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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
  • G03C5/39—Stabilising, i.e. fixing without washing out
• • 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
  • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
• • 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
  • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

• This invention relates to a method for processing of a light-sensitive silver halide color photographic material (hereinafter called light-sensitive material) in which water washing processing step is omitted, more particularly to a processing method without water washing of a light-sensitive material in which stain generation at an unexposed portion by continuous processing is prevented.
• light-sensitive material a light-sensitive silver halide color photographic material
• light-sensitive materials after imagewise exposure, are processed according to the processing steps such as color developing, bleaching, fixing, stabilizing, bleach-fixing, water washing, etc. And, in such processing steps, the increased cost for water washing due to exhaustion of water resources, and rise in price of crude oils are becoming a serious problem increasingly in recent years.
• an object of the present invention is to provide a method for processing in which contamination at the unexposed portion of a light-sensitive material generated in the case of continuous processing by use of a stabilizing solution substituting for water washing is prevented.
• Another object of the present invention is to provide a method for processing in which deterioration of storage stability, particularly deterioration of light fading characteristic of the dye image when continuously processed by use of a stabilizing solution substituting for water washing is prevented.
• a method for processing a light-sensitive silver halide color photographic material which comprises subjecting a light-sensitive silver halide color photographic material having a total dried film thickness of the light-sensitive silver halide emulsion layer and the non-light-sensitive layer on one surface of a support of l0 ⁇ m or more to imagewise expo­sure, then processing the exposed material with a color forming developing solution containing substantially no benzyl alcohol, thereafter processing the material with a processing solution having fixing ability and subsequent­ly processing the material with a stabilizing solution substituting for water washing having a surface tension of 8 to 50 dyne/cm and containing substantially no aldehyde compound, followed by drying.
• each of Z1 and Z2 represents a group of atoms necessary for formation of benzoxazole nucleus, naphtoxazole nucleus, benzothiazole nucleus, naphtothiazole nucleus, benzoselenazole nucleus, naphtoselenazole nucleus, benzoimidazole nucleus, naphtoimidazole nucleus, pyridine nucleus or quinoline nucleus
• each of R1 and R2 represents an alkyl group, an alkenyl group or an aryl group
• R3 represents a hydrogen atom, a methyl group or an ethyl group
• X1 ⁇ represents an anion and l represents 0 or l.
• the stabilizing solution substitut­ing for water washing will be stored over a long term due to lowering in the rate of renewal thereof, and the stabilizing solution substituting for water washing is considerably colored due to the coloring components of the above substances in the stabilizing solution substi­tuting for water washing. Accordingly, it may be esti­mated that these coloring components are adsorbed onto the light-sensitive material in the stabilizing solution substituting for water washing, or washing-out from the light-sensitive material is inhibited, whereby the unex­posed portion of the light-sensitive material becomes stained.
• Benzyl alcohol has been used for a long time in a color developing solution generally as a developing accelerator. Also, it is well known in the art that formalin which is an aldehyde compound has been used in the final stabilizing solution for the purpose of image stability in the final step of conventional color processing steps.
• processing with a processing solution having fixing ability after color developing refers to the step by use of a fixing bath or a bleach-fixing bath for the purpose of fixing of the light-sensitive material after processing with a conven­tional color developing solution. That is, the present invention has solved the problem with the stabilizing solution substituting for water washing after a process­ing in a bleaching bath - fixing bath or a bleach-fixing bath after color developing.
• the present invention is particularly effective for the latter, namely processing in a bleach-fixing bath.
• the color developing solution containing substantially no benzyl alcohol refers to a color developing solution containing benzyl alcohol in such an amount that the color developing solution has substantially no developing accelerating effect. More specifically, the color developing solution containing benzyl alcohol in an amount of l ml or less per liter of the color developing solution, and more preferably it contains no benzyl alcohol.
• processing with a stabilizing solution substituting for water washing refers to a processing for stabilizing processing in which stabilizing processing is performed without sub­stantial water washing processing, or without using flow­ing water immediately after processing with a processing solution having fixing ability. That is, while a large amount of water is required for conventional water wash­ing using flowing water which is led into a processing machine from outward thereof, in the present invention, since the stabilizing solution substituting for water washing may be a stabilizing solution or water pooled in a processing machine, its amount is extremely small. Further, the processing solution used for said stabiliz­ing processing is called the stabilizing solution substituting for water washing, and the processing tank is called a stabilizing bath or a stabilizing tank.
• the effect of the present invention is great when the stabilizing tank consists of l to 5 tanks, particularly preferably l to 3 tanks. That is, with the same amount of supplementing solution, the effect of the present invention becomes weaker as the number of the tanks is increased, because concentrations of contaminating components in the final stabilizing tank becomes lower.
• the surface tension of the stabilizing solution substituting for water washing to be used in the process­ing of the present invention is measured according to the general measuring method as described in "Analysis and Test Method of Surfactants” (written by Fumio Kitahara, Shigeo Hayano and Ichiro Hara, published by Kodansha K.K., March l, l982), etc., and, in the present inven­tion, the surface tension is the value measured according to the conventional general measuring method at 20 °C.
• the stabilizing solution of the present invention may be used any compound which can give a surface tension of 8 to 50 dyne/cm (20 °C), but it is particularly pre­ferable to use at least one compound selected from the compounds of the following formula (II), formula (III) and water-soluble organic siloxane type compounds with respect to the effect for the object of the present invention.
• A is a monovalent organic group, for example, an alkyl group having 6 to 20, preferably 6 to l2 carbon atoms such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
• it may be an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent may be preferably an alkyl group having 3 to l2 carbon atoms such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
• the aryl group may be phenyl, tolyl, xylyl, biphenyl or naphthyl, preferably phenyl or tolyl.
• the position at which the alkyl group is bonded to the aryl group may be either ortho-, meta-­or para-position.
• B represents ethylene oxide or propylene oxide, and m represents an integer of 4 to 50.
• X2 represents a hydrogen atom, SO3Y or PO3Y2, and Y represents a hydrogen atom, an alkali metal (Na, K or Li, etc.) or ammonium ion.
• each of R4, R5, R6 and R7 represents a hydrogen atom, an alkyl group or a phenyl group, and the total carbon atoms of R4, R5, R6 and R7 is 3 to 50.
• X3 represents an anion such as a halogen atom, a hydroxyl group, a sulfate group, a carbonate group, a nitrate group, an acetate group, a p-toluenesulfonate group, etc.
• the water-soluble organic siloxane type compound of the present invention means water-soluble organic siloxane type compounds in general as described in, for example, Japanese Provisional Patent Publication No. l8333/l972, Japanese Patent Publication No. 5ll72/l980, Japanese Patent Publication No. 37538/l976, Japanese Provisional Patent Publication No. 62l28/l974 and U.S. Patent No. 3,545,970, etc.
• the compounds represented by the formula (IV) shown below can be more preferably be used, since they can exhibit well the effect of the object of the present invention.
• R8 represents a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group
• Each of R9, R10 and R11 represents a lower alkyl group (preferably an alkyl group having l to 3 carbon atoms such as methyl, ethyl, propyl, etc.), and the above R9, R10 and R11 may be either the same or different.
• n represents an integer of l to 4
• each of p and q represents an integer of l to l5.
• those capable of giving a surface tension of 8 to 50 dyne/cm to the second stabilizing solution are particularly preferred in aspect of the effect for the present invention.
• the stabilizing solution substituting for water washing containing substantially no aldehyde compound refers to a stabilizing solution substituting for water washing with a concentration of 0.l g/l or less of the aldehyde which has been added at a concentration of l.5 to 2.0 g/l for the purpose of improvement of storability of the dye image into the final stabilizing solution in the processing step accom­panying water washing of the prior art.
• a concentration of about 0.02 g/l comes within the region containing substantially no aldehyde, but it is particularly preferred to contain no aldehyde at all.
• aldehyde As the aldehyde to be used in the stabilizing bath in the processing step of the prior art, formaldehyde has been exclusively used, and other examples of aldehyde may include glutaraldehyde, chloral, mucochloric acid, form­aldehyde sodium bisulfite, glutaraldehyde sodium bisbi­sulfite, etc., and they will not only deteriorate stora­bility of the dye image but also gives troubles such as precipitation formation or others in the stabilizing solution substituting for water washing of the present invention.
• the nucleus represented by Z1 and Z2 may be substituted, and examples of the substituent may include halogen atoms, (e.g. chlorine), alkyl groups (e.g. methyl, ethyl), alkoxy groups (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), aryl groups (e.g. phenyl), cyano group, etc.
• halogen atoms e.g. chlorine
• alkyl groups e.g. methyl, ethyl
• alkoxy groups e.g. methoxy, ethoxy
• alkoxycarbonyl groups e.g. methoxycarbonyl, ethoxycarbonyl
• aryl groups e.g. phenyl
• cyano group etc.
• the alkyl group and the alkenyl group represented by R1 and R2 may preferably have 5 or less carbon atoms, and R1 and R2 may preferably be alkyl groups.
• the amount of the sensitizing dye represented by the above formula (I) added in the emulsion may be appropriately within the range of from 2 ⁇ l0 ⁇ 6 to l ⁇ l0 ⁇ 3 mole, preferably from 5 ⁇ l0 ⁇ 6 to 5 ⁇ l0 ⁇ 4 mole per mole of silver halide.
• sensitizing dyes are sensitizing dyes having spectral sensitizing ability at the wave-­length region which is called green-sensitive or blue-­sensitive in light-sensitive materials
• the light-­sensitive material to be used in the present invention should desirably be spectrally sensitized with the above sensitizing dye within the limit afforded by spectral sensitizing ability, and it is preferred that at least the sensitizing dye in the sum of green-sensitive emulsion and blue-sensitive emulsion may comprise for the greater part (50 mole % or more) the above sensitizing dye.
• mildewproofing agent in the stabilizing solution substituting for water washing of the present invention.
• mildew­proofing agents preferably used are salicylic acid, sorbic acid, dehydroacetic acid, hydroxy benzoic acid type compounds, alkylphenol type compounds, thiazole type compounds, pyridine type compounds, guanidine type com­pounds, carbamate type compounds, morpholine type com­pounds, quaternary phosphonium type compounds, ammonium type compounds, urea type compounds, isoxazole type compounds, propanolamine type compounds, sulfamide derivatives and amino acid type compounds.
• hydroxybenzoic acid type compounds include hydroxybenzoic acid and ester compounds of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., preferably n-butyl ester, isobutyl ester and propyl ester of hydroxybenzoic acid, more preferably a mixture of the aforesaid three kinds of hydroxybenzoic acid esters.
• the alkylphenol type compounds are compounds in which the alkyl group has, as the substituent, an alkyl group having l to 6 carbon atoms, preferably ortho­phenylphenol and ortho-cyclohexylphenol.
• the thiazole type compound is a compound having nitrogen atom and sulfur atom in a five-membered ring, including preferably l,2-benzisothiazolin-3-one, 2-­methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-­3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-(4-­thiazolyl)-benzimidazole.
• pyridine compounds may include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, sodium-2-pyridinethiol-l-oxide, etc., preferably sodium-­2-pyridinethiol-l-oxide.
• the guanidine type compounds may be specifically cyclohexidine, polyhexamethylenebiguanidine hydrochlo­ride, dodecylguanidine hydrochloride, etc., preferably dodecylguanidine and salts thereof.
• the carbamate type compounds may be exemplified by methyl-l-(butylcarbamoyl)-2-benzimidazolecarbamate, methylimidazolecarbamate, etc.
• Typical examples of the morpholine type compounds are 4-(2-nitrobutyl)morpholine, 4-(3-nitrobutyl)morpho­line, etc.
• the quaternary phosphonium type compounds may include tetraalkylphosphonium salt, tetraalkoxy­phosphonium salt, etc., preferably tetraalkylphosphonium salt, more preferably tributyl ⁇ tetradecylphosphonium chloride and triphenyl ⁇ nitrophenylphosphonium chloride.
• quaternary ammonium com­pounds include benzalconium salt, benzetonium salt, tetraalkylammonium salt, alkylpyridinium salt, etc., more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, laurylpyridinium chloride, etc.
• Urea type compounds may be exemplified by N-(3,4-­dichlorophenyl)-N'-(4-chlorophenyl)urea, N-(3-trifluoro­methyl-4-chlorophenyl)-N'-(4-chlorophenyl)urea, etc.
• a typical example of the isoxazole type compound is 3-hydroxy-5-methyl-isoxazole, etc.
• the propanolamine type compounds may include n-propanols and isopropanols, specifically DL-2-benzyl­amino-l-propanol, 3-diethylamino-l-propanol, 2-dimethyl­amino-2-methyl-l-propanol, 3-amino-l-propanol, isopropa­nolamine, diisopropanolamine, N,N-dimethylisopropanol­amine, etc.
• sulfamide derivatives may include fluorinated sulfamide, 4-chloro-3,5-dinitro­benzenesulfamide, sulfanylamide, acetosulfamine, sulfa­pyridine, sulfaguanidine, sulfathiazole, sulfadiadine, sulfameladine, sulfamethadine, sulfaisooxazole, homo­sulfamine, sulfisomidine, sulfaguanidine, sulfametizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfa­thiazole, etc.
• amino acid type compound is N-lauryl- ⁇ -alanine.
• the compounds preferably used in the present invention are pyridine type compounds, guanidine type compounds and quaternary ammonium type compounds.
• the amount of the antifungal agent added in the stabilizing solution substituting for water washing may be within the range of from 0.002 g to 50 g, preferably from 0.005 to l0 g, per l l of the stabilizing solution substituting for water washing.
• the pH of the stabilizing solution substituting for water washing in the present invention may preferably be within the range of from 3.0 to l0.0, more preferably from 5.0 to 9.5, particularly preferably from 6.0 to 9.0.
• the pH adjustor which can be contained in the stabilizing solution substituting for water washing of the present invention there may be employed any of the alkali agents or acid agents generally known in the art.
• the present invention can exhibit great effect when the amount of the stabilizing solution substituting for water washing supplemented into the stabilizing bath is small, and it is preferred that said supplemented amount should be within the range of from l to 50-fold of the amount brought in from the previous bath per unit area of the light-sensitive material to be processed, and the effect of the present invention is particularly marked when said amount is within the range of from 2 to 20-fold.
• the processing temperature for the stabilizing processing may be l5 °C to 60 °C, preferably be 20 °C to 45 °C.
• the processing time may preferably as short as possible from the standpoint of rapid processing, but generally 20 seconds to l0 minutes, most preferably l minute to 3 minutes.
• the processing time should be shorter for earlier stage tanks and longer for later stage tanks.
• the method for feeding the stabilizing solution substituting for water washing in the stabilizing pro­cessing step according to the present invention may be preferivelyably to feed the solution to the later bath and permitted to overflow from the earlierier bath.
• the method for adding the above compounds they can be added according to any desired addition method. For example, they can be added into the stabilizing solution as a con­centrated solution.
• the above compounds and other additives may be added to the stabilizing solu­tion substituting for water washing to be fed into the stabilizing tank and this is used as the feed solution for the stabilizing supplementing solution substituting for water washing.
• the bleaching solution or bleach-fixing solution to be used in the present invention should preferably contain an organic acid ferric complex salt as the bleaching agent.
• organic acid for forming the organic acid ferric complex salt may include those as set forth below.
• the organic acid ferric complex salt is not limited to these, and any desired one species selected from these can be used or a combination of two or more species can be used, if desired.
• organic acids for forming the organic acid ferric complex salt to be used in the present invention particularly preferable ones include the following.
• the organic acid ferric complex salt to be used in the present invention may be used in the form of a free acid (hydroacid salt), an alkali metal salt such as sodium salt, potassium salt, lithium salt, etc., or an ammonium salt, or a water-soluble amine salt such as triethanol amine, etc., preferably potassium salt, sodium salt and ammonium salt.
• a free acid hydroacid salt
• an alkali metal salt such as sodium salt, potassium salt, lithium salt, etc.
• an ammonium salt or a water-soluble amine salt such as triethanol amine, etc., preferably potassium salt, sodium salt and ammonium salt.
• bleaching agents are used in amounts of 5 to 450 g/l, more preferably 20 to 250 g/l.
• a solution having a composition contain­ing a silver halide fixing agent other than the above bleaching agent and also containing a sulfite as the preservative, if desired, is applied.
• a bleach-fixing solution such as a bleach-fix­ing solution comprising a composition in which a small amount of a halide such as ammonium bromide other than the organic acid iron (III) complex salt bleaching agent and the above silver halide fixing agent, or a bleach-­fixing solution comprising a composition in which a halide such as ammonium bromide is conversely added in a large amount, or further a special bleach-fixing solution comprising a composition in which the organic acid iron (III) complex salt bleaching agent is combined with a large amount of a halide such as ammonium bromide or the like.
• a bleach-fixing solution such as a bleach-fix­ing solution comprising a composition in which a small amount of a halide such as ammonium bromide other than the organic acid iron (III) complex salt bleaching agent and the above silver halide fixing agent
• a bleach-­fixing solution comprising a composition in which a halide such as ammonium
• halide other than the ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc., may be also used.
• the silver halide fixing agent contained in the fixing solution or bleach-fixing solution there may be employed compounds capable of forming water-soluble complex salts by reaction with silver halide as used in the conventional fixing processing, including typically thiosulfates such as potassium thiosulfate, sodium thio­sulfate, ammonium thiosulfate, etc., thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc., thiourea, thioether, etc.
• These fixing agents may be used in an amount of 5 g/l or more within the range which can be dissolved, but generally within the range of from 70 to 250 g/l.
• the bleach-fixing solution can contain various kinds of pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc., either alone or as a combination of two or more kinds. Further, various kinds of fluorescent brighteners, defoaming agents or surfactants may be contained.
• pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
• organic chelating agents such as hydroxylamine, hydrazine, aminopolycarboxylic acid, etc., stabilizers such as nitroalcohol, nitrate, etc., or organic solvents such as methanol, dimethylsulfoamide, dimethyl sulfoxide, etc., may be contained appropriately.
• various bleaching accelerators can be added as disclosed in Japanese Provisional Patent Publi­cation No. 280/l97l, Japanese Patent Publications No. 8506/l970 and No. 556/l97l, Belgian Patent No. 770,9l0, Japanese Patent Publications No. 8836/l970 and No. 9854/­l978, Japanese Provisional Patent Publications No. 7l634/­l979 and No. 42349/l974, etc.
• the bleach-fixing solution is used at pH of 4.0 or higher, generally from pH 5.0 to pH 9.5, desirably from pH 6.0 to pH 8.5, most preferably at pH 6.5 to pH 8.5.
• the processing temperature is 80 °C or lower and lower by 3 °C or more, preferably 5 °C or more than the processing solution temperature in the color developing tank, desirably 55 °C or lower while suppressing evaporation, etc.
• the light-sensitive material to be used in the method of the present invention comprises silver halide emulsion layers and non-light-sensitive layers (non-­emulsion layers) coated on a support.
• the silver halide emulsion any silver halide such as silver chlo­ride, silver bromide, silver iodide, silver chlorobro­mide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, etc.
• all couplers and additives known in the field of photography can be contained.
• dye forming couplers there may be contained appropriately yellow dye forming couplers, magenta dye forming couplers, cyan dye forming couplers, stabilizers, sensitizing dyes, gold compounds, high boiling point organic solvents, antifog­gants, dye image fading preventives, color staining preventives, fluorescent brighteners, antistatic agents, film hardeners, surfactants, plasticizers, wetting agents and UV-ray absorbers, etc.
• the light-sensitive material to be used in the method of the present invention can be prepared by providing by coating the respective constituent layers of emulsion layers and non-light-sensitive layers containing various additives for photography as mentioned above, if necessary, on a support applied with corona discharging treatment, flame treatment or UV-ray irradiation treat­ment, or alternatively through intermediary subbing layer or intermediate layer on the support.
• the support advantageously used may be, for example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate or polyester film such as polyethylene terephthalate, etc., polyamide film, polycarbonate film, polystyrene film, etc.
• Most of the above silver halide emulsion layers and non-light-sensitive layers are generally in the form of hydrophilic colloid layers containing a hydrophilic binder.
• a hydrophilic binder gelatin or gelatin derivatives such as acylated gelatin, guanidylated gelatin, phenylcarbamylated gelatin, phthalated gelatin, cyanoethanolated gelatin, esterified gelatin, etc., may be preferably used.
• the film hardening agent for hardening the hydrophilic colloid layer it is possible to use, for example, chromium salts (chrome alum, chromium acetate, etc.) aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methylol­dimethylhydantoin, etc.), dioxane derivatives (2,3-­ dihydroxydioxane), etc., active vinyl compounds (l,3,5-­triacryloyl-hexahydro-s-triazine, l,3-vinylsulfonyl-2-­propanol, etc.), active halide compounds (2,4-dichloro-6-­hydroxy-s-triazine, etc.), mucohalogenic acids (muco­chloric acid, mucophenoxychloric acid, etc.) and the like, either alone or
• the present invention is particularly effec­tive in the case of the so-called oil protect type in which a dispersion of a coupler contained in a high boil­ing point organic solvent is contained.
• the effect of the present invention is great when using, as such a high boiling point organic solvent, organic acid amides, car­bamates, esters, ketones, urea derivatives, etc., parti­cularly phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, diamyl phtha­late, dinonyl phthalate, diisodecyl phthalate or the like; phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, tri-(2-ethylhexyl)phosphate, tri­nonyl phosphate or the like; se
• the layer constitution of the light-sensitive material to be used in the present invention can be a constitution known in color negative film, color paper and reversal color film.
• it can include an embodiment having a blue-sensitive silver halide emulsion layer containing a yellow dye forming coupler, a green-­sensitive silver halide emulsion layer containing a magenta dye forming coupler and a red-sensitive silver halide emulsion layer containing a cyan dye forming coupler on one surface of a support (these respective color-sensitive layers may consist of one layer or two or more layers).
• R1 represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group each of which may have a substituent
• R2 represents a cyano group or an N-phenylcarbamyl group which may have a substituent
• Y represents -CO-, -SO2-, a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom having no oxygen atom bonded with a double bond
• Z represents a group of non-metallic atoms necessary for completion of a 4- to 6-membered nitrogen containing heterocyclic nucleus.
• the effect of the present invention can be exhibited when the total dried film thickness of the light-sensitive silver halide emulsion layers on one surface of a support is l0 ⁇ m or more, and the effect of the present invention is particularly remarkable when it is preferably 30 ⁇ m or less, particularly within the range of from l5 to 25 ⁇ m. If the total dried film thickness is less than l0 ⁇ m, the improved effect against staining of the present invention becomes small.
• aromatic primary amine color forming agents are used and various known compounds widely used in color photographic process are included in said developing agent.
• These developing agents are inclusive of aminophenol type and p-phenylenediamine type derivatives.
• These compounds are used generally in the form of a salt such as hydro­chloride or sulfate, since it is more stable than in the form of a free state.
• These compounds are used generally at a concentration of about 0.l g to about 30 g per l l of the color developing solution, preferably at a concen­tration of about l g to about l.5 g per l l of color developing solution.
• aminophenol type developing agent examples include o-aminophenol, p-aminophenol, 5-amino-2-hydroxy­toluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-l,4-­dimethylbenzene, etc.
• Particularly useful aromatic primary amine type color developing agents are N,N'-dialkyl-p-phenylenedi­amine type compounds of which the alkyl group and phenyl group may be substituted with any desired substituent.
• examples of particularly useful compounds may include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-­p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-­dodecylamino)-toluene, N-ethyl-N- ⁇ -methanesulfoneamido­ethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N- ⁇ -­hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethyl­aniline, 4-amino-N-(2-
• the color developing solution containing substantially no benzyl alcohol contains substantially no benzyl alcohol, namely at a concentration of l ml/l or lower, which is contained at a concentration of l0 to 20 ml/l in a conventional color developing solution.
• a concentration of about 0.5 ml/l comes within the region containing substantially no benzyl alcohol, but it is particularly preferred to contain no benzyl alcohol at all.
• the color developing solution in addition to the above aromatic primary amine type color developing agent, various components generally added in color developing solution, for example, alkali agents such as sodium hydroxide, sodium carbonate, potassium carbonate, etc., alkali metal thiocyanates, alkali metal halides, water softeners and thickeners, etc., can be contained as desired.
• alkali agents such as sodium hydroxide, sodium carbonate, potassium carbonate, etc.
• alkali metal thiocyanates alkali metal halides
• water softeners and thickeners etc.
• the pH value of the color developing solution using the aromatic primary amine type color developing agent as the color developing agent may be usually 7 or higher, most generally about l0 to about l3.
• the soluble silver complex salt contained in the stabilizing solution substituting for water washing and the bleach-fixing solution to be used in the processing method of the present invention may be subjected to silver recovery accoring to the known method.
• the electrolytic method (disclosed in French Patent No. 2,299,667)
• the precipitation method (disclosed in Japanese Provisional Patent Publication No. 73037/l977 and West German Patent No. 23 3l 220)
• the ion exchange method (disclosed in Japanese Provisional Patent Publication No. l7ll4/l976 and West German Patent No. 25 48 237)
• the metal substitution method (disclosed in U.K. Patent No. l,353,805).
• the processing method of the present invention can be advantageously applied for processing of color nega­tive film, reversal color film, color negative paper, color positive paper and reversal color paper.
• processing steps for which the present invention can be applied particularly effectively include the following (l) and (2).
• the polyethylene coated paper used was prepared by forming a coated layer of a composition comprising a mixture of 200 parts by weight of a polyethylene having an average molecular weight of l00,000 and a density of 0.95 and 20 parts by weight of a polyethylene having an average molecular weight of 2,000 and a density of 0.80 added with 6.8 % by weight of an anatase type titanium oxide according to the extrusion coating method to a thickness of 0.035 mm onto the surface of a pure paper with a weight of l70 g/m2 and providing a coated layer with a thickness of 0.040 mm only of a polyethylene on the back surface. After application of pre-treatment by corona discharging on the polyethylene coated surface on the support surface, the respective layers were coated successively.
• This is a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion contain­ing 80 mole % of silver bromide, and said emulsion contains 450 g of gelatin per mole of silver halide, is sensitized with 2.5 ⁇ l0 ⁇ 3 mole of a sensitizing dye of the present invention (exemplary compound I - l2) per mole of silver halide (isopropyl alcohol is used as the solvent), contains 200 mg/m2 of 2,5-di-t-butyl hydro­quinone dispersed by dissolving in dibutylphthalate and 2 ⁇ l0 ⁇ 3 mole per mole of silver halide of Y - 5 as the yellow coupler, and is coated to a silver quantity of 500 mg/m2.
• This is a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion contain­ing 85 mole % of silver bromide, and said emulsion contains 450 g of gelatin per mole of silver halide, is sensitized with 2.5 ⁇ l0 ⁇ 3 mole of a sensitizing dye having the following structure: per mole of silver halide, contains l50 mg/m2 of 2,5-di-­t-butylhydroquinone dispersed by dissolving in a solvent comprising a mixture of 2 : l of dibutylphthalate and tricresyl phosphate and l.5 ⁇ l0 ⁇ 1 mole of l-(2,4,6-tri­chlorophenyl)-3-(2-chloro-5-octadecenylsuccinimido­anilino)-5-pyrazolone per mole of silver halide as the magenta coupler, and is
• This is a red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion contain­ing 85 mole % of silver bromide, and said emulsion contains 500 g of gelatin per mole of silver halide, is sensitized with 2.5 ⁇ l0 ⁇ 3 mole of a sensitizing dye having the following structure: per mole of silver halide, contains 55 mg/m2 of 2,5-di-­t-butylhydroquinone dispersed by dissolving in dibutyl phthalate and 3.5 ⁇ l0 ⁇ 1 mole of 2,4-dichloro-3-methyl-­ 6-[ ⁇ -(2,4-diamylphenoxy)butyramido]phenol per mole of silver halide as the cyan coupler, and is coated to a silver quantity of 400 mg/m2.
• This is a gelatin layer and is coated to a gelatin quantity of l000 mg/m2.
• the silver halide emulsions used for the respec­tive light-sensitive emulsion layers were prepared according to the method as described in Japanese Patent Publication No. 7772/­l97l, and each of them was chemically sensitized with sodium thiosulfate pentahydrates and incorporated with 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene as the stabilizer, bis(vinylsulfonylmethyl)ether as the film hardener and saponin as the coating aid.
• the film thickness after coating and drying as described above was measured to be l7 ⁇ m.
• the color paper prepared according to the above method was exposed to light and then the experiments were conducted with the use of the following processing steps and processing solutions.
• Benzyl alcohol 20.0 ml Potassium sulfite 3.0 g Potassium carbonate 30.0 g Hydroxylamine sulfate 4.0 g 3-Methyl-4-amino-N-ethyl-N-( ⁇ -methane­sulfonamidoethyl)aniline sulfate 7.5 g Fluorescent brightener 2.5 g l-Hydroxyethylidene-l,l-diphosphonic acid 0.5 g Hydroxyethyliminodiacetic acid 5.0 g Magnesium chloride.hexahydrates 0.8 g l,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3 g (made up to l liter with addition of water, and adjusted to pH l0.70 with potassium hydroxide).
• Ferric methyliminodiacetate 60 g Methyliminodiacetic acid 3 g Ammonium thiosulfate (70 % solution) l00 ml Ammonium sulfite (40 % solution) 27.5 ml (made up to l liter with addition of water, and adjusted to pH 7.l with potassium carbonate or glacial acetic acid).
• Ammonium thiosulfate (70 % solution)500 ml Ammonium sulfite (40 % solution)250 ml Methyliminodiacetic acid l7 g Glacial acetic acid 85 ml (made up to the total amount of l liter with addition of water; this solution has a pH of 5.3 ⁇ 0.l).
• An automatic developing machine was filled with the above color developing tank solution, bleach-fixing tank solution and the stabilizing tank with tap water and continuous processing was performed by processing color paper while supplementing the color developing supple­menting solution and the bleach-fixing supplementing solutions A and B as described above through quantitating cups at intervals of 3 minutes.
• the amounts supplemented were, per l m2 of color paper, l90 ml for the color developing tank, and each 50 ml of the bleach-fixing supplementing solutions A and B for the bleach-fixing tank, and 20 l of tap water were flowed to the stabiliz­ing processing bath per l m2.
• the stabilizing processing tank in the automatic developing machine was made a stabilizing tank consisting of the first tank to the third tank in the direction of the flow of the light-sensitive material, and a multi­tank countercurrent system was employed in which supple­menting was conducted from the final tank, the overflow from the final tank was permitted to flow into the tank in the preceding stage, and further the overflow from this stage was permitted to flow into the tank in the stage preceding thereto.
• a light-­sensitive material was prepared in entirely the same manner except for removing the sensitizing dye (exemplary compound I - l2) added in the first layer, by use of this light-sensitive material, processing as shown in Table l was conducted similarly as Experiments l to 9.
• the sixth layer was coated after coating of the first layer to prepare a light-sensitive material in which none of the second layer to the fifth layer were provided.
• light-sensitive materials were prepared by varying the amount of the first layer coated to 2-fold, 3-fold, 4-fold, 5-fold and 6-fold. These dried film thicknesses were found to be 7.l ⁇ m, l2.8 ⁇ m, l8.4 ⁇ m, 24.2 ⁇ m, 29.9 ⁇ m and 35.7 ⁇ m, respectively.
• the present invention is effective when the light-sensitive material has a dried film thickness of l0 ⁇ m or more, particularly effective in the range from about l0 ⁇ m to 30 ⁇ m, most preferably in the range from about l5 ⁇ m to 25 ⁇ m.
• a halation preventive layer and a gelatin layer were provided, and a red-sen­sitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver and a blue-sensitive silver halide emulsion layer were coated thereon to a total silver quantity of 70 mg/l00 cm2.
• the above emulsion layers comprise a silver iodo­bromide containing about 4.5 mole % of silver iodide and, in this case, Y - l2 was employed as the yellow coupler in the blue-sensitive silver halide emulsion layer; 1-(2, 4,6-trichlorophenyl)-3- ⁇ [ ⁇ -(2,4-di-t-amylphenoxy)acet­amido]-benzamido ⁇ -3-pyrazolone and l-(2,4,6-trichloro­phenyl)-3- ⁇ [ ⁇ -(2,4-di-t-amylphenoxy)acetamido]benzamido ⁇ -­4-(4-methoxyphenylazo)-5-pyrazolone were employed as the magenta coupler in the green-sensitive silver halide emulsion layer; 1-hydroxy-N- ⁇ -(2,4-t-amylphenoxy)butyl ⁇ -­2-naphthoamide was
• the color negative film thus obtained was found to have a dried film thickness of 23 ⁇ m.
• the above light-sensitive material was applied with exposure in a conventional manner and then experiment was conducted with the use of the following processing steps and processing solutions.
• Potassium carbonate 30 g Sodium sulfite 2.0 g Hydroxylamine sulfate 2.2 g Potassium bromide l.2 g Diethylenetriaminepentaacetic acid 2.0 g Sodium hydroxide 3.4 g N-ethyl-N- ⁇ -hydroxyethyl-3-methyl-­4-aminoaniline sulfate 4 6 g (made up to l liter with addition of water and adjusted to pH l0.06 with potassium hydroxide).
• Potassium carbonate 30 g Sodium sulfite 2.0 g Hydroxylamine sulfate 2.2 g Potassium bromide l.2 g Diethylenetriaminepentaacetic acid 2.0 g Sodium hydroxide 3.4 g N-ethyl-N- ⁇ -hydroxyethyl-3-methyl-­4-aminoaniline sulfate 4.6 g (made up to l liter with addition of water and adjusted to pH l0.35 with potassium hydroxide).
• Diethylenetriaminepentaacetic acid ferric complex salt 0.3l mole Nitrilotriacetic acid 5.0 g Ammonium sulfite l5 g Ammonium thiosulfate l50 g (made up to l liter with addition of water and adjusted to pH 7.0 with aqueous ammonia (28 % solution)).
• Formalin 35 % aqueous solution
• 7.0 ml made up to l liter with addition of water.
• An automatic developing machine was filled with the above color developing tank solution, the bleach-fix­ing tank solution, the washing water and the stabilizing tank solution, and continuous processing was performed by processing the color negative film while supplementing the above color developing supplementing solution, the bleach-fixing supplementing solution and the stabilizing supplementing solution through quantitating cup at the intervals of 3 minutes.
• the amounts supplemented were, per l m2 of the color negative film, l475 ml for the color developing tank, 926 ml for the bleach-fixing tank and 926 ml of the stabilizing supplementing solution for the stabilizing processing tank, respectively.
• the amount of the washing water in the washing step was 30 l/m2.
• a multi-tank countercurrent system in which the stabilizing tank consisted of the first tank to the third tank in the direction of the flow of the light-­sensitive material, and supplement was performed from the final tank, with the overflow from the final tank being flowed into the tank in the preceding stage and further the overflow from this stage being flowed into the tank in the stage preceding thereto.
• the amount supplemented of the stabilizing solution substituting for water washing was the same as the stabilizing solution in Experiment l2.
• Dodecylguanidine hydrochloride 0.l g Ethylene glycol l.0 g (made up to l liter with water, and adjusted to pH 7.0 with sulfuric acid or potassium hydroxide).

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• 1985
  • 1985-09-27 JP JP60216010A patent/JPS6275451A/ja active Pending
• 1986
  • 1986-09-24 AU AU63097/86A patent/AU596118B2/en not_active Ceased
  • 1986-09-25 EP EP86307394A patent/EP0217643B1/de not_active Expired - Lifetime
  • 1986-09-25 DE DE8686307394T patent/DE3677120D1/de not_active Expired - Fee Related
  • 1986-09-26 CA CA000519227A patent/CA1294814C/en not_active Expired - Fee Related
  • 1986-09-26 KR KR1019860008066A patent/KR940002541B1/ko not_active Expired - Fee Related

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