halide containing silver bromide from the viewpoint of solubility, with more preference given to a silver iodobromide having a silver iodide content of not more than 15 mol%, still more preferably 1 to 10 mol%, and ideally 2 to 8 mol%.
• the silver halide grains may be physically ripened with rhodane ion, cyano ion, thiocyanate ion, etc, and may be etched with a silver halide solvent. These silver halide grains are produced by various methods such as the neutral method, the half ammoniacal method and the ammoniacal method in combination with the simultaneous mixing method, the conversion method and other methods.
• the amount of silver halide coated on the non-light-sensitive layer is preferably 0.1 to 3.0 g/m 2 , more preferably 0.3 to 2.0 g/m 2 , and still more preferably 0,5 to 1.0 g/m 2 , where the amount is as of silver.
• the non-light-sensitive layer may concurrently contain matting agents such as colloidal silica and polymethyl methacrylate, high boiling solvents such as tricresyl phosphate and dioctyl phthalate, UV absorbents, antioxidants, lipophilic components such as hydroquinone derivatives, coating aids such as surfactants and gelatin hardening emulsions.
• matting agents such as colloidal silica and polymethyl methacrylate
• high boiling solvents such as tricresyl phosphate and dioctyl phthalate
• UV absorbents such as tricresyl phosphate and dioctyl phthalate
• UV absorbents such as tricresyl phosphate and dioctyl phthalate
• UV absorbents such as tricresyl phosphate and dioctyl phthalate
• UV absorbents such as tricresyl phosphate and dioctyl phthalate
• gelatin as a binder for non-light-sensitive layer
• the gelatin can be partially or totally replaced with proteins, sugar derivatives and starch derivatives such as colloidal albumin, agar, gum arabic, alginic acid and cellulose derivatives.
• a formalin scavenger may be added to the light-sensitive material of the present invention.
• Examples of preferably used formalin scavengers include those described in Japanese Patent O.P.I. Publication Nos. 87028/1975, 133450/1982 and 150950/1983, US Patent Nos. 2,895,827, 3,652,278, 3,811,891, 4,003,748, 4,411,987, 4,414,309, 4,418,142 and 4,464,463, US Defense Patent No. 900,028, West German Patent Nos. 3,223,699, 3,227,961 and 3,227,962 and RD Number 10133.
• a matting agent may be added for reducing gloss, improving retacheability, preventing aggregation of light-sensitive material and other purposes.
• Examples of preferably used matting agents include the organic matting agents described in British Patent No. 1,055,713, US Patent Nos. 1,939,213, 2,221,873, 2,268,662, 2,322,037, 2,376,005, 2,391,181, 2,701,245, 2,992,101, 3,079,257, 3,262,782, 3,443,946, 3,516,832, 3,539,344, 3,591,379, 3,754,924 and 3,767,448 and the inorganic matting agents described in West German Patent No. 2,529,321, British Patent Nos. 760,775 and 1,260,772 and US Patent Nos.
• the grain size of matting agent can be selected as appropriate according to the thickness of photographic structural layer, preferably 0.05 to 10 am.
• the amount of matting agent added is preferably 1 to 300 mg/m 2 .
• the dry film thickness of the photographic component layer is preferably not more than 16 ⁇ m.
• the photographic component layer involves the red-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, the blue-sensitive silver halide emulsion layer and the interlayer, filter layer, protective layer and other layers formed as necessary, and does not include the support.
• Dry film thickness is determined under controlled conditions of 23 °C temperature and 55% humidity. It can be measured on a scanning electron micrograph of a cross section of the dry sample, whereby the film thickness of each layer of a multiple-layered structure can be determined separately.
• the thickness between the upper face of the emulsion layer farthermost from the support and the lower face of the emulsion layer closest to the support is preferably not more than 14 ⁇ m.
• the light-sensitive material for the present invention preferably has a water absorption rate of 170 to 230%, as determined using the following equation 1.
• A weight of light-sensitive material under controlled conditions of 23°C temperature and 55% RH,
• Supports for light-sensitive materials incorporating the silver halide emulsion of the present invention include flexible reflective supports such as papers laminated with a-olefin polymer (e.g., polyethylene, polypropylene, ethylene-butene copolymer) and synthetic papers, flexible supports comprising a film of a semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate or polyamide, whether provided with a reflective layer, glass, metals and porcelain.
• a-olefin polymer e.g., polyethylene, polypropylene, ethylene-butene copolymer
• synthetic papers flexible supports comprising a film of a semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate or polyamide, whether provided
• Cellulose acetate films and elongated polyethylene terephthalate films are particularly preferred.
• the silver halide material of the present invention may be coated directly or via one or more subbing layers for improving support surface adhesive properties, antistatic property, dimensional stability, abrasion resistance, hardness, anti-halation property, tribology and/or other properties after the support surface has been treated by corona discharge, ultraviolet irradiation, flaming or otherwise treated as necessary.
• subbing layers for polyethylene terephthalate film which are preferably used include the subbing layers described in Japanese Patent O.P.I. Publication Nos. 19941/1984, 77439/1984 and 224841/1984 and Japanese Patent Examined Publication No. 53029/1983.
• subbing layers preferred for cellulose triacetate film support include those described in US Patent No. 2,852,378 and Japanese Patent Examined Publication No. 13826/1968.
• the hydrophilic colloid layer may be a light-sensitive silver halide emulsion layer or non-light-sensitive layer.
• the preferred method of storing the light-sensitive material at a relative humidity of not more than 55% is sealing packaging.
• Scaling packaging for the present invention means moisture-resistant packaging which is well known in the field of ordinary packaging.
• packaging materials which can be used for the invention include metal plates and metal foils such as aluminum plates, tin plates and aluminum foils, glass, polymers such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate and polyamide, complex laminated materials of various polymers with cellophane, paper, aluminum foil and other materials.
• Sealing can be achieved by adhesive methods, which use various adhesives, thermal fusion methods such as heat sealing, methods using a patrone case, which are common in the photographic industry, and other methods. These sealing methods are described in detail in "Syokuhin Hoso Gijyutsu Binran", edited by Japan Packaging Institute, pp. 573-609 and other publications.
• Preferable conditions for the present invention are such that the weight difference AW 30 at 25 ° C temperature and 30% relative humidity has a negative value, more preferably the weight change AW 35 at 25 ° C temperature and 35% relative humidity has a negative value.
• a patrone case made of a polymer such as polyethylene or polypropylene is preferred for a roll of photographic light-sensitive material; a heat sealed polyethylene etc, are preferred for a sheet of photographic light-sensitive material.
• These modes of sealing packaging may be doubled.
• packaging at reduced relative humidity may be achieved by packaging the silver halide photographic light-sensitive material in a low humidity room, by drying the light-sensitive material to a degree higher than usual during the drying process, or by keeping a low humidity in the presence of a desiccant such as silica gel in the package.
• a desiccant such as silica gel
• fluorine compound known as an antistatic agent.
• fluorine compounds which can be used for this purpose include those described in Japanese Patent Examined Publication No. 43130/1973 and Japanese Patent O.P.I. Publication Nos. 7781/1970 and 55052/1980.
• the bleach and bleach-fixer for the present invention contain at least one of imidazole, its derivatives and the compounds represented by the following formulas I through IX, the desired effect of the invention is enhanced. Since these additives offer an additional effect of suppressing precipitation attributable to silver in the bleacher, they are more preferably used.
• Q represents a group of atoms necessary to form a nitrogen-containing heterocyclic group (including those condensed with a 5- or 6-membered unsaturated ring);
• R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic group (including those condensed with a 5- or 6-membered unsaturated ring) or amino group.
• R 2 and R 3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, hydroxyl group, carboxyl group, amino group, acyl group having 1 to 3 carbon atoms, aryl group or alkenyl group.
• A represents or an n -valent heterocyclic residue (including those condensed with a 5- or 6-membered unsaturated ring);
• Z represents a hydrogen atom, alkali metal atom, ammonium group, amino group, nitrogen-containing heterocyclic residue, alkyl group or M represents a divalent metal atom;
• R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic residue (including those condensed with a 5- or 6-membered unsaturated ring) or amino group; n 1 through n 6 and m 1 through m 5 independently represent an integer of 1 to 6.
• B represents an alkylene group having 1 to 6 carbon atoms;
• Y represents or -CH ⁇ ;
• R4 and R 5 have the same definitions as R 2 and R 3 , respectively.
• R 4 and R 5 may independently represent -B-SZ;
• R 4 and R 5 may bind to form a ring.
• R 6 and R 7 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, hydroxyl group, carboxyl group, amino group, an acyl group having 1 to 3 carbon atoms, aryl group, alkenyl group or -B 1 -S-Z 1 .
• R 6 and R 7 may bind to form a ring.
• Y 1 represents N- or ⁇ CH-;
• B 1 represents an alkylene group having 1 to 6 carbon atoms,
• Z 1 represents a hydrogen atom, alkali metal atom, ammonium group, amino group, nitrogen-containing
• n 7 represents an integer of 1 to 6.
• R 1 represents an alkyl group or -(CH 2 ) n8 SO 3 ⁇ ; when R 1 o is - (CH 2 ) n8 SO 3 ⁇ , l represents 0; when R 1 o is an alkyl group, l represents 1.
• G 8 represents an anion.
• n 8 represents an integer of 1 to 6.
• Q 1 represents a group of atoms necessary to form a nitrogen-containing heterocyclic group (including those condensed with a 5- or 6-membered unsaturated or saturated ring)
• R 11 represents a hydrogen atom, alkali metal atom, or alkyl group.
• Q' has the same definition as Q1.
• Di, D 2 , D 3 and D 4 independently represent a bond, an alkylene group having 1 to 8 carbon atoms or vinylene group; qi, q 2 , q 3 and q 4 independently represent 0, 1 or 2.
• the ring formed with sulfur atoms may be condensed with a 5- or 6-membered saturated or unsaturated ring.
• X 2 represents -COOM', -OH, -SO 3 M', -CONH 2 , -S0 2 NH 2 , -NH 2 , -SH, -CN, -CO 2 R 16 , -SO 2 R 16 , -OR 16 , -NR 16 R 17 , -SR 16 , -SO 3 R 16 , -NHCOR 16 , -NHS0 2 R 16 , -OCOR 16 or -S0 2 R 16 ; Y 2 represents or a hydrogen atom; m 9 and n 9 independently represent an integer of 1 to 10.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 17 and R 18 independently represent a hydrogen atom, lower alkyl group, acyl group or
• R 16 represents a lower alkyl group
• R 19 represents -NR 20 R 21 , -OR 22 or -SR 22
• R 2 o and R 21 independently represent a hydrogen atom or lower alkyl group
• R 22 represents a group of atoms necessary to form a ring together with R 18 .
• R 2 o or R 11 may bind with R 18 to form a ring.
• M' represents a hydrogen atom or cation.
• Ar represents a divalent group or a divalent organic group comprising a combination of an aryl group and an oxygen atom and/or an alkylene group
• B 2 and B 3 independently represent a lower alkylene group
• R 23 , R 24 , R 25 and R 26 independently represent a hydroxy-substituted lower alkyl group
• x and y independently represent 0 or 1
• G' represents an anion
• z represents 0, 1 or 2.
• R 29 and R 30 independently represent a hydrogen atom, alkyl group, aryl group or heterocyclic group
• R 3 represents a hydrogen atom or alkyl group
• R 32 represents a hydrogen atom or carboxyl group.
• the compounds represented by Formulas I through IX which are preferably used for the present invention, are usually used as bleaching accelerators and hereinafter referred to as the bleaching accelerators for the present invention.
• Typical examples of the bleaching accelerators for the present invention represented by Formula I through IX include the following compounds, but these are not to be construed as limitative.
• bleaching accelerators may be used singly or in combination. Good results are obtained when the amount of addition falls in the range of from about 0.01 to 100 g per liter of bleacher or bleach-fixer. In general, however, too small amounts do not offer a significant bleaching accelerating effect; too large amounts cause precipitation and can stain the silver halide color photographic light-sensitive material to be processed. For this reason, the amount of addition is preferably 0.05 to 50 g, more preferably 0.05 to 15 g per liter of bleacher or bleach-fixer.
• bleaching accelerator When using a bleaching accelerator, it may be added and dissolved as such, but it is the common practice to add it in solution in water, alkali, organic acid or another solvent; methanol, ethanol, acetone and other organic solvents may be used as necessary to dissolve the bleaching accelerator.
• the bleacher for the present invention can be used at the pH range from 0.2 to 8.0, and it is preferable to use it at a pH between 1.0 and 7.0, more preferably between 2.0 and 6.5.
• Processing temperature is normally 20 to 45 C, desirably 25 to 42 C.
• the bleacher for the present invention is used normally in the presence of a halide such as ammonium bromide.
• the bleacher for the present invention may contain one or more pH buffers comprising various acids or salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
• pH buffers comprising various acids or salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
• acids or salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
• Various brightening agents, defoaming agents, surfactants and fungicides may also be added.
• the bleaching agent for the bleach and bleach-fixer for the present invention is preferably a ferric complex salt of aminocarboxylic acid or aminophosphonic acid.
• the aminocarboxylic acid or aminophosphonic acid is an amino compound having at least two carboxylic acid groups or at least two phosphonic acid groups, respectively.
• Compounds represented by the following formulas XII and XIII are preferred.
• E represents a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R 83 0R 83 0R 83 - or -R 83 ZR 83 -;
• Z represents N-R83-A6 or N-A 6 ;
• R 79 and R 83 independently represent a substituted or unsubstituted alkylene group;
• a 2 through A 6 independently represent a hydrogen atom, -OH, -COOM or -PO 3 M 2 ;
• M represents a hydrogen atom or alkali metal atom. Examples of preferred compounds represented by Formulas XII and XIII are given below.
• XII-1, XII-2, XII-4, XII-6, XII-7, XII-10, XII-19, XIII-1 and XIII-5 are particularly preferable from the viewpoint of the desired effect of the invention, with more preference given to XII-4 for the same reason.
• the ferric complex salt of organic acid for the present invention is used in the form of a free acid (hydrogen salt), a salt of an alkali metal such as sodium, potassium or lithium, ammonium salt, or a water-soluble amine salt such as triethanolamine salt, but potassium salts, sodium salts and ammonium salts are preferably used. These ferric complex salts may be used singly or in combination.
• the amount of their use can be selected according to the amount of silver coated, silver halide composition and other factors in the light-sensitive material to be processed. For example, they can be used at not less than 0.01 mol, preferably 0.05 to 1.0 mol per mol of bleacher or bleach-fixer. When using a replenisher, it is desirable to use it at a maximum possible high concentration for the purpose of replenishment with a small amount of dense replenisher.
• the amount of replenisher for the bleacher for the present invention is normally 20 to 500 ml, more preferably 30 to 350 ml, still more preferably 40 to 300 ml, and ideally 50 to 250 ml per m 2 of silver halide color photographic light-sensitive material.
• the bleacher and bleach-fixer for the present invention must contain a fixing agent.
• fixing agents include compounds which form a water-soluble complex salt upon reaction with silver halide, such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate and other thiosulfates, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate and other thiocyanates, thiourea and thioether.
• fixer and bleach-fixer may contain one or more pH buffers comprising various acids or salts such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite and other sulfites, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
• pH buffers comprising various acids or salts such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite and other sulfites, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bi
• a rehalogenating agent such as an alkali halide or ammonium halide, e.g., potassium bromide, sodium bromide, sodium chloride or ammonium bromide. It is also acceptable to add as necessary ordinary additives known to be added to fixer and bleach-fixer, such as borates, oxalates, acetates, carbonates, phosphates and other pH buffers and alkylamines and alkylene oxides.
• the fixing agent is used normally at not less than 0.1 mol per liter of processing solution. It is preferable from the viewpoint of the desired effect of the invention to use the fixing agent in the range from 0.6 to 4 mol, more preferably 0.9 to 3.0 mol, and still more preferably 1.1 to 2.0 mol.
• air blowing or oxygen blowing may be carried out as necessary in the processing bath or processing bath replenisher tank, or an appropriate antioxidant, such as hydrogen peroxide, hydrobromate or persulfate may be added as necessary.
• the amount of replenisher for the fixer or bleach-fixer for the present invention is not more than 800 ml per m 2 of light-sensitive material, the desired effect of the invention is enhanced. Still better results are obtained when the amount of replenisher is 20 to 650 ml, more preferably 30 to 400 ml per m 2 of light-sensitive material.
• the fixer or bleach-fixer for the present invention contains an iodide such as ammonium iodide, potassium iodide, sodium iodide or lithium iodide at 0.11 to 10 g/I, the effect of the invention is enhanced. Still better results are obtained when the iodide content is 0.3 to 5 g/I, more preferably 0.5 to 3 g/I, and ideally 0.8 to 2 g/I.
• an iodide such as ammonium iodide, potassium iodide, sodium iodide or lithium iodide
• These compounds represented by Formulas FA and FB may be used singly or in combination.
• preferred combinations include the combination of thiourea, ammonium thiocyanate and ammonium iodide, the combination of thiourea and ammonium thiocyanate, the combination of FA-12 and thiourea, the combination of FA12 and ammonium thiocyanate, the combination of FA-12 and ammonium iodide, the combination of FA-12 and FA-32 and the combination of FA-12 and FA-38.
• a sulfite adduct to the fixer and bleach-fixer for the present invention.
• Examples of such a compound which forms a stable sulfite adduct with sulfite ion include compounds having an aldehyde group, compounds having a cyclic hemiacetal, compounds having an a-dicarbonyl group and compounds having a nitrile group, with preference given to the compounds represented by Formulas A-I and A-II.
• alkyl groups having 1 to 6 carbon atoms, whether linear or branched, include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-valer group, isovaler group, hexane group and isohexane group. These groups may be substituted.
• substituted group examples include formyl groups such as formylmethyl and 2-formylethyl groups, amino groups such as aminomethyl and aminoethyl groups, hydroxyl groups such as hydroxymethyl, 2-hydroxyethyl and 2-hydroxypropyl groups, alkoxy groups such as methoxy and ethoxy groups, halogenated groups such as chloromethyl, trichloromethyl and dibromomethyl groups.
• the alkenyl group may be substituted or not, including vinyl and 2-propenyl groups as unsubstituted groups, and 1,2-dichloro-2-carboxyvinyl and 2-phenylvinyl groups as substituted groups.
• sulfite adducts are used preferably at 0.1 to 80 g, more preferably 0.5 to 40 g per liter of processing solution.
• forced stirring does not mean ordinary diffusive migration of liquid but means forced stirring by a mechanical means for stirring.
• Forced stirring can be achieved by the following methods.
• the high pressure spraying method is a method in which a processing solution is sprayed directly to the light-sensitive material in the processing solution via a spray nozzle at a discharge pressure of not less than 0.1 kg/cm 2 .
• the blow stirring method is a method in which a processing solution is blown directly to the light-sensitive material in the processing solution via a nozzle at a discharge pressure of not less than 0.1 kg/cm 2 .
• Pressure pumps and liquid supply pumps are usually used as pressure sources. Pressure pumps include plunger pumps, gear pumps, magnet pumps and cascade pumps, specifically the 15-LPM model, 10-BFM model, 20-BFM model and 25-BFM model, all produced by Maruyama Seisakusho.
• liquid supply pumps examples include the MD-30 model, MO-56 model, MDH-25 model and MDK-32 model, all produced by Iwaki Company.
• Nozzles and spray nozzles are available in various types such as the straight type, fan type, circular type, entire surface type and ring type, which exert strong impact to such extent that the subject light-sensitive material undergoes fine vibration.
• Spray impact force is determined mainly by flow rate (I/min) and spray pressure (kg/cm 2 ). Therefore, to ensure a satisfactory effect, a pressurizing apparatus is required which permits pressure adjustment in proportion to the number of spray nozzles. Best pressure is 0.3 to 10 kg/cm 2 . Lower pressures do not offer the desired effect; higher pressures can damage or break the light-sensitive material.
• the air bubbling method is a method in which air or inert gas is supplied to a sparger installed beneath the lower transport roller of the processing bath, the light-sensitive material is vibrated by bubbles discharged from the sparger and the processing solution is efficiently brought into contact with the top, back and side faces of the light-sensitive material.
• Materials suitable for spargers include hard vinyl chloride, polyethylene-coated stainless steel, sintered metals and other corrosion-resistant materials. Pore size is set to yield a bubble diameter of 2 to 30 mm, preferably 5 to 15 mm for better results.
• Examples of means for supplying air include air compressors such as Babicon (0.4 kW, BU7TL, produced by Hitachi Ltd.) and air pumps such as the Air Pump Ap 220 model, produced by Iwaki Company. As for air flow rate, 2 to 30 I/min per transport rack of automatic developing machine is necessary, with more preference given to 5 to 20 I/min for better results.
• the amount of air or inert gas supplied should be adjusted according to the size of processing tank and the amount of light-sensitive material, but it is preferable to supply air or inert gas in such an amount that the amplitude of vibration of the light-sensitive material by bubbles will be 0.2 to 20 mm.
• the ultrasonic vibration method is a method in which the light-sensitive material is subjected to ultrasonic wave using an ultrasonic wave oscillator installed in the bottom or side wall space of the processing tank of the automatic developing machine to increase development accelerating efficiency.
• ultrasonic wave oscillators include the magnetostrictive nickel vibrator (horn type) and magnetostrictive barium titanate vibrator (holder type), both produced by Choonpa Kogyo Company.
• Vibrator frequency of the ultrasonic wave oscillator is 5 to 1000 kHz, with preference given to 10 to 50 kHz from the viewpoint of the desired effect of the invention and prevention of damage of the automatic developing machine.
• ultrasonic waves may be irradiated directly to the light-sensitive material or indirectly via a reflecting board, direct irradiation is preferred because ultrasonic waves are attenuated in proportion to irradiation distance.
• Irradiation time is preferably at least 1 second. In the case of partial irradiation, it may be conducted in the initial, middle or last stage of processing.
• the vibration method is a method in which the light-sensitive material is vibrated between the upper and lower rollers in the processing tank of the automatic developing machine for effective immersion treatment.
• vibrators commonly used as sources of vibration include the V-2B and V-4B models of Shinko Electric Co., Ltd..
• the vibrator is installed firmly on the upper portion of the immersion treatment tank of the automatic developing machine so that the vibrator faces the back face of the light-sensitive material.
• Vibrator frequency is preferably 100 to 10000/min, most preferably 500 to 6000/min.
• the amplitude of vibration of the light-sensitive material to be treated is 0.2 to 30 mm, preferably 1 to 20 mm. Lower frequencies fail to offer the desired effect; higher frequencies can damage the light-sensitive material.
• the number of vibrators used varies depending on the size of automatic developing machine, better results are obtained when at least one vibrator is installed for every processing tank if there are a plurality of processing tanks.
• Another preferred mode of embodiment of the processing method of the present invention is to allow a part or all of the overflow from the color developer for the present invention to enter in the bleaching bath which follows. This is preferable because occurrence of sludge in the bleacher is suppressed by flowing a given amount of the color developer for the present invention into the bleacher.
• silver recovery efficiency improves when a part or all of the overflow from the stabilizing bath which follows is flown in the bleach-fixer or fixer.
• the time of processing the silver halide color photographic light-sensitive material with the color developer is preferably not longer than 240 seconds, more preferably not longer than 220 seconds, and still more preferably 20 to 150 seconds.
• the color developer contains an aromatic primary amine based color developing agent at preferably not less than 5.0 x 10- 3 mol, more preferably not less than 1.0 x 10- 2 , and still more preferably 1.5 x 10- 2 to 2 x 10- 1 per liter of the processing solution.
• Color developing agents for color developers which are preferably used for the present invention are described in detail below.
• Aromatic primary amine based color developing agents for the color developer which is preferably used include known color developing agents which are widely used in various color photographic processes. These developing agents include aminophenol derivatives and p-phenylenediamine derivatives. These compounds are used normally in the form of a salt such as hydrochloride or sulfate, since salt forms are more stable than free forms.
• aminophenol developing agents examples include o-aminophenol, p-aminophenol, 5-amino-2-ox- ytoluene, 2-amino-3-oxytoluene and 2-oxy-3-amino-1,4-dimethylbenzene.
• aromatic primary amine based color developing agents have an amino group with at least one water-soluble group are especially useful because the desired effect of the invention is enhanced and crystal deposition on the inside wall of the color developing layer of the automatic color developing machine is suppressed, with more preference given to the compound represented by the following formula E.
• R 1 represents a hydrogen atom, halogen atom or alkyl group, which alkyl group represents a linear or-branched alkyl group having 1 to 5 carbon atoms and which may have a substituent.
• R 2 and R 3 independently represent a hydrogen atom, alkyl group or aryl group, which groups may have a substituent. At least one of R 2 and R 3 is an alkyl group substituted by a water-soluble group such as a hydroxyl group, carboxylic acid group, sulfonic acid group, amino group or sulfonamide group, or
• This alkyl group may have an additional substituent.
• R 4 represents a hydrogen atom or alkyl group, which alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms; p and q independently represent an integer of 1 to 5.
• p-phenylenediamine derivatives represented by Formula E can be used in the form of salts of organic or inorganic acid, including hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, oxalate and benzenedisulfonate.
• Compounds which are preferably used in the color developer for the present invention are sulfites, hydroxylamine and developing inhibitors.
• sulfites examples include sodium sulfite, sodium hydrogen sulfite, potassium sulfite and potassium hydrogen sulfite. These sulfites are used at preferably 0.1 to 40 g/l, more preferably 0.5 to 10 g/l.
• the hydroxylamine is used as a counter salt for hydrochloride, sulfate or other salt. It is used at preferably 0.1 to 40 g/l, more preferably 0.5 to 1 0 g/l.
• Examples of developing inhibitors which are preferably used in the color developer include halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide and organic developing inhibitors.
• the amount of their addition is preferably 0.005 to 30 g/l, more preferably 0.01 to 20 g/l.
• Examples of the organic developing inhibitor which is preferably used for the present invention include nitrogen-containing heterocyclic compounds, mercapto-containing compounds, aromatic compounds, onium compounds and compounds substituted by a group having an iodine atom. These compounds are exemplified below. The examples given below are not to be construed as limitative.
• the organic developing inhibitors represented by Formulas R-I through R-XIII, described in Japanese Patent Application No. 12781/1986, pp. 96-100 can be used. Using such an organic developing inhibitor with the organic developing inhibitor for the present invention enhances the effect of the invention.
• the organic developing inhibitor for the present invention is more specifically exemplified by Compounds Z-1 through Z-3, Z-6, Z-8 through Z-13, Z-15 through Z-17, Z-19, Z-22 through Z-25, Z-29, Z-31 through Z-38, Z-40, Z-41, Z-43 through Z-64 and Z-66 through Z-73, shown in pp. 101-113 in the same publication as above.
• the color developer for the present invention may contain various ordinary additives, for example, alkalis such as sodium hydroxide and sodium carbonate, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners and developing accelerators.
• alkalis such as sodium hydroxide and sodium carbonate
• alkali metal thiocyanates such as sodium hydroxide and sodium carbonate
• alkali metal thiocyanates such as sodium hydroxide and sodium carbonate
• alkali metal thiocyanates alkali metal halides
• alkali metal halides such as sodium benzyl alcohol, water softeners, thickeners and developing accelerators.
• additives to the color developer include antistaining agents, anti-sludge agents, preservatives, laminating effect enhancers and chelating agents.
• the color developer for the present invention is used at a pH of preferably not less than 9, more preferably between 9 and 13.
• Temperature of processing with the color developer is preferably over 38 ° C, more preferably between 40 ° C and 70 ° C, and ideally between 43 ° C and 60 ° C for enhancement of the desired effect of the invention.
• the processing method for photographic light-sensitive material of the present invention is not limited, affording every method of processing.
• a chelating agent represented by one of the following formulas I" through V" enhances the desired effect of the invention.
• R represents an alkyl group having 1 to 5 carbon atoms.
• L represents an alkylene group, cycloalkylene group, phenylene group, -L 8 -O-L 8 -O-L 8 or -L 9 -Z-L 9 -, wherein Z represents
• L through L 13 independently represent an alkylene group.
• R 3 through R 13 independently represent a hydrogen atom, hydroxyl group, carboxylic acid group (including its salt) or phosphonic acid group (including its salt).
• At least two of R 3 through R 6 represent a carboxylic acid group (including its salt) or phosphonic acid group (including its salt); at least two of R 7 through R 9 represent a carboxylic acid group (including its salt) or phosphonic acid group (including its salt).
• Ri, R 2 , R 3 and R 4 independently represent a hydrogen atom, halogen atom, sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -ORs-COOR 6 , or phenyl group.
• R 6 , R 7 and R 8 independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• R 2 represents -OH or a hydrogen atom
• R 1 represents a halogen atom, sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -ORs-COOR 6 , or phenyl group
• n represents an integer of 1 to 3.
• Examples of the compound represented by Formula I" include 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid and 1-hydroxy-1,1-diphosphonomethanoic acid, with more preference given to 1-hydroxyethylidene-1,1-diphosphonic acid. These compounds can be used as alkali metal salts, ammonium salts and other forms.
• the amount of these compounds added is preferably 1 x 10- 4 mol to 0.5 mol, more preferably 4 x 10- 4 mol to 0.1 mol per liter of color developer.
• the alkylene group, cycloalkylene group and phenylene group represented by L and the alkylene groups represented by L 1 through L 13 include those having a substituent.
• II"-1, II"-2, II"-5, II"-8, II"-19, III"-1 and III"-4 are particularly preferably used from the viewpoint of the desired effect of the invention, with more preference given to 11-2 because precipitation is suppressed during elapse of time.
• the amount of these chelating agents added is preferably 0.1 to 20 g per liter of color developer, with more preference given to the range from 0.3 to 5 g from the viewpoint of the desired effect of the invention.
• R i , R 2 , R 3 and R 4 independently represent a hydrogen atom, halogen atom, sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -ORs, -COOR 6 , or phenyl group.
• R5, R6, R7 and R 8 independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• R 2 represents -OH or a hydrogen atom
• R 1 represents a halogen atom, sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -ORs, -COOR 6 , or phenyl group.
• Examples of the alkyl groups represented by R i , R 2 , R 3 and R 4 include methyl group, ethyl group, i-propyl group, propyl group, t-butyl group, butyl group, hydroxymethyl group, hydroxyethyl group, methyl- carboxylic acid group and benzyl group.
• the alkyl groups represented by R s , R 6 , R 7 and R 8 have the same definitions as above but include octyl groups.
• Examples of the phenyl groups represented by R i , R 2 , R 3 and R 4 include phenyl group, 2-hydroxyphenyl group and 4-aminophenyl group.
• 1,2-dihydroxybenzene-3,5-disulfonic acid is preferably used for the present invention and can be used as a salt of an alkali metal such as sodium or potassium.
• the compounds described above can be used in the content range from 5 mg to 20 g, with preference given to the range from 10 mg to 10 g, and more preferably 20 mg to 3 g per liter of developer for better results.
• the compounds for the present invention may be used singly or in combination.
• combinations of aminopolycarboxylic acid, organic phosphonic acid, etc. are preferred.
• the color developer for the present invention preferably contains the compound represented by the following formula 2', since the desired effect of the invention is enhanced.
• R 1 and R 2 independently represent an alkyl group, alkenyl group, aryl group or hydrogen atom. Not both R 1 and R 2 represent a hydrogen atom at the same time. R 1 and R 2 may form a ring.
• R 1 and R 2 independently represent a substituted or unsubstituted alkyl group, aryl group or hydrogen atom but not both R 1 and R 2 represent a hydrogen atom at the same time; the alkyl groups and alkenyl groups represented by R 1 and R 2 may be identical or not.
• the alkyl groups, alkenyl groups and aryl groups represented by R 1 and R 2 include those having a substituent. Examples of the ring formed by R 1 and R 2 include heterocyclic groups such as piperidineforyl ring.
• R 1 or R 2 examples include hydroxyl groups, alkoxy groups, alkyl groups, arylsulfone groups, amide groups, carboxyl groups, cyano groups, sulfo groups, nitro groups and amino groups.
• hydroxylamine compounds are used normally in the form of hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and free compound.
• the concentration of the compound represented by Formula 2' in the color developer is normally 0.2 to 50 g/I.
• the stabilizing solution for the present invention (hereinafter also referred to as the stabilizer) preferably contains an aldehyde derivative.
• the aldehyde derivative is represented by one of the following formulas IV' through VI'.
• R 16 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, formyl group, acetyl group, acetonitrile group or hydroxyl group, which alkyl group may be substituted by an alkoxy group, formyl group, amino group, hydroxyimino group, halogen atom or another substituent.
• R 17 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
• R 18 represents an alkyl group having 1 to 5 carbon atoms which may be substituted;
• M represents an alkali metal;
• R 19 and R 2 o independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted;
• n represents an integer of 0 to 4.
• aldehyde derivatives are used in the range of preferably from 2.0 x 10- 5 to 2.0 x 10- 2 mol per liter of stabilizer for the compound represented by Formula IV', and 2.0 x 10- 5 to 8.0 x 10- 2 mol for the compounds represented by Formulas V and VI.
• the compound represented by Formula V' is advantageously used from the viewpoint of prevention of environmental pollution and sulfation.
• the stabilizer for the present invention preferably contains a hexamethylenetetramine or N-methylol compound.
• Hexamethylenetetramine compounds include hexamethylenetetramine and its derivatives.
• hexamethylenetetramine derivatives include halogen adducts, inorganic acid adducts, metal salt adducts, phenol derivative adducts, alkylsulfonic acid adducts, arylsulfonic acid adducts, alkylsul- fate adducts, alkylcarboxylic acid adducts, arylcarboxylic acid adducts and alkyl halide adducts of hexamethylenetetramine.
• hexamethylenetetramine and its derivatives are exemplified by the compounds described in "Beilsteins Handbuch der Organishcen Chemie", suppl. II, vol. 26, pp. 200-212.
• Typical examples of hexamethylenetetramine compounds are given below, but these examples are not to be construed as limitative.
• hexamethylenetetramine compounds may be used singly or in combination.
• the amount of their addition is preferably not less than 0.05 g, more preferably 0.3 to 20 g per liter of stabilizer.
• N-methylol compounds are given in US Patent No. 4,859,574, including dimethylol guanidine, trimethylol urea, dimethylol urea, trimethylol melamine and hexamethylol melamine.
• the amount of their addition is normally 0.05 to 20 g, preferably 0.1 to 10 g per liter of stabilizer, in which range the effect of the invention is enhanced.
• dye image stability improves. It is preferable from the viewpoint of the desired effect of the invention to use at least one compound selected from the group comprising the compounds represented by the following formulas I' and II' and water-soluble organic siloxane compounds.
• the surface tension of the stabilizer used to process the light-sensitive material of the present invention is determined by the ordinary method described in "Kaimen Kasseizai no Bunseki to Shikenho", edited by Fumio Kitahara, Shigeo Hayano and Ichiro Hara, March 1, 1982, Kodansha Ltd. using ordinary procedures at 20 ° C.
• R 1 represents a monovalent organic group such as an alkyl group having 6 to 20, preferably 6 to 12 carbon atoms, specifically hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, or an aryl group substituted by an alkyl group having 3 to 20 carbon atoms.
• the substituent is preferably an alkyl groups having 3 to 12 carbon atoms, specifically propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
• the aryl group is exemplified by phenyl, tolyl, xynyl, biphenyl and naphthyl, with preference given to phenyl and tolyl.
• the site of bonding of an alkyl group to the aryl group may be any of the ortho, meta and para positions.
• R 2 represents an ethylene group or propylene group; m represents an integer of 4 to 50.
• X represents a hydrogen atom, -SO 3 M or -P0 3 M 2 ;
• M represents a hydrogen atom, alkali metal such as sodium, potassium or lithium, or -NH 4 .
• R 3 , R 4 , R 5 and R 6 independently represent a hydrogen atom, alkyl group or phenyl group, with the total number of carbon atoms in R 3 , R 4 , R 5 and R 6 reaching 3 to 50.
• X 2 represents an anion of halogen atom, hydroxyl group, sulfuric acid group, carbonic acid group, nitric acid group, acetic acid group or p-toluenesulfonic acid group.
• These compounds represented by Formulas I' and II' and water-soluble organic siloxane compounds may be used singly or in combination. Good results are obtained when they are used in the content range of from 0.01 to 20 g per liter of stabilizer. Amounts of under 0.01 cause significant stain on the light-sensitive material surface; amounts exceeding 20 g lead to adhesion of a large amount of water-soluble organic siloxane compound on the light-sensitive material surface and cause stain.
• the compound represented by Formula I' is preferably used for the present invention, which offers an additional effect of suppression of occurrence of silver sulfide.
• the water-soluble organic siloxane compound for the present invention means an ordinary water-soluble organic siloxane compound as described in Japanese Patent O.P.I. Publication Nos. 18333/1972 and 62128/1974, Japanese Patent Examined Publication Nos. 51172/1980 and 37538/1976 and US Patent No. 3,545,970.
• the compound represented by the following formula III' is preferably used.
• R 8 represents a hydrogen atom, hydroxyl group, lower alkyl group, alkoxy group,
• R 9 , R 10 and R 11 whether identical or not, independently represent a lower alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl or propyl; l represents an integer of 1 to 4; p and q independently represent an integer of 1 to 15.
• the amount of replenisher for the stabilizer for the present invention should be 1 to 80 times, preferably 2 to 60 times the amount of carry-over from the previous bath per unit area of the picture taking color light-sensitive material to be processed, and the previous bath component (bleach-fixer or fixer) concentration in the stabilizer is normally not more than 1/500, preferably not more than 1/1000 in the final stabilizing bath. It is necessary, however, to configure the stabilizing bath so that the previous bath component concentration becomes 1/500 to 1/100000, preferably 1/2000 to 1/50000 from the viewpoint of prevention of environmental pollution and the storage stability of the processing solution.
• the stabilizing bath is configured with a plurality of tanks, preferably 2 to 6 tanks.
• the counter current method the method in which the stabilizer is supplied to a bath and allowed to overflow from the previous bath
• 2 to 6 tanks more preferably 2 to 3 tanks, and ideally 2 tanks.
• the amount of carry-over varies depending on the type of light-sensitive material, the transportation speed and transportation method for the automatic developing machine, the method of squeezing the light-sensitive material surface and other factors
• the amount of carry-over is usually 50 to 150 ml/m 2 for an ordinary picture taking color light-sensitive material (roll film).
• the effect of the invention is enhanced when the amount of replenisher is in the range of from 50 ml to 4.0 I/m 2 , and is more enhanced when the amount of replenisher is in the range of from 200 to 1500 ml/m2.
• Temperature of processing with the stabilizer is normally 15 to 60 C, preferably 20 to 45 C.
• the stabilizer preferably contains a chelating agent represented by one of the following formulas VII' through IX' for improving the brightness in the unexposed portion and preventing yellow stain of dye images after storage.
• a chelating agent represented by one of the following formulas VII' through IX' for improving the brightness in the unexposed portion and preventing yellow stain of dye images after storage.
• E represents an alkylene group, cycloalkylene group, phenylene group, -R 5 -O-R 5 -, -R 5 -O-R 5 -O-R 5 -or -R 5 -Z-R 5 -.
• Z represents
• R 1 through R 6 independently represent an alkylene group.
• a through A3 independently represent -COOM or -P0 3 M 2 ;
• M represents a hydrogen atom or alkali metal atom.
• R 7 represents an alkyl group, aryl group or nitrogen-containing 6-membered ring.
• M represents a hydrogen atom or alkali metal atom.
• R 8 , R 9 and R 10 independently represent a hydrogen atom, hydroxyl group, -COOM, -P0 3 M 2 or alkyl group;
• B 1 , B 2 and B 3 independently represent a hydrogen atom, hydroxyl group, -COOM, -P0 3 M 2 or
• J represents a hydrogen atom, alkyl group, -C 2 H 4 OH or - PO 3 M 2 .
• M represents a hydrogen atom or alkali metal atom; n and m independently represent 0 or 1.
• the chelating agent preferably used in the stabilizer is used at preferably 0.01 to 100 g, more preferably 0.05 to 50 g, and still more preferably 0.1 to 20 g per liter of stabilizer.
• the pH value of the stabilizer which is preferably used for the present invention, it is preferably in the range of from 4.0 to 9.0, more preferably 4.5 to 9.0, and still more preferably 5.0 to 8.5 for improving image storage stability as well as the effect of the invention.
• Any generally known alkali or acid can be used as a pH regulator for the stabilizer which is preferably used for the present invention.
• the stabilizer which is preferably used for the present invention may contain salts of organic acids such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid, pH regulators such as phosphate, borate, hydrochloride and sulfate, surfactants, preservatives and salts of metals such as Bi, Mg, Zn, Ni, Al, Sn, Ti and Zr. These compounds can be added in any amount and in any combination, as long as their addition is necessary to keep the stabilizing bath at a desired pH level for the invention and does not adversely affect the storage stability and occurrence of precipitation during storage of color photographic images.
• organic acids such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid
• pH regulators such as phosphate, borate, hydrochloride and sulfate
• surfactants preservatives and salts of metals
• preservatives and salts of metals such as Bi, Mg, Zn
• fungicides which are preferably used in each stabilizer for the present invention include hydroxybenzoate compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen releasing compounds and benzotriazole compounds.
• the hydroxybenzoate compounds include the methyl ester, ethyl ester, propyl ester and butyl ester of hydroxybenzoic acid, with preference given to the butyl ester, i-butyl ester and propyl ester of hydroxybenzoic acid, with more preference given to a mixture of these three esters of hydroxybenzoic acid.
• the phenol compounds which are preferably used as fungicides for the present invention are compounds which may have as a substituent an alkyl group, halogen group, nitro group, hydroxyl group, carboxylic acid group, amino group or phenyl group, with preference given to o-phenylphenol, o-cyclohexylphenol, phenol, nitrophenol, chlorophenol, cresol, guaiacol and aminophenol.
• the most preferable is a combination of o-phenylphenol and a bisulfite adduct of aldehyde derivative, which has a marked fungicidal effect.
• the thiazole compounds have a nitrogen atom and a sulfur atom in their 5-membered ring, with preference given to 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-chloro-4-thiazolyl-benzimidazole.
• the pyridine compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine and sodium-2-pyridinethiol-1-oxide, with preference given to sodium-2-pyridinethiol-1-oxide.
• the guanidine compounds include cyclohexizine, polyhexamethylene, biguanidine hydrochloride and dodecylguanidine hydrochloride, with preference given to dodecylguanidine and its salt.
• the carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate.
• the morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine.
• the quaternary phosphonium compounds include tetraalkylphosphonium salts and tetraalkox- yphosphonium salts, with preference given to tetraalkylphosphonium salts, specifically tributyl-tetradecyl- phosphonium chloride and triphenyl-nitrophenylphosphonium chloride.
• the quaternary ammonium compounds include benzalkonium salts, benzetonium salts, tetraalkylammonium salts and alkylpyridinium salts, specifically dodecyldimethylbenzylammonium chloride, didecyl- dimethylammonium chloride and laurylpyridinium chloride.
• the urea compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)ureaand N-(3-trifluoromethyl-4-chlorophenyl)-N'-(4-chlorophenyl)urea.
• the isoxazole compounds include 3-hydroxy-5-methylisoxazole.
• the propanolamine compounds include n-propanols and i-propanols, specifically DL-2-benzylamino-1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol, i-propanolamine, di-i-propanolamine and N,N-dimethyl-i-propanolamine.
• the sulfamide compounds include o-nitrobenzene sulfamide, p-aminobenzene sulfamide, 4-chloro-3,5-dinitrobenzene sulfamide and a-amino-p-toluene sulfamide.
• the amino acid compounds include N-lauryl-,8-alanine.
• the active halogen releasing compounds include sodium hypochlorite, sodium dichloroisosianurate, trichloroisosianuric acid, chloramine T, chloramine B, dichloromethylhydantoin and chlorobromodimethyl- hydantoin, with preference given to sodium hypochlorite, sodium dichloroisocyanurate and trichloroisocyanuric acid.
• the benzotriazole compounds are exemplified as follows.
• fungicides shown above are preferably used phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, active halogen releasing compounds and benzotriazole compounds, with more preference given to phenol compounds, thiazole compounds, active halogen releasing compounds and benzotriazole compounds from the viewpoint of the storage stability of processing solution.
• the amount of fungicide added to the stabilizer is not more than 0.001 g per liter of stabilizing solution for non-water washing treatment, the desired effect of the invention is not obtained; if it exceeds 50 g, cost rises undesirably and dye image storage stability is deteriorated. For this reason, it is used in the range of from 0.001 to 50 g, preferably 0.005 to 10 g.
• silver may be recovered by various methods from processing solutions containing a soluble silver salt such as the fixer and bleach-fixer as well as the stabilizer.
• methods which serve well for this purpose include the electrolytic method described in French Patent No. 2,299,667, the precipitation method described in Japanese Patent O.P.I. Publication No. 73037/1977 and West German Patent No. 2,331,220, the ion exchange method described in Japanese Patent O.P.I. Publication No. 17114/1976 and German Patent No. 2,548,237 and the metal replacement method described in British Patent No. 1,353,805.
• silver may be recovered from the overflow from a processing solution containing the soluble silver salt by one of the above-mentioned methods, and the waste liquid may be disposed or recycled for use as a replenisher or bath processing solution in the presence of a re-activating agent. It is particularly preferable to recover silver after mixing the stabilizer with the fixer or bleach-fixer.
• the stabilizer may be subjected to ion exchange treatment, electrodialytic treatment (Japanese Patent Application No. 96352/1984), reverse osmotic treatment (Japanese Patent Application No. 96352/1984) and other treatments.
• deionized water for the stabilizer. This is because the fungicidal effect on the stabilizer, stabilizer stability and image stability improve. Any means of deionization can be used, as long as the electric conductivity of washing water after treatment is not more than 50 us/cm or the Ca and Mg ion concentration of the treated washing water is not more than 5 ppm, and it is preferable to use an ion exchange resin or reverse osmotic membrane treatment singly or in combination.
• Ion exchange resins and reverse osmotic membranes are described in the Journal of Technical Disclosure No. 87-1984. It is preferable to use a strongly acidic H type cation exchange resin and a strongly alkaline OH type anion exchange resin.
• the salt concentration in the stabilizer is preferably not more than 1000 ppm, more preferably not more than 800 ppm, since the washing effect is enhanced and brightness and fungicidal property improve.
• Stabilizing time for the present invention is normally not longer than 2 minutes, preferably not longer than 1 minute 30 seconds, and still more preferably not longer than 1 minute for enhancement of effects of the invention, particularly the effect on the stabilizing solution.
• the amount of addition in silver halide color photographic light-sensitive material is expressed in gram per m 2 , unless otherwise stated.
• the figures for silver halide and colloidal silver have been converted to the amounts of silver.
• Figures for the amount of sensitizing dyes are shown in mol per mol of silver in the same layer.
• compositions surfactants SU-1 and SU-2, a viscosity controlling agent, hardeners H-1 and H-2, a stabilizer ST-1, an antifogging agent AF-1, AF-2 comprising two kinds of antifogging agent having average molecular weights of 10,000 and 1,100,000, respectively, samples AI-1 and AI-2 and a compound DI-1 were added to appropriate layers.
• the amount of DI-1 added was 9.4 mg/m 2.
• Sample Nos. 102 through 108 were prepared in the same manner as with sample No. 101 except that the couplers in layers 6 and 7 and the method of their dispersion were changed as shown in Table 1, wherein couplers M-2 and D-4 were represented by the following chemical formulas:
• Table 2 summarizes the coupler solvents for dispersion methods (A), (B) and (C) and the solvents for dispersing or precipitating the dissolved couplers.
• the color developer used had the following composition:
• the color developer replenisher used had the following composition:
• the bleacher used had the following composition:
• the bleacher replenisher used had the following composition:
• the fixer and fixer replenisher used had the following composition:
• the stabilizer and stabilizer replenisher used had the following composition:
• Sample Nos. 101 through 108 were subjected to optical wedge exposure of white light and of blue (B), green (G) and red (R) light obtained by passing white light through Wratten filter Nos. 98, 99 and 26, respectively, produced by Eastman Kodak, followed by development in accordance with the processing time and temperature shown above.
• Table 3 shows the relationships between sample numbers and processing solutions involved in the running processing.
• the ⁇ values corresponding to the blue, green and red transmission densities obtained by white light exposure are given the symbols y NB , ⁇ NG and y NR , respectively.
• the ⁇ values obtained by color separation exposure are given the symbols ⁇ SB , ⁇ SG and ⁇ SR , respectively.
• Table 4 shows relative ⁇ values and ⁇ ratios for each sample for each processing.
• the relative ⁇ values mean relative values of y NG , that is, values relative to the value from sample No. 101 treated with processing solution, taken as 1.0; and the ⁇ ratios for B, G and R mean respectively the ⁇ SB / ⁇ NB , ⁇ SG / ⁇ NG and ⁇ SR / ⁇ NR values for each sample and for each processing.
• IIE interlayer interimage effect

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• 1990
  • 1990-11-30 JP JP33942890A patent/JPH04204940A/ja active Pending
• 1991
  • 1991-11-28 EP EP91120429A patent/EP0488310A1/fr not_active Withdrawn

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