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
  • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
  • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols
  • G03C7/346—Phenolic couplers

Definitions

• This invention concerns silver halide based color photographic photosensitive materials and, more precisely, it concerns color photographic photosensitive materials in which the fading of the dye image which is caused by the fungi which develop when processed color photographs are stored under conditions of high temperature and humidity is prevented effectively.
• This invention further concerns a method of forming a color image by processing the above materials.
• Photographic photosensitive materials are often stored by being adhered or sandwiched in an album made from paper or on a mounting board, or by being sandwiched on Japanese paper with a mounting board on the surface.
• the paste used for adhesion and the paper fibers themselves provide nutrient sources. Fungi grow and proliferate, especially under conditions of high temperature and humidity, and problems arise with fading of the image dyes, especially the cyan dyes, as a result of the action of products excreted by the fungi.
• JP-A as used herein refers to a "published unexamined Japanese patent application"
• JP-A-61-233743 It has been indicated in JP-A-61-233743 that a fungicidal effect can be obtained with little staining and without the occurrence of photostaining by using combinations of specified fungicides and pyrazoloazole based magenta couplers.
• JP-A-60-135942 corresponding to EP 147016 A2
• an ammonium salt for example, ammonium sulfate
• a technique is desired by which the fading due to action of material excreted by fungi can be prevented even when fungi are present.
• a combination of a cyan coupler, a high boiling organic solvent and a water-insoluble and organic solvent-soluble polymer is disclosed in e.g. WO 88/00723, EP 280238 and JP-A-63-104050.
• European Patent Application (Laid Open) 0,276,319A1 discloses a color photographic material comprising a support having thereon a silver halide emulsion layer containing a dispersion of oleophilic fine particles obtained by emulsifying or dispersing a mixture of a coupler which forms a nondiffusible dye, a water-immiscible coupler solvent having a boiling point of not less than 140 °C and a water-insoluble and organic solvent-soluble homo- or copolymer.
• One object of the present invention is to provide silver halide color photosensitive materials for color photographs without image deterioration, such as fading, even on storage under adverse conditions of high temperature and humidity under which fungi flourish.
• a further object of the invention is to provide silver halide color photosensitive materials for color photographs in which the cyan image has the proper hue, and which have good light fastness and little fading due to fungi.
• a light-sensitive silver halide material composed of a support having thereon at least one light-sensitive silver halide emulsion layer containing silver halide grains having a halogen composition of from 0 to 1 mol% of silver iodide, 95 mol% or more silver chloride and the remainder silver bromide, said at least one light-sensitive silver halide emulsion layer or an adjacent layer thereto containing an oil droplet dispersion in a hydrophilic binder, the oil droplets containing the combination of (a) a polymer insoluble in water and soluble in an organic solvent and (b) at least one coupler capable of forming a nondiffusible cyan dye by a coupling reaction with an oxidized form of a primary aromatic amine developing agent, characterized in that the oil droplets further contain (c) a high boiling point organic solvent having the formula (III): W 1 -COOW 2 (
• the present invention further provides a method of forming a color image comprising developing an exposed light-sensitive silver halide photographic material composed of a support having thereon at least one light-sensitive silver halide emulsion layer containing silver halide grains having a halogen composition of from 0 to 1 mol % of silver iodide, 95 mol % or more silver chloride and the remainder silver bromide, said at least one light-sensitive silver halide emulsion layer or an adjacent layer thereto containing an oil droplet dispersion in a hydrophilic binder, the oil droplets containing the combination of (a) a polymer insoluble in water and soluble in an organic solvent and (b) at least one coupler capable of forming a nondiffusible cyan dye by a coupling reaction with an oxidized form of a primary aromatic amine developing agent, with a color developing solution having a benzyl alcohol concentration of less than 2ml/l, characterized in that the oil droplets further contain (c) a high
• a coupler represented by formula (I) is a preferred cyan dye-forming coupler.
• Y represents -NHCO- or -CONH-
• R 1 represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted amino group
• X represents hydrogen, a halogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted acylamino group
• R 2 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted acylamino group
• X and R 2 may be linked to form a 5- to 7-membered ring
• Z 1 represents hydrogen or a group which can be eliminated on coupling with the oxidized form of a
• R 1 preferably represents a linear or cyclic aliphatic group which preferably has from 1 to 32 carbon atoms (for example, methyl, butyl, pentadecyl, cyclohexyl), an aromatic group (for example, phenyl, naphthyl), a heterocyclic group, preferably including a nitrogen atom, (for example, 2-pyridyl, 3-pyridyl, 2-furanyl, 2-oxazolyl) or an amino group, and these groups are preferably substituted with at least one substituent group selected from the alkyl groups, aryl groups, alkyloxy or aryloxy groups (for example, methoxy, dodecyloxy, methoxyethoxy, phenoxy, 2,4-di-tert-amylphenoxy, 3-tert-butyl-4-hydroxyphenoxy, naphthyloxy), carboxyl groups, alkylcarbonyl or arylcarbonyl groups (for example, acet
• aliphatic group signifies a linear chain, branched or ring aliphatic hydrocarbyl group, and this group may be either saturated or unsaturated, being an alkyl group, an alkenyl group or an alkynyl group.
• R 2 preferably represents an alkyl group which has from 1 to 20 carbon atoms (for example, methyl, ethyl, butyl, pentadecyl) or an acylamino group (for example, tetradecanoylamino, benzoylamino, 2-(2,4-di-tert-amylphenoxy)butanamido).
• alkyl group which has from 1 to 20 carbon atoms (for example, methyl, ethyl, butyl, pentadecyl) or an acylamino group (for example, tetradecanoylamino, benzoylamino, 2-(2,4-di-tert-amylphenoxy)butanamido).
• X represents hydrogen, a halogen atom, aliphatic group, preferably lower alkyl group, (for example, methyl, propyl, allyl, alkoxy group (for example, methoxy, butoxy) or acylamino group (for example, acetamido).
• the aforementioned compounds are preferably carbostyryl based cyan couplers in which R 2 and X are joined together to form a 5-, 6- or 7-membered ring which preferably includes a nitrogen atom, rather than phenol based cyan couplers, and oxyindole and imidazol-2-one cyan couplers are especially desirable as condensed couplers of this type.
• Z 1 represents hydrogen or a coupling-off group and examples of such groups include halogen atoms (for example, fluorine, chlorine, bromine), alkoxy groups (for example, ethoxy, dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy groups (for example, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy groups (for example, acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy groups (for example, methanesulfonyloxy, toluenesulfonyloxy), amido groups (for example, dichloroacetylamino, heptabutyrylamino, methanesulfonylamino, toluenesulfonylamino), alkoxycarbonyloxy groups (for example, eth
• R 2 is preferably an alkyl group which has from 1 to 15 carbon atoms, and most desirably from 1 to 4 carbon atoms.
• Z 1 is preferably hydrogen or a halogen atom, and most preferably a halogen atom.
• X is preferably a halogen atom.
• the cyan coupler used in the present invention is preferably used in an amount of from 1 ⁇ 10 -3 to 1 mol, more preferably from 0.1 to 0.5 mol, per mol of silver halide.
• the color sensitive materials of the present invention may contain yellow couplers and magenta couplers in addition to cyan couplers.
• 3-anilino-5-pyrazolone based couplers 3-acylamino-5-pyrazolone based couplers and pyrazolotriazole based couplers as magenta couplers is preferred.
• the imidazo[1,2-b]pyrazoles disclosed in U.S. Patent 4,500,630 are preferred from the viewpoint of their low absorbance on the yellow side and the light fastness of the colored dye, and the pyrazolo[1,5-b][1,2,4]triazoles disclosed in U.S. Patent 4,540,654 are especially preferred.
• oil-soluble magenta and yellow couplers which can be used in the invention are tabulated below.
• the high boiling point organic solvents having a viscosity of at least 500 cp (25°C) and having a boiling point of at least 120°C which are used in the invention are represented by formula (III) and may be selected from the compounds of formula (III) indicated below.
• W 5 represents a substituted or unsubstituted alkyl, cycloalkyl or aryl group, and the number of carbon atoms in the W 5 group is at least 12.
• X represents a halogen atom.
• substituent groups are preferably groups which have one or two linking groups selected from (where R 8 represents a 2- to 6-valent phenyl group which is derived from a phenyl group by removing hydrogen atoms therefrom and -O-.
• the alkyl groups represented by W 1 , W 2 , W 3 , W 4 and W 5 may be linear chain or branched chain alkyl groups.
• Examples of such groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
• the substituent groups for these alkyl groups may be, for example, halogen atoms, cycloalkyl groups, aryl groups or ester groups.
• Examples of such substituted alkyl groups with halogen (F, Cl, Br) substituents include -C 2 HF 4 , -C 5 H 3 F 8 , -C 9 H 3 F 16 , -C 2 H 4 Cl, -C 3 H 6 Cl, -C 3 H 5 Cl 2 , -C 3 H 5 ClBr and -C 3 H 5 Br 2 .
• Examples of such substituted alkyl groups with cycloalkyl substituent groups include Examples of such alkyl groups which have aryl substituent groups include and Examples of such substituted alkyl groups with substituents which provide dibasic esters include -CH 2 CH 2 COOC 12 H 25 , - (CH 2 ) 4 COOC 10 H 21 , -(CH 2 ) 4 COOCH 2 (CF 2 CF 2 ) 2 H, -(CH 2 ) 7 COOC 4 H 9 and -(CH 2 ) 8 COOC 12 H 25 .
• Examples of such substituted alkyl groups with substituents which provide lactic acid esters include and Examples of such alkyl groups with substituent groups which provide citrate esters include Examples of such substituted alkyl groups which give malate esters include -CH 2 CH(OH)COOC 6 H 13 and -CH 2 CH(OH)COOC 12 H 25 . Examples of such substituted alkyl groups which provide tartrate esters include -CH(OH)CH(OH)COOC 8 H 17 , -CH(OH)CH(OH)COOC 18 H 37 , and and
• W 1 and W 2 in general formula (VI) may include an oxylane, oxolane or oxane ring which forms a condensed ring.
• the cycloalkyl groups represented by W 1 , W 2 , W 3 , W 4 or W 5 are, for example, and examples of substituted cycloalkyl groups include
• Examples of the aryl groups represented by W 1 , W 2 , W 3 , W 4 or W 5 include and and examples of substituted aryl groups include
• alkenyl groups include -C 4 H 7 , -C 5 H 9 , -C 6 H 11 , -C 7 H 13 , -C 8 H 15 , -C 10 H 19 , -C 12 H 23 and -C 18 H 35
• the boiling point of the high boiling point organic solvents used in the invention is preferably at least 140°C, and most desirably at least 160°C.
• the total number of carbon atoms in the aforementioned groups W 1 and W 2 in these compounds and W 1 to W 5 in the other compounds is preferably at least 8, these being alkyl groups.
• organic solvent generally suggests that the material is itself a liquid, but in the present invention the organic solvents of which the viscosity measured at 25°C is at least 500 cp include solids, and they are selected from compounds represented by formula (III) which preferably have a viscosity of at least 700 cp or which, most desirably, are solid with a melting point of at least 25°C.
• the dialkyl (secondary and tertiary alkyl) or dicycloalkyl esters of phthalic acid are especially desirable. Dicycloalkyl esters of phthalic acid are the most desirable.
• the viscosities can be measured using a cone plate type rotary viscometer (Visconisemd, made by Tokyo Keiki).
• the amounts of the above-mentioned high boiling point organic solvents used can be varied appropriately according to the type and amount of cyan coupler used, but a ratio (by weight) of high boiling point solvent to cyan coupler in the range from 0.05 to 20 is preferred.
• the high boiling point solvents used in this invention can be used individually or in the form of mixtures, or they can be used in the form of mixtures with other conventional high boiling point organic solvents.
• high boiling point organic solvents include phosphate ester based solvents such as tricresyl phosphate, tri-2-ethylhexyl phosphate, 7-methyloctyl phosphate and tricyclohexyl phosphate, and phenol based solvents such as 2,5-di-tert-amylphenol and 2,5-di-sec-amylphenol.
• high viscosity high boiling point organic solvents which can be used in the invention are compounds S-5 to S-16, S-20 to S-30, S-34 to S-49, S-62 and S-63 indicated below.
• the preferred polymers for use in silver halide photographic photosensitive materials of this invention are polymers which have a relative fluorescence yield K value of at least 0.10 and preferably of at least 0.20. The larger this value more preferred the polymer.
• K value as used herein is the relative fluorescence quantum yield in the polymer of the compound A of which the structural formula is shown below, this being a type of dye which is widely used as a fluorescence probe.
• ⁇ a and ⁇ b are the fluorescence quantum yields of the compound A in each of the polymers a and b, and they are determined, for example, using the method described in Macromolecules , 14 , 587 (1981). In practice, the value is obtained by calculation from ⁇ a and ⁇ b measured at room temperature using thin polymer films with concentrations of 0.5 mM of the aforementioned compound. The film is spin coated onto a slide glass to a thickness such that the optical density at ⁇ max of the absorbance of compound A is from 0.05 to 0.1. Furthermore, in the present invention, the K values used are those obtained using poly(methyl methacrylate) (number average molecular weight 20,000) for the above-mentioned polymer b.
• Monomers which can be used to form vinyl polymers include acrylic acid esters, including methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, see-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocydlohexyl acrylate, cyclohex
• Methacrylic acid esters examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, diethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl meth
• Vinyl esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate and vinyl salicylate.
• Acrylamides for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethyl- acrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, ⁇ -cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetoneacrylamide and tert-octylacrylamide.
• Methacrylamides for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, ⁇ -cyanoethylmethacrylamide and N-(2-acetoacetoxyethyl)methacrylamide.
• Olefins for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene.
• Styrenes for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene and methyl vinylbenzoate.
• Vinyl ethers for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether.
• Other compounds include, for example, butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyloxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, methylenemalonitrile and vinylidene.
• Two or more of the monomers (for example, the above-mentioned monomers) which can be used in polymers can be used as comonomers for various purposes (for example, for improving solubility).
• monomers which have acid groups, such as those indicated below, can also be used as comonomers for the adjustment of solubility provided that the copolymer remains insoluble in water.
• hydrophilic monomer here, this signifies a monomer which forms a water-soluble homopolymer
• vinyl monomers indicated above and other vinyl monomers which can be used in the invention no particular limitation is imposed on the proportion of hydrophilic monomer which is included in the copolymer provided that the copolymer does not become water-soluble but, normally, such monomers are used in an amount not exceeding 40 mol%, preferably in an amount not exceeding 20 mol% and, most desirably, in an amount not exceeding 10 mol%.
• the proportion in the copolymer of the comonomer which has acid groups is normally not more than 20 mol%, and preferably not more than 10 mol%, while the absence of copolymers of this type is most desirable from the point of view of the image storage properties as described earlier.
• the monomers in the polymer are preferably methacrylate based, acrylate based and methacrylamide based monomers.
• the acrylate and methacrylate based monomers are especially desirable.
• Polyesters formed from polyhydric alcohols and polybasic acids, and polyamides formed from diamines and dibasic acids and from ⁇ -amino- ⁇ '-carboxylic acids, are generally known as condensation polymers, and polymers such as the polyurethanes which are formed from diisocyanates and dihydric alcohols are known as polymers which have been formed by means of a polyaddition reaction.
• Glycols which have an OH-R 1 -OH structure (where R 1 is a hydrocarbon chain, especially an aliphatic hydrocarbon chain, which has from 2 to about 12 carbon atoms), or polyalkylene glycols, are effective as polyhydric alcohols, and acids which have an HOOC-R 2 -COOH structure (where R 2 represents a single bond or a hydrocarbon chain which has from 1 to about 12 carbon atoms) are effective as polybasic acids.
• polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylenediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol and sorbitol.
• polybasic acids examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohymelic acid, cyclopentadiene-maleic anhydride adducts and rosinmaleic anhydride adducts.
• diamines examples include hydrazine, methylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecylmethylenediamine, 1,4-diaminocyclohexane, 1,4-diaminomethylcyclohexane, o-aminoaniline, p-aminoaniline, 1,4-diaminomethylbenzene and bis(4-aminophenyl) ether.
• ⁇ -amino- ⁇ -carboxylic acids examples include glycine, ⁇ -alanine, 3-aminopropanoic acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 11-aminododecanoic acid, 4-aminobenzoic acid, 4-(2-aminoethyl)benzoic acid and 4-(4-aminophenyl)butanoic acid.
• diisocyanates examples include ethylene-diisocyanate, hexamethylenediisocyanate, m-phenylene-diisocyanate, p-phenylenediisocyanate, p-xylenediiso-cyanate and 1,5-naphthyldiisocyanate.
• polyesters and polyamides which are obtained by ring opening polymerization:
• X represents an -O- group or an -NH- group
• m represents an integer of value 4 to 7.
• the -CH 2 - groups may be branched.
• Monomers of this type include 4-propiolactone, ⁇ -caprolactone, dimethylpropiolactone, ⁇ -pyrrolidone, ⁇ -piperidone, ⁇ -caprolactam and ⁇ -methyl- ⁇ -caprolactam.
• A represents a repeating unit which has in the main chain at least one bond which is an ether bond or an -SO 2 - bond.
• B represents a repeating unit which has in the main chain at least one bond, ether bond, bond, -SO 2 - bond or ester bond, or a single bond, and this may be the same as, or different from, A.
• R represents hydrogen, an alkyl group, aryl group or aralkyl group, and these groups may be substituted or unsubstituted groups.
• n is an integer of value at least 5.
• the vinyl polymers are preferred as the polymers, and the use of acrylic based polymers, especially acrylamide based polymers, is especially desirable.
• the molecular weights and degrees of polymerization of the polymers used in this invention are not particularly limited, but problems arise with the increased time which is required to dissolve the polymer in an auxiliary solvent as the molecular weight increases, and emulsification and dispersion become more difficult because of the higher viscosity. Coarse particles are formed, and this can result in a worsening of coloring properties, and problems with coating properties are also liable to arise.
• the use of a larger amount of auxiliary solvent and reduction of the solution viscosity to overcome these problems gives rise to new processing problems.
• the viscosity of the polymer is preferably such that the viscosity on dissolving 30 g of the polymer in 100 ml of the auxiliary solvent which is being used is less than 5,000 cps, and most desirably such that this solution viscosity is less than 2,000 cps.
• the molecular weight of the polymers which can be used in the invention is preferably less than 150,000 and most desirably less than 100,000.
• a "water-insoluble polymer” is a polymer of which the solubility in 100 g of distilled water is 3 g or less, and preferably 1 g or less.
• the ratio of the polymer used in this invention to the auxiliary solvent differs according to the type of polymer which is being used, and it varies over a wide range depending on the solubility in the auxiliary solvent, the degree of polymerization, and the solubility of the coupler.
• the amount of auxiliary solvent required to provide a sufficiently low viscosity such that the solution consisting of at least a coupler, a high boiling point organic solvent and a polymer in an auxiliary solvent can be dispersed easily in water or in an aqueous hydrophilic colloid solution is used.
• the viscosity of the solution increases as the degree of polymerization of the polymer increases and so it is difficult to generally define the ratio of polymer to auxiliary solvent irrespective of the type of polymer, but normally ratios within the range from 1:1 to 1:50 (by weight) are preferred.
• the proportion of polymer with respect to coupler is preferably from 1:20 to 20:1, and most desirably from 1:10 to 10:1.
• Methyl methacrylate 500 g
• poly(sodium acrylate) 0.5 g
• 200 ml of distilled water 200 ml
• Dimethyl azobisisobutyrate 500 mg was added as a polymerization initiator and polymerization started.
• the reaction mixture was cooled after polymerizing for a period of 2 hours, and 48.7 g of Polymer P-3 was obtained by recovering by filtration, and washing with water, the polymer which had been formed in the form of beads.
• a mixture of 500 g of t-butylacrylamide and 250 ml of toluene was introduced into a 500 ml three-necked flask and heated to 80°C with stirring under a blanket of nitrogen.
• a toluene solution (10 ml) containing 500 mg of azobisisobutyronitrile was added as a polymerization initiator and polymerization was started.
• the reaction mixture was cooled after polymerizing for a period of 3 hours, and 47.9 g of Polymer P-17 was obtained on recovering by filtration of the solid which precipitated out on pouring the mixture into 1 liter of hexane, washing the solid with hexane, and drying the product by heating under reduced pressure.
• Dispersions of lipophilic fine particles containing coupler, high boiling point coupler solvent and polymer can be prepared as indicated below.
• the polymer being a linear polymer prepared by e.g. a solution polymerization procedure, an emulsion polymerization procedure or a suspension polymerization procedure (without crosslinking), the high boiling point coupler solvent and the coupler are all dissolved completely in an auxiliary organic solvent and the resulting solution is dispersed in the form of fine particles in water, or preferably in an aqueous hydrophilic colloid solution and most desirably in an aqueous gelatin solution, with the aid of a dispersing agent, using ultrasonics or a colloid mill, for example, and this dispersion is included in the silver halide emulsion.
• water or an aqueous hydrophilic colloid solution such as an aqueous gelatin solution can be added to an auxiliary organic solvent which contains a dispersion promotor such as a surfactant, the polymer, the high boiling point coupler solvent and the coupler and an oil-in-water dispersion can be formed by phase reversal
• a dispersion promotor such as a surfactant, the polymer, the high boiling point coupler solvent and the coupler
• an oil-in-water dispersion can be formed by phase reversal
• the auxiliary solvent may be removed from the dispersion so prepared by distillation, noodle washing or by ultra-filtration, for example, after which the dispersion may be mixed with a photographic emulsion.
• auxiliary solvent signifies an organic solvent which is used at the time of emulsification and dispersion but which is ultimately eliminated from the photosensitive material during the drying process at the time of coating or by the methods mentioned above, for example.
• solvents are low boiling point organic solvents or solvents which have some solubility in water and which can be removed by washing with water.
• auxiliary solvents include the acetates of lower alcohols, such as ethyl acetate and butyl acetate, ethyl propionate, sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate, methyl cellosolve acetate, methylcarbitol acetate, methylcarbitol propionate and cyclohexanone.
• lower alcohols such as ethyl acetate and butyl acetate, ethyl propionate, sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate, methyl cellosolve acetate, methylcarbitol acetate, methylcarbitol propionate and cyclohexanone.
• an organic solvent which is completely miscible with water such as methyl alcohol, ethyl alcohol, acetone or tetrahydrofuran, can be used conjointly, as required.
• the fine lipophilic particles are included in a silver halide emulsion layer or adjacent layers to the silver halide emulsion layer, preferably in a silver halide emulsion layer.
• the average particle size of the fine lipophilic particles obtained in this way is preferably from 0.04 ⁇ m to 2 ⁇ m, and most preferably from 0.06 ⁇ m to 0.4 ⁇ m.
• the particle size of the fine lipophilic particles can be measured using a device such as the "Nanosizer" made by the British Coal Tar Co.
• photographically useful hydrophobic substances can also be included in the fine lipophilic particles used in this invention.
• photographically useful hydrophobic substances include colored couplers, non-color-forming couplers, developing agents, developing agent precursors, development inhibitor precursors, ultraviolet absorbers, development accelerators, gradation controlling agents such as hydroquinones, dyes, dye-releasing agents, antioxidants, fluorescent whiteners, and antifading agents.
• these hydrophobic substances can be used conjointly.
• the compounds of formulae (A) to (C) indicated below improve the color-forming properties and increase the fading prevention of the light-sensitive material of this invention. Their use is especially effective as photographically useful hydrophobic substances which are included in the fine lipophilic particle which contains coupler, high boiling point organic solvent and polymer.
• A represents a divalent electron-attracting group
• R 1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted anilino group, or a substituted or unsubstituted heterocyclic group; and l is an integer of 1 or 2;
• R 2 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a hydroxyl group or a halogen atom; and
• m is 0 or an integer from 1 to 4;
• Q represents a benzene ring or a heterocyclic ring which may be condensed with the phenol ring.
• R 3 , R 4 and R 5 which may be the same or different, each represents hydrogen, a halogen atom, a nitro group, a hydroxyl group or a substituted or unsubstituted alkyl, alkoxy, aryl, aryloxy or acylamino group.
• R 6 and R 7 each represents hydrogen or a substituted or unsubstituted alkyl group, alkoxy group or acyl group;
• X represents -CO- or -COO-; and n is an integer of 1 to 4.
• At least one light-sensitive silver halide emulsion layer of the light-sensitive material of the invention contains silver halide grains having a halogen composition of from 0 to 1 mol% of silver iodide, 95 mol% or more of silver chloride and the remainder of silver bromide.
• a halogen composition of from 0 to 1 mol% of silver iodide, 95 mol% or more of silver chloride and the remainder of silver bromide.
• Essentially silver iodide free silver chlorobromides in which at least 95 mol% of all the silver halide in the same silver halide emulsion layer consists of silver chloride are especially desirable halogen compositions for the silver halide grains in cases where rapid processing is envisaged.
• the grains have a local silver bromide phase which has a silver bromide content of more than 10 mol% but less than 70 mol%.
• the arrangement of such a local silver bromide phase is variable, depending on the intended purpose, and it may be in the interior of the silver halide grains, or in the surface or sub-surface parts of the silver halide grains, or it may be divided between the interior and surface or sub-surface regions of the silver halide grains.
• the local phase may have a layer-like structure surrounding the silver halide grains internally or at the surface, or it may have a discontinuous, isolated structure.
• a silver bromide local phase of which the silver bromide content is at least 10 mol%, and preferably in excess of 20 mol% is grown locally on the surface of the silver halide grains (even on the corners).
• the silver bromide content of the local phase is preferably in excess of 20 mol%, but if the silver bromide content is too high the photosensitive material may be desensitized when pressure is applied, and undesirable characteristics in the photosensitive material such as marked variation in speed and gradation due to variations in processing bath composition arise.
• the silver bromide content of the local phase is preferably within the range from 20 to 60 mol%, and most desirably within the range from 30 to 50 mol%.
• the other silver halide of the local phase is preferably silver chloride.
• the silver bromide content of the local phase can be measured, for example, using the X-ray diffraction method (for example, as described in the Japanese Chemical Society publication New Experimental Chemistry Series 6, Structural Analysis , published by Maruzen), or the XPS method (for example, as described in Surface Analysis--Application of IMA, and Auger Electron and Photoelectron Spectra , published by Kodansha).
• the local phase is preferably formed using from 0.1 to 20%, and most desirably from 0.5 to 7%, of the total amount of silver used to form the silver halide grains in this invention.
• the boundary between such a local phase and the other phase may be a distinct phase boundary or the silver halide composition may change gradually to form a short transition region.
• the position of the silver bromide local phase can be ascertained by observation using an electron microscope or by using the method described in European Patent Application (Laid Open) 273,430.
• a soluble silver salt and a soluble halide can be reacted using a one sided or simultaneous mixing method to form a local phase.
• the local phase can be formed using the conversion method, which includes a process in which silver halide which has already been formed is converted to another silver halide which has a lower solubility product.
• a local phase can be formed by adding fine silver bromide grains and recrystallizing these grains onto the surface of silver chloride grains.
• the local phase is preferably precipitated along with at least 50% of all the iridium which is added during the formation of the silver halide grains.
• the term "precipitated together with the iridium” signifies that an iridium compound is supplied at the same time as the silver and/or halide is being supplied to form the local phase, or immediately before or immediately after adding the silver and/or halide.
• the preferred silver halide grains used in this invention may have a (100) plane or a (111) plane for the outer surface, or they may have both of these planes for outer surfaces, and they may include higher order planes.
• the form of the silver halide grains used in the invention may be a regular crystalline form, such as cubic, tetradecahedral or octahedral form, an irregular crystalline form, such as a spherical or tabular form, or a composite form consisting of these crystalline forms.
• Mixtures of grains which have various crystalline forms can also be used, but in such mixtures the presence of at least 50%, preferably at least 70%, and most desirably at least 90%, of grains which have a regular crystalline form is desirable.
• the silver halide emulsions used in the invention may be emulsions in which tabular grains of which the average aspect ratio (length/thickness ratio) is at least 5, and most desirably at least 8, account for at least 50% of the total projected area of the grains.
• the size of the silver halide grains used in this invention may be within the range normally used, but an average grain size within the range from 0.1 ⁇ m to 1.5 ⁇ m is preferred.
• the grain size distribution may be polydispersed or monodispersed, but monodispersions are preferred.
• the particle size distribution which represents the extent of monodispersivity is preferably such that the statistical variation coefficient (the value S/d obtained by dividing the standard deviation S by the diameter d in cases where the projected area is approximately circular) is not more than 20%, and most desirably not more than 15%.
• Two or more types of tabular grain emulsions and monodispersed emulsions of this type can be mixed together.
• at least one emulsion preferably has a variation coefficient as described above, and the variation coefficient of the mixed emulsion is preferably within the above range of values.
• the substrate may have different phases for the interior and surface parts or it may consist of a uniform phase.
• Silver halide photographic emulsions which can be used in the invention can be prepared using the methods described, for example, Chemie et Physique Photographique , by P. Glafkides, published by Paul Montel, 1967; Photographic Emulsion Chemistry , by G.F. Duffin, published by Focal Press, 1966; and Making and Coating Photographic Emulsions , by V.L. Zelikman et al., published by Focal Press, 1964, etc.
• Silver halide solvents for example, ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds (for example, those disclosed in U.S. Patents 3,271,157, 3,574,628, 3,704,130, 4,297,439 and 4,276,374), thione compounds (for example, those disclosed in JP-A-53-144319, JP-A-53-82408 and JP-A-55-77737) and amine compounds (for example, those disclosed in JP-A-54-100717), can be used to control grain growth during the formation of the silver halide grains.
• ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds for example, those disclosed in U.S. Patents 3,271,157, 3,574,628, 3,704,130, 4,297,439 and 4,276,374
• thione compounds for example, those disclosed in JP-A-53-144319, JP-A-53-82408 and J
• the silver halide grains used in the invention are preferably of the surface latent image type, and some degree of chemical sensitization of the surface is desirable.
• Chemical sensitization can be achieved using sulfur sensitization methods in which use is made of active gelatin or compounds which contain sulfur which can react with silver (for example, thiosulfates, thioureas, mercapto compounds and rhodanines), reduction sensitization methods in which use is made of reducing substances (for example, stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid and silane compounds) and precious metal sensitization methods in which use is made of metal compounds (for example, gold complex salts, and complex salts of metals of group VIII of the Periodic Table, such as Pt, Ir, Pd, Rh and Fe), and these methods may be used individually or in combination.
• sulfur sensitization methods in which use is made of active gelatin or compounds which contain sulfur which can react with silver (for example, thiosulfates,
• the sensitive materials of this invention typically have a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer established in this order on a support, or the order of the layers can be changed appropriately. At least one layer of each color sensitivity is coated and layers in which spectral sensitization in the prescribed wavelength region has been provided using sensitizing dyes are preferred.
• the methine dyes such as the cyanine dyes and merocyanine dyes normally used for photographic purposes can be used as spectrally sensitizing dyes. Examples of these sensitizing dyes are disclosed at pages 77 to 124 of JP-A-62-215272.
• Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives can be used, for example, as anti-color-fogging agents in the photosensitive materials of this invention.
• antifading agents can be used in the photosensitive materials of this invention.
• examples of compounds which can be used as organic antifading agents for use with the cyan, magenta and/or yellow images include hydroquinones, 6-hydroxychromans, 5-hydroxy-coumarans, spirochromans, p-alkoxyphenols, hindered phenols based on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives of those compounds wherein the phenolic hydroxyl groups have been silylated or alkylated.
• metal complexes as typified by (bissalicylaldoximato)nickel and (bis-N,N-dialkyldithiocarbamato) nickel can also be used for this purpose.
• Hydroquinone derivatives have been disclosed, for example, in U.S. Patents 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and 4,430,425, British Patent 1,363,921 and U.S. Patents 2,710,801 and 2,816,028; 6-hydroxychromans, 5-hydroxycoumarans and spirochromans have been disclosed, for example, in U.S. Patents 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, and in JP-A-52-152225; spiroindanes have been disclosed in U.S.
• Patent 4,360,589 p-alkoxyphenols have been disclosed, for example, in U.S. Patent 2,735,765, British Patent 2,066,975, JP-A-59-10539 and JP-B-57-19765 (the term "JP-B" as used herein refers to an "examined Japanese patent publication”); hindered phenols have been disclosed, for example, in U.S. Patent 3,700,455, JP-A-52-72224, U.S. Patent 4,228,235 and JP-B-52-6623; gallic acid derivatives, methylenedioxybenzenes and aminophenols have been disclosed, for example, in U.S.
• Patents 4,155,765, 4,174,220, 4,254,216 and 4,264,720, JP-A-54-145530, JP-A-55-6321, JP-A-58-105147, JP-A-59-10539, JP-B-57-37856, U.S. Patent 4,279,990 and JP-B-53-3263; and metal complexes have been disclosed, for example, in U.S. Patents 4,050,938 and 4,241,155, and in British Patent 2,027,731(A). These compounds can be used to achieve the intended purpose by addition to the photosensitive layer after coemulsification with the coupler in an amount normally ranging from 5 to 100 wt% with respect to the corresponding color coupler.
• the introduction of ultraviolet absorbers into the layers on both sides adjacent to the cyan color forming layer is effective for preventing deterioration of the cyan dye image due to heat and, more especially, light.
• the spiroindanes and hindered amines are especially desirable among the above-mentioned antifading agents.
• a compound (A) which bonds chemically with any aromatic amine based developing agent remaining after color development processing and produces chemically inactive and essentially colorless compounds and/or a compound (B) which bonds chemically with any of the oxidized form of the aromatic amine based developing agent remaining after color development processing and produces chemically inactive and essentially colorless compounds is desirable for preventing the occurrence of staining and other side effects due to the reaction of residual color developing agent or oxidized form of the color developing agent in the film with a coupler and colored dye formation during storage after processing.
• Compound (A) is preferably a compound which reacts with p-anisidine with a second order reaction rate constant k 2 (at 80°C in trioctyl phosphate) within the range from 1.0 liter/mol ⁇ s to 1 ⁇ 10 -5 liter/mol ⁇ s.
• the value of k 2 is larger than this range, the compound itself will be unstable and it may react with gelatin or water and decompose. If, on the other hand, the value of k 2 is smaller than this range, reaction with the residual aromatic amine based developing agents is slow and it is not possible to prevent the occurrence of the side reactions of the residual aromatic amine based developing agents which is the purpose of the invention.
• the most desirable compounds (A) of this type are represented by formulae (AI) or (AII): R 1 -(A) n -X (AI) wherein R 1 and R 2 each represents an aliphatic group, aromatic group or heterocyclic group; B represents hydrogen, an aliphatic group, aromatic group, heterocyclic group, acyl group or sulfonyl group; and Y represents a group which promotes the addition of aromatic amine based developing agents to the compounds of formula (AII); here, R 1 and X, and Y and R 2 or B, may be linked to form a ring structure.
• Ultraviolet absorbers may be included in the hydrophilic colloid layers in the photosensitive materials of this invention.
• benzotriazole compounds substituted with aryl groups as disclosed, for example, in U.S. Patent 3,533,794), 4-thiazolidone compounds (as disclosed, for example, in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (as disclosed, for example, in JP-A-46-2784), cinnamic acid ester compounds (as disclosed, for example, in U.S. Patents 3,705,805 and 3,707,375), butadiene compounds (as disclosed, for example, in U.S.
• Patent 4,045,229), and benzoxidol compounds can be used for this purpose.
• Ultraviolet absorbing couplers for example, ⁇ -naphthol based cyan dye forming couplers
• ultraviolet absorbing polymers can also be used for this purpose. These ultraviolet absorbing agents can be mordanted in specified layers.
• Water-soluble dyes may be included as filter dyes or for anti-irradiation or various other purposes in the hydrophilic colloid layers of photosensitive materials made using this invention.
• Dyes of this type include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
• the oxonol dyes, hemioxonol dyes and merocyanine dyes are useful among these dyes.
• gelatin is effective as the binding agent or protective colloid which is used in the emulsion layers of photosensitive materials of this invention, but other protective colloids can be used, either individually or in combination with gelatin.
• the gelatin used in the invention may be a lime treated gelatin or an acid treated gelatin. Details of methods for the preparation of gelatins have been described by Arthur Weise in The Macromolecular Chemistry of Gelatin (published by Academic Press, 1964).
• Cellulose nitrate films, transparent films of polyethylene terephthalate or reflective type supports as normally used for photographic materials can be used for the supports which are used in the present invention.
• the use of a reflective type support is preferred, in line with the purpose of the invention.
• reflective support used in this invention signifies that the reflectance is high and that the dye image formed in the silver halide emulsion layer is clear, and such reflective supports include those in which the support is covered with a hydrophobic resin which contains a dispersion of a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, for example, and those in which hydrophobic resins which contain light reflecting substances are used for the support itself.
• baryta paper polyethylene coated paper, polypropylene based synthetic papers, and transparent supports such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate and cellulose nitrate films, polyamide films, polycarbonate films, polystyrene films and vinyl chloride resin films on which a reflecting layer has been established or in which a reflecting substance has been used conjointly, and the supports can be selected appropriately according to the intended purpose of the resulting material.
• White pigments may be milled thoroughly in the presence of a surfactant as light reflecting materials and the use of those white pigments of which the surfaces of the fine pigment particles have been treated with a di-hydric to tetra-hydric alcohol is preferred.
• the occupied area factor (%) for the area occupied by fine white pigment particles per specified unit surface area can be obtained most typically by dividing the area observed into adjoining unit areas measuring 6 ⁇ m ⁇ 6 ⁇ m and measuring the occupied area factor (%) (R i ) of the fine grains projected in each unit area.
• the variation factor of the occupied area factor (%) can be obtained using the ratio s/ R ⁇ of the standard deviation s of R i with respect to the average value of R i ( R ⁇ ).
• the number of unit areas taken as subjects for observation is preferably at least six.
• the variation coefficient s/ R ⁇ can be obtained from the following expression:
• the variation factor of the occupied area factor (%) of the fine pigment grains is preferably not more than 0.15, and most desirably not more than 0.12.
• the dispersion of the particles can be said to be "uniform" when the variation coefficient has a value of not more than 0.08.
• scanning exposure methods can be used for exposing the sensitive materials of this invention.
• Methods in which a combination of a laser and a wavelength varying element consisting of a non-linear optical material is used to provide a second harmonic fcr the light source as disclosed in JP-A-63-113534 are preferred for making such scanning exposures.
• the color development baths used for color development processing are preferably aqueous alkaline solutions which contain primary aromatic amine based color developing agents as the principal components.
• Aminophenol based compounds are useful as color developing agents, but the use of p-phenylenediamine based compounds is preferred.
• Typical examples of these compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and the sulfate, hydrochloride and p-toluenesulfonate salts of these compounds. Two or more of these compounds can be used conjointly, depending on the intended purpose.
• the color development baths generally contain pH buffers, such as alkali metal carbonates, borates or phosphates, and development inhibitors or antifogging agents, such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
• pH buffers such as alkali metal carbonates, borates or phosphates
• development inhibitors or antifogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
• They may also contain, as required, various preservatives, such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine(1,4-diazabicyclo[2,2,2]octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, poly(ethylene glycol), quaternary ammonium salts and amines, dye forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents, as typified by the aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, typical examples of which include ethylenediaminetetraacetic acid, nitrilotriace
• Color development is carried out after a normal black-and-white development in the case of reversal processing.
• the known black-and-white developing agents for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol, can be used individually, or in combinations, in these black-and-white development baths.
• the pH of these color development baths and black-and-white development baths is generally within the range from 9 to 12. Furthermore, the replenishment rate of these development baths depends on the color photographic material which is being processed, but it is generally 3 liters or less per square meter of photo-sensitive material and it is possible, by reducing the bromide ion concentration in the replenisher, to use replenishment rates of 500 ml or less per square meter of photosensitive material.
• the prevention of loss of liquid by evaporation, and aerial oxidation, by minimizing the contact area with the air in the processing tank is desirable in cases where the replenishment rate is low.
• the replenishment rate can be reduced further by suppressing the accumulation of bromide ion in the developer.
• the photographic emulsion layers are subjected to a normal bleaching process after color development.
• the bleaching process may be carried out at the same time as the fixing process (in a bleach-fix process) or it may be carried out as a separate process.
• a bleach-fix process can be carried out after a bleaching process in order to speed-up processing.
• processing can be carried out in two connected bleach-fix baths, a fixing process can be carried out before carrying out a bleach-fix process, or a bleaching process can be carried out after a bleach-fix process, according to the intended purpose of the processing.
• bleaching agents include ferricyanides; dichromates; organic complex salts of iron(IIII or cobalt(III), for example, complex salts with aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or citric acid, tartaric acid, malic acid; persulfates; bromates; permanganates and nitrobenzenes.
• aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or citric acid,
• aminopolycarboxylic acid iron(III) complex salts principally ethylenediaminetetraacetic acid iron(III) complex salts, and persulfates
• the aminopolycarboxylic acid iron(III) complex salts are especially useful in both bleach baths and bleach-fix baths.
• the pH of a bleach or bleach-fix bath in which aminopolycarboxylic acid iron(IIII) complex salts are being used is normally from 5.5 to 8. Processing can be speeded up by using a bleach-fixing solution having preferably a pH of 6.0 or less, and more preferably a pH of 5.5 or less.
• Bleach accelerators can be used, as required, in the bleach baths, bleach-fix baths, or bleach or bleach-fix prebaths.
• Examples of useful bleach accelerators have been disclosed in the following specifications: the compounds which have a mercapto group or a disulfide group disclosed, for example, in U.S.
• Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and Research Disclosure , No.
• these compounds those which have a mercapto group or a disulfide group are preferred in view of their large accelerating effect, and the use of the compounds disclosed in U.S.
• Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 is especially preferred.
• the use of the compounds disclosed in U.S. Patent 4,552,834 is also preferred.
• These bleach accelerators may be added to the sensitive material. These bleach accelerators are especially effective when bleach-fixing camera color photosensitive materials.
• Thiosulfates, thiocyanates, thioether based compounds, thioureas, and large quantities of iodides can be used as fixing agents, but thiosulfates are generally used for this purpose and ammonium thiosulfate, in particular, can be used in the widest range of applications. Sulfites or bisulfites, or carbonyl-bisulfite addition compounds, are preferred as preservatives for bleach-fix baths.
• the silver halide color photographic materials of this invention are generally subjected to water washing and/or stabilizing process after the desilvering process.
• the amount of water used in the water washing process can be fixed within a wide range according to the nature of the photosensitive material (for example, the materials, such as couplers, which are being used), the application, the wash water temperature, the number of washing tanks (the number of washing stages), the replenishment system, i.e., whether a counter flow or a sequential flow system is used, and various other conditions.
• the relationship between the amount of water used and the number of water washing tanks in a multistage counter flow system can be obtained using the method outlined on pages 248 to 253 of the Journal of the Society of Motion Picture and Television Engineers , Vol. 64 (May, 1955).
• the amount of wash water can be greatly reduced by using the multistage counter flow system there described, but bacteria proliferate due to the increased residence tine of the water in the tanks and problems arise as a result of the sediments which are formed becoming attached to the photosensitive material.
• the method in which the calcium ion and manganese ion concentrations are reduced disclosed in JP-A-62-288838 can be used very effectively to overcome problems of this sort in the processing of color photosensitive materials of this invention.
• isothiazolone compounds and thiabendazoles disclosed in JP-A-57-8542 and chlorine based disinfectants such as chlorinated sodium isocyanurate, and benzotriazoles, and the disinfectants disclosed in Chemistry of Biocides and Fungicides by Horiguchi, Killing Microorganisms, Biocidal and Fungicidal Techniques , published by the Health and Hygiene Technical Society, and in A Dictionary of Biocides and Fungicides , published by the Japanese Biocide and Fungicide Society, can be used for this purpose.
• the pH of the wash water used in the processing of the photosensitive materials of the invention is within the range from 4 to 9, and preferably within the range from 5 to 9.
• the wash water temperature and the washing time can be set variously according to the nature of the photosensitive material and the application, etc., but, in general, washing conditions of from 20 seconds to 10 minutes at a temperature of from 15°C to 45°C, and preferably of from 30 seconds to 5 minutes at a temperature of from 25°C to 40°C, are selected.
• the photosensitive materials of this invention can be processed directly in a stabilizing bath instead of being subjected to a water wash as described above.
• the known methods disclosed in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can all be used for this purpose.
• stabilizing baths which contain formalin and surfactant which are used as a final bath for camera color photosensitive materials are an example of such a process.
• Various chelating agents and fungicides can be added to these stabilizing baths.
• the overflow which accompanies replenishment of the above-mentioned wash water and/or stabilizer can be reused in other processes such as the desilvering process.
• a color developing agent may also be incorporated into the silver halide color photosensitive materials of this invention in order to simplify and speed-up processing.
• the use of various color developing agent precursors is preferred for such incorporation.
• the indoaniline based compounds disclosed in U.S. Patent 3,342,597, the Schiff's base type compounds disclosed in U.S. Patent 3,342,599 and Research Disclosure , Nos. 14850 and 15159, the aldol compounds disclosed in Research Disclosure , No. 13924, the metal salt complexes disclosed in U.S. Patent 3,719,492, and the urethane based compounds disclosed in JP-A-53-135628 can be used for this purpose.
• the various processing baths used in this invention are used at a temperature of from 10°C to 50°C.
• the standard temperature is normally from 33°C to 38°C, but processing is accelerated and the processing time is shortened at higher temperatures and, conversely, increased picture quality and improved stability of the processing baths can be achieved at lower temperatures.
• processes using hydrogen peroxide intensification or cobalt intensification as disclosed in West German Patent 2,226,770 or U.S. Patent 3,674,499 can be carried out in order to economize on silver in the photosensitive material.
• the silver halide color photographic photosensitive material which has on a single layer reflecting support at least one photo-sensitive layer which contains silver halide grains and at least one type of coupler which forms a dye by means of a coupling reaction with the oxidized form of a primary aromatic amine based color developing agent is preferably processed for a developing time of not more than 2 minutes 30 seconds in a color development bath which is essentially benzyl alcohol free and which contains not more than 0.002 mol/liter of bromide ions.
• benzyl alcohol free signifies that the benzyl alcohol concentration is less than 2 ml per liter, and preferably less than 0.5 ml per liter, of color development bath, and most preferably that the color development bath contains no benzyl alcohol at all.
• the multilayer silver halide photosensitive material Sample 101 having the layer structure indicated below was prepared on a paper support which had been laminated on both sides with polyethylene. Moreover, ethyl acetate was used as an auxiliary solvent together with the high boiling point organic solvent for the coupler solvents referred to below.
• composition of each layer was as indicated below.
• the values indicate coated weights (g/m 2 ).
• the weights of silver halide emulsions are indicated as weights calculated as silver.
• Second Layer Anti-Color Mixing Layer
• Monodispersed silver chlorobromide emulsion (EM5) spectrally sensitized with the sensitizing dyes (ExS-4, ExS-5) 0.07
• cyan coupler two kinds of cyan coupler, three kinds of colored image stabilizer, ultraviolet absorber and polymer for dispersion were dissolved in ethyl acetate and a mixture of the solution thus obtained and solvent (SV-6) were dispersed to form an emulsion into an aqueous gelatin solution in the presence of dodecylbenzenesulfonic acid (surfactant) with a high speed homogenizer.
• the emulsified dispersion thus obtained was one containing fine grains.
• the surfactant was used in an amount of 1/10 (by weight) the above additives. Then, the emulsified dispersion and silver halide emulsion were mixed to be used for coating.
• Cpd-11 and Cpd-12 were used as anti-irradiation dyes.
• "Alkanol XC” (made by the Du Pont Co.), sodium alkylbenzenesulfonate, succinic acid esters and "Megafac F-120" (made by the Dainippon Ink co.) were used in each layer as emulsification, dispersion and coating promotors.
• Cpd-13 and Cpd-14 were used as silver halide stabilizers.
• 1-oxy-3,5-dichloro-s-triazine, sodium salt was used as a gelatin hardening agent in each layer, and Cpd-2 was used as a viscosity increasing agent.
• Samples 102 to 130 were prepared in the same way as Sample 101 except that the type of polymer used for dispersion purposes and the type of high boiling point solvent in the red-sensitive layer of Sample 101 were modified as shown in Table 1.
• composition of each of the processing baths was as indicated below.
• Color Development Bath Tank Solution Replenisher Water 800 ml 8000 ml Diethylenetriaminepentaacetic acid 1.0 g 1.0 g Nitrilotriacetic acid 2.0 g 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g 2.0 g Benzyl alcohol 16 ml 16 ml Diethylene glycol 10 ml 10 ml Sodium sulfite 2.0 g 2.5 g Potassium bromide 0.5 g -- Potassium carbonate 30 g 30 g N-Ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline hydrochloride 5.5 g 5.5 g Hydroxylamine sulfate 2.0 g 2.5 g Fluorescent whitener ("Whitex 4B" made by Sumitomo Chemicals) 1.5 g 2.0 g Water to make 1,000 ml 1,000 m
• Bleach-Fix-Bath Tank Solution Replenisher Water 400 ml 400 ml Ammonium thiosulfate solution (70%) 200 ml 200 ml Sodium sulfite 20 g 40 g Ethylenediaminetetraacetic acid Fe(III) ammonium salt 60 g 120 g Ethylenediaminetetraacetic acid disodium salt 5 g 10 g Water to make 1,000 ml 1,000 ml pH (25°C) 6.70 6.30
• Deionized water (calcium and magnesium ion concentrations both less than 3 ppm)
• Samples 101 to 130 prepared in this way were subjected to a gray exposure and processed in the same way as before and the resulting samples were subjected to a fading test with fungi which was carried out in the way described below.
• Fungi which had grown on a color paper were cultured on a potato dextrose agar medium, spores were collected and a spore suspension of concentration approximately 1.5 ⁇ 10 6 spores/ml was prepared. Next, 0.5 ml of the spore suspension was dripped onto each sample and the samples were maintained at 28°C under conditions of 95% humidity for a period of 10 months, during which time fungi developed and propagated, and the extent of fading of the cyan image in the region in which the fungi had propagated was investigated.
• Photosensitive material Samples 210 to 230 were prepared in the same way as the photosensitive material Samples 101 to 130 in Example 1 except that the silver halide emulsions and magenta couplers were changed as indicated below.
• Emulsions EM1 and EM2 were replaced by Emulsion EM7
• Emulsions EM3 and EM4 were replaced by Emulsion EM8,
• Emulsions EM5 and EM6 were replaced by Emulsion EM9.
• magenta coupler was changed from M-5 in Example 1 to M-2.
• Ammonium thiosulfate solution (700 g/liter) 100 ml Ammonium sulfite 18 g Ethylenediaminetetraacetic acid ferric ammonium salt dihydrate 55 g Ethylenediaminetetraacetic acid disodium salt 3 g Ammonium bromide 40 g Glacial acetic acid 8 g Water to make 1,000 ml pH (25°C) 5.5
• the processed Samples 201 to 230 were subjected to fading tests with fungi in the same way as in Example 1 and the results obtained were the same as those obtained in Example 1, confirming that fading due to fungi was effectively prevented irrespective of the type of silver halide emulsion or the type of development processing used.
• the multilayer silver halide photosensitive material Sample 301 having the layer structure indicated below was prepared on a paper support which had been laminated on both sides with polyethylene.
• composition of each layer was as indicated below.
• the values indicate coated weights (g/m 2 ).
• the weights of silver halide emulsions are indicated as weights calculated as silver.
• Second Layer Anti-Color-Mixing Layer
• Cpd-11 and Cpd-12 were used as anti-irradiation dyes at this time.
• "Alkanol XC” (made by the Du Pont Co.), sodium alkylbenzene-sulfonate, succinic acid esters and "Megafac F-120" (made by the Dainippon Ink Co.) were used in each layer as emulsification, dispersion and coating promotors.
• Cpd-13 and Cpd-14 were used as silver halide stabilizers.
• 1-oxy-3,5-dichloro-s-triazine, sodium salt was used as a gelatin hardening agent in each layer, and Cpd-2 was used as a viscosity increasing agent.
• Emulsion Form Average Grain Size Br Content Variation Coefficient ( ⁇ m) (mol%) EM7 Cubic 0.85 0.6 0.10 EM8 Cubic 0.45 1.00 0.09 EM9 Cubic 0.34 1.8 0.10 Variation Coefficient Standard Deviation/Average Grain Size
• Samples 302 to 330 were prepared in the same way as Sample 301 except that the type of polymer for dispersion purposes and the type of high boiling point organic solvent in the red-sensitive layer of Sample 301 were changed as shown in Table 3.
• TABLE 3 Sample High Boiling Point Solvent Polymer for Dispersion Purposes 301 C* SV-7 P-17 302 C SV-7 -- 303 C SV-2 -- 304 C SV-5 -- 305 C SV-9 -- 306 C -- -- 307 C -- p-3 308 C S-3 -- 309 C S-1 -- 310 C S-5 -- 311 C S-51 -- 312 C S-9 -- 313 C S-12 -- 314 C S-21 -- 315 C S-22 -- 316 C SV-7 P-3 317 C SV-2 P-17 318 C SV-5 P-47 319 C SV-9 P-55 320 C SV-8 P-17 321 C S-3 P-17 322 C S-4 P-17 323 I* S-8 P-57 324 I S-9 P-53 325 I S-12
• Type Fading Factor 301 Comparison ⁇ 302 " ⁇ 303 " ⁇ 304 " ⁇ 305 “ ⁇ 306 “ ⁇ 307 “ ⁇ 308 “ ⁇ 309 “ ⁇ 310 " ⁇ 311 “ ⁇ 312 “ ⁇ 313 “ ⁇ 314 “ ⁇ 315 “ ⁇ 316 “ ⁇ 317 “ ⁇ 318 “ ⁇ 319 “ ⁇ 320 “ ⁇ 321 “ ⁇ 322 “ . ⁇ 323 “ . ⁇ 324 Invention . ⁇ 325 “ ⁇ 326 “ . ⁇ 327 “ . ⁇ 328 “ . ⁇ 329 “ . ⁇ 330 Comparison . ⁇

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• 1988
  • 1988-08-04 JP JP19486088A patent/JPH0243541A/ja active Pending
• 1989
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