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
  • G03C5/40—Chemically transforming developed images
  • G03C5/44—Bleaching; Bleach-fixing

Definitions

• a step for removal of developed silver from the silver halide emulsion layer (the socalled bleaching step) is included.
• a step for the removal of silver images formed in color development is carried out in order to retain only color images formed in the color development; and analogously, in the processing of black-white reversalphotographic materials a step for the removal of silver images formed in an initial exposure and development is carried out for thepurpose oflformation of positive images.
• Ferricyanides and iron-aminopolycarboxylic acid complexes are known as bleaching agents used in these steps. These conventional bleaching agents, however, are not completelysatisfactory with respect to both non-toxicity and bleaching ability, and therefore, recently, discovery of other practical photographic bleaching agents 7 as well as photographic bleaching methods have been desired.
• An object of this invention is to provide a photographic bleaching methodwhere a less toxic bleaching agent of a high bleaching rate is used.
• Another object of this invention is to provide a method'of formation of color photographic images at a much reduced bleaching time.
• Still another object of this invention is to provide a method for processing color photographic materials which does not give rise to pollution problems.
• the method of this invention comprises processing an exposed and developed silver halide emulsion layer with a bleaching solution containing a polyvalent cation-organic phosphonic acid complex as the bleaching agent.
• M represents a hydrogen atom or a cation which 1 or o-acetamidobenzyl group, especially an aralkyl group having 7 to 9 carbon atoms), an alicyclic group (e.g., a cyclohexyl or cyclopentyl group), or a heterocyclic group (e.g., a pyrrolidylmethyl, pyrrolidylbutyl,
• R especially when representing an alkyl group
• R can be substituted with a hydroxyl group, an alkoxy group (e.g. a methoxy or ethoxy group), a halogen atom (e.g., a chlorine atom), PO M Cl-l- PO M or N(C l-I PQ M where M has the same meaning as described above.
• Ethylenediamine-N,N,N',N'-tetramethylene phonic acid Nitrilo-N,N,N-trimethylene phosphonic acid 1 ,2-Cyclohexanediamine-N,N,N ',N'-tetramethylene phosphonic acid o-Carboxyaniline-N,N-dimethylene phosphonic acid Propylamine-N,N-dimethylene phosphonic acid 4-(N-Pyrrolidino)butylamine-N,N-bis(methylene phosphonic acid) l ,3-Diaminopropanol-N,N,N',Nfftetramethylene phosphonic acid l,3-Propanediamine-N,N,N',N'- tetra methylene phosphonic acid l,-l lexanediamine-N,N,N,N-tetramethylene phos- 'phonicacid I o-Acetamidobenzylamine
• R represents a hydrogen atom, or an alkyl, aralkyl, alicyclic or heterocyclic group which is defined above, 01' -PO M and R represents a hydrogen atom, a hydroxyl group or an alkyl group, or the above defined substituted alkyl group or --P0 M where M has the same meaning as described above.
• Representative examples of compounds of the above general formula (II) are given below.
• the bleaching solution used in the present invention contains as a bleaching agent the above specified polyvalent cation-organic phosphonic acid complex.
• the amount of this complex is generally about 20 to 200 g, preferably 50 to 150 g, per 1 liter of the bleaching solution.
• the lower limit of the amount of complex depends upon the bleaching ability thereof, and the upper limit thereof mainly depends upon factors such as solubility and economics. Accordingly, the upper limit of the amount of the complex can be extended further by the use of an appropriate dissolution aid, and so, the upper limit thereof is not limited to within the above mentioned scope. In the present invention it is only important that the bleaching solution contain the above described complex, and therefore, the method of addition thereof can be broadly.
• a convenient method comprises adding a complex which was previously prepared to an aqueous solution, but apart from this, it also is possible to form the complex in an aqu'eoussolution by adding a salt of poly-valent cation and an organic phosphonicacid to the aqueous solution.
• the amount of both compounds preferably 50to 200 g, per 1 liter'of the bleaching solution.
• the bleaching solution of this invention can further contain other additives known in this technical field as being capable of being added to a bleaching solution or a bleaching-fixation solution.
• additives include nitrates such as sodium nitrate, sulfites such as sodium sulfite, mercapto compounds such as mercaptotriazole, pH buffers such'as borates, oxalates,
• a suitable pH for the bleaching solution of this invention is a pH of about 3 to 8, preferably 5 to 7.
• the method of this invention comprises the individual steps of development, bleaching and fixation.
• development is generally color development, but development also means black-white development or blackwhite development and color development.
• the abovedescribed three steps need not be necessarily carried out without interruption, and other additional steps can be carried out before and after each of these steps.
• additional steps include subjecting the photographic material to a fixation bath, an image stabilization bath, a hardening bath, a neutralization bath, a water-washing including rinsing), etc., and, as the case may be, the bleaching and fixation step can further be included.
• the color developer used in the present invention is an alkaline aqueous solution of a known aromatic primary amine color developing agent, and preferably contains 1 g/liter or more, or as the case may be, less than 1 g/liter, of benzyl alcohol.
• color developing agents are phenylenediamine derivatives such as N,N-diethyl-p-phenylenediamine sulfate, 4-amino-N-ethyl-N-B-hydroxyethylaniline sulfate, 3-methyl-4-amino-N-ethyl-B-methanesulfoamidoethylaniline-sesquisulfatemonohydrate, 3-methyl-4- amino-N-ethyl-N-fl-hydroxyethylaniline sulfate, 3- methyl-4 amino-N,N-diethylaniline chloride, etc.
• phenylenediamine derivatives such as N,N-diethyl-p-phenylenediamine sulfate, 4-amino-N-ethyl-N-B-hydroxyethylaniline sulfate, 3-methyl-4-amino-N-ethyl-B-methanesulfoamid
• the color developer can contain known developer additives such as alkali metal sulfites, carbonates, bisulfites, bromides, iodides as well as anti-fogging agents, development accelerating agents and solvents such as diethylene glycol.
• developer additives such as alkali metal sulfites, carbonates, bisulfites, bromides, iodides as well as anti-fogging agents, development accelerating agents and solvents such as diethylene glycol.
• the color developer contains a color coupler (for example, as described in US. Pat. Nos. 2,252,718; 2,592,243 and 2,590,970).
• an alkaline aqueous solution is used as a developer, containing developing agents such as the dihydroxybenzenes (e.g., hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichloro-hydroquinone, 2,5- dimethyl-hydroquinone), the 3-pyrazolidones (e.g., l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3- pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, l-phenyl-5-methyl-3-pyrazolidone), the aminophenols (e.g., o-ami nophenol, p-aminophenol, N-methyl-o-aminophenol, N-rnethyl-p
• each and every conventional fixing solution can be used.
• about 50 to 200 g/liter or so of ammonium, sodium or potassium thiosulfate can be used as a fixing agent, and additionally, a stabilizer such as sulfite or metabisulfite, a hardening agent such as potassium alum, and a pH buffer such as acetate or borate can also be contained in the fixing solution.
• the fixing solution has a pH value of about 3 to 10.
• Photographic materials to which the method of this invention can be applied contain at least one silver halide emulsion layer.
• the silver halide emulsion is prepared by dispersing a silver halide such as silver chloride, silver iodide, silver bromide, silver bromochloride, silver bromoiodide, or silver bromoiodochloride, in a hydrophilic colloid (binder).
• hydrophilic colloids are,
• galatin for example, galatin, colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, saccharide derivatives such as agar, sodium alginate and starch derivatives, and synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyacrylic acid copolymers,
• polyacrylamide and derivatives thereof a compatible mixture of two or more of these colloids can be used.
• these colloids the most common one is gelatin, and a part or all of the gelatin can be replaced by synthetic high molecular weight substances.
• the gelatin can also be substituted by the so-called gelatin derivatives (that is, those prepared by treating the functional groups contained in the molecule such as amino groups, imino groups, hydroxy groups or carboxyl groups, with an agent having one group capable of reacting with these functional groups) or by gelatin graft-polymers grafted with molecular chains of other high molecular weight substances.
• agents for preparing gelatin derivatives are, for example, the isocyanates, acid chlorides and acid anhydrides as described in U.S. Pat. No. 2,614,928; the acid anhydrides described in U.S. Pat. No. 3,118,766; the bromoacetic acids described in Japanese Pat. Publication No. 5514/64; the phenylglycidylethers described in Japanese Pat. Publication No. 26845/67; the vinylsulfone compounds described in U.S. Pat. No. 3,132,945; the N-allylvinyl-sulfonamides described in British Pat. No. 861,414; the maleinimide compounds described in U.S. Pat. No.
• Silver halide emulsions can be prepared using conventional techniques which are generally well known in this technical field (e.g., the single-jet process, the double-jet process, the control-jet process) where a water-soluble silver salt (e.g., silver nitrate) and a water-soluble halide are admixed in the presence of water and the hydrophilic colloid and the mixture is subjected to physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization.
• spectral sensitizer e.g. cyanine dyes, merocyanine dyes or mixtures thereof, for example, as disclosed in U.S. Pat. Nos. 2,493,748;
• stabilizers e.g., 4-hydroxy-6-methyll,3,3a,7-tetrazaindene
• sensitizers e.g., the compounds described in U.S. Pat. No. 3,619,198
• anti-fogging agent's e.g., benzotriazole, S-nitrobenzimidazole, polyethyleneoxide
• hardening agents e.g., aldehyde compounds such as formaldehyde and glyoxal, nonaldehyde compounds such as mucochloric acid and 2-hydr0xy-4,6-dichloro-s-triazine, for example, as de- 3,543,292; etc.
• coating auxiliaries e.g., saponin, sodium lauryl sulfate, dodecylphenolpolyethyleneoxide ether, hexadecyltrimethylammonium bromide
• At least one silver halide emulsion layer can contain a color coupler (i.e., a compound forming a dye after reaction with an oxidation product of a color developing agent).
• a color coupler i.e., a compound forming a dye after reaction with an oxidation product of a color developing agent.
• a color coupler i.e., a compound forming a dye after reaction with an oxidation product of a color developing agent.
• a color coupler i.e., a compound forming a dye after reaction with an oxidation product of a color developing agent.
• a color coupler i.e., a compound forming a dye after reaction with an oxidation product of a color developing agent.
• each of a cyan, magenta and yellow color coupler is used in color'photography. Suitable examples of color couplers are described as follows: cyan couplers;
• a color coupler which hasa naphthol or phenol skeleton and can form an indoaniline dye by coupling is used as a cyan coupler; a color coupler which has active methylene groups and a S-pyrazolone ring structure sleketon is used as a magenta coupler; and a color coupler of a benzoylacetanilide, pivalylacetanilide or acrylacetanilide structure with or without a substituent in the coupling position, is used as a yellow coupler.
• the bleaching solution of this invention has a sufficient oxidizability to increase the color density.
• Repr'esentative of pyrazolone color couplers are those represented by the general formula (III) wherein, R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R represents an alkyl group, a carbamyl group, an amino group or an amido group. Examples of compounds represented by the above formula are as follows:
• yellow couplers such as benzoylacetanilide or pivaloylacetanilide couplers
• benzoylacetanilide or pivaloylacetanilide couplers are described in British Pat. No. 1,113,038 and US. Pat. Nos.
• couplers often do not sufficiently color in a bleaching-fixation solution since a relatively stable leuco type structure occurs therebetween when a dye is formed by coupling, being different from other two-equivalent couplers. According to the steps of the method of this invention, however, even such couplers can fully be used for coloration, and in addition, the difficult problem of discharge of harmful substances is extremely improved.
• Couplers can be synthesized by conventional methods as described, for example, In U.S. Pat. Nos. 3,277,155 and 3,408,194; German Pat. (OLS) No. 2,057,941; U.S. Pat. Nos.
• magenta dye forming couplers Suitable examples are disclosed in the hereinbefore described U.S. Pa-
• Silver halide emulsions thus prepared are applied and dried on a support such as glass, baryta paper, resin coated paper, cellulose acetate film or polyethylene terephthalate film using a dip method, an air-knife method, a bead method, an extrusion doctor method or a both surfaces, coating metho'd.
• the emulsion layer preferably comprises the three layers of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, and as the case may be, at least one of these layers can comprise a number of layer.
• the green-sensitive emulsion layer can comprise two layers, e.g., a highly sensitive layer and low sensitive layer.
• conventional auxiliary layers which are generally well known in this field such as a protective layer, an intermediate layer, a filter layer, an anti-halation layer and a backing layer can optionally be added.
• the method of this invention can be applied to the processing of any and all conventional silver halide photographic materials where removal of silver is necessary, such as color negative films, color papers, color positive films, color reversal films for slides, color reversal films for television use and black-white reversal films.
• Suitable temperatures at which the bleaching method of this invention can be employed in the processing of silver halide photographic materials can range from about to 60C, preferably to 50C,
• bleaching processing time of about seconds to 20 minutes, preferably 1 minute to 10 minutes.
• the toxicity of the bleaching agent used is low and the bleaching rate thereof is relatively high, and therefore, it is possible to carry out the bleaching step in a more stable manner as compared with other conventional bleaching agents. Accordingly, the time necessary for photographic processing is reduced and there is no danger of environmental pollution resulting from the discharged solution. It is a matter of course that color images fi-' nally obtained by the present method are free from any color fog and stain.
• Another advantage attainable by the present method is that recovery and use of the fatigued bleaching solution are simplified. This is because bleaching agents of the kinds of the presentinvention can be recovered simply by blowing air or oxygen thereinto when fatigued, and therefore, recovery of silver is also easy. In view of the fact that such an advantage cannot be attained when conventional bleaching-fixation solutions are used, this advantage is considered an important additional merit of this invention.
• the bleaching ability thereof does not decrease even if the content of the silver halide or the silver iodide of the photographic material treated is increased.
• a conventional non-toxic photographic bleaching agent such as a Fe(III)-aminopolycarboxylic acid complex
• the bleaching ability thereof decreases if the content of silver halide or silver iodide is increased.
• the standard content thereof is in general about 40 mg/lOO cm of silver EXAMPLE 1 l-I-lydroxy-4-chloro-2-m-dodecylnaphthamide as a,
• cyan coupler was emulsified and mixed in a red-sensitive silver bromoiodide emulsion (Agl 7 mole%), and analogously, 1-(2',4,6-trichlorophenyl)-3-[3"-(2",- 4 '-di-t-amylphenoxyacetamido )benzamido -5 pyrazolone as a magenta coupler in a green-sensitive silver bromoiodide emulsion (Agl 6 mole%) and apyvalyl-a-[4-(4-benzyloxysulfonyl)phenoxy]-2-chloro- 5-[y-(2,4-di-t-amylphenoxy)-butylamido]acetanilide as a yellow coupler in a blue-sensitive silver bromoiodide (Agl 6 mole%), and these were applied on a triacetate film base to form a color negative photographic material, which was used in the following experiment
• Bleaching Solution llged dispersion, a silver bromochloride emulsion (silver chloride 70 mole containing a cyan coupler emulsifled dispersion, and a gelatin layer containing an ultraviolet absorbing agent, to prepare a color paper.
• Each coupler emulsion used in the preparation of this color paper was prepared as follows: Each coupler was dissolved in a mixture of dibutyl phthalate and tricresyl phosphate, and the resulting solution was dispersed in a gelatin solution in the form of an o/w dispersion using sorbitan monolaurate, Turkey red oil and dodecylbenzene sodium sulfonate as dispersing and emulsifying agents.
• the treating solutions used had the following compositions:
• COLOR DEVELOPER COMPOSITION Benzyl Alcohol 12 ml Diethyleneglycol 3.5 g Sodium Hydroxide 20 g Sodium Sultite 20 g Potassium Bromide 0.4 g Sodium Chloride 1.0 g Borax 4.0 g Hydroxylamine Sulfate 20 g Ethylenediaminetetraacetic Acid 20 g 4-Amino-3-methyl-N-ethyl-N-(B-sulfonamido- 50 g ethyl)aniline-sesquisulfate-monohydrate Water to make 1 liter Stopping Solution Sodium Thiosulfate 10 g Ammonium Thiosulfate 30 cc Sodium Acetate 5 g Acetic Acid 30 cc Potassium Alum 15 Water to make 1 fiter Bleaching Solution Ferric Chloride (6H,O) 30 g kHcyl'droxyethylidene-l,l-diphosphonic 25 g c
• Bleaching Solution II was Prosessmg Step5 Tempeame easily regenerated simply by blowing air thereinto and Pro-hardening 317C 2 min. and 30 secthe regenerated solution could be used analogously to a g fgfgtfigg fresh solution, but Bleaching Solution I cannot be re- First Sto pin 30 sec. generated by such simple treatment.
• Bleaching Solution I gives rise to extreme environmen- Wate' ,Washiflg 1 i tal pollution if the solution thereof is discharged, but Bleaching 3 min. Fixation 1 mm there IS no such danger with Bleaching Solution II. Water Washing l min. EEC? processing slolution has the following composition:
• bleaching and fixing comprising separate steps in said method, the improvement comprising bleaching the silver halide photographic material with a bleaching solution containing a polyvalent cation-organic phosphonic acid complex as the bleaching agent and a rehalogenating agent selected from the group consisting of an alkali metal halide and an ammonium halide.
• organic phosphonic acid is an aminopolymethylene phosphonic acid or a water-soluble salt thereof.
• aminopolymethylene phosphonic acid is represented by the following general formula (I) R
• M is an alkali metal, ammonium or water-soluble substituted ammonium ion; wherein the alkyl group for R is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group; wherein said aryl group for R is a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a p-carboxyphenyl group, or a water-soluble salt of a p-carboxyphenyl group; wherein said aralkyl group for R is a benzyl group, an a-phenyl group or an o-acetamidobenzyl group; wherein said alicyclic.
• R is a cyclohexyl group or a cyclopentyl group; and wherein said heterocyclic group for R is a pyrrolidylmethyl group, a pyrrolidylbutyl group, a benzothiazolymethyl group or a tetrahydroquinolylmethyl group.
• R is an alkyl group substituted with a hydroxyl group, an alkoxyl group, a halogen atom, -PO M CH PO M or N(CH PO N wherein M represents a hydrogen atom or a cation which imparts water-solubility.
• said organic phosphonic acid is a compound respresentably the general formula (II) A z a a :)2 where R represents a hydrogen atom or an alkyl group, an aralkyl group, an alicyclic group or a heterocyclic group, or PO M and R represents a hydrogen atom, a hydroxyl group, an alkyl group, -PO M wherein M is a hydrogen atom or a cation which im- 36' parts water-solubility. solubility.
• M is an alkali metal, ammonium or water-soluble substituted ammonium ion; wherein the alkyl group for R is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group.
• alkyl group for R is an alkyl group substituted with a hydroxyl group, an alkoxyl group, a halogen atom, PO M CH -PO M or N(CH PO N wherein M is a hydrogen atom or a cation which imparts water-solubility.
• M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
• M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
• M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
• M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
• aminopolymethylene phosphonic acid is selected from those represented by the following general formulae (l) or II i 2 a z)z where M represents a hydrogen atom or a cation which imparts water-solubility; R represents an alkyl group having 1 to 4 carbon atoms; an aryl group; an aralkyl group; an alicyclic group; or a heterocyclic group; or
• M is an alkali metal, ammonium or water-soluble substituted ammonium ion.

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• 1973
  • 1973-07-07 JP JP48076842A patent/JPS5026543A/ja active Pending
• 1974
  • 1974-07-05 GB GB30025/74A patent/GB1442470A/en not_active Expired
  • 1974-07-08 US US486737A patent/US3928040A/en not_active Expired - Lifetime
  • 1974-07-08 DE DE2432721A patent/DE2432721A1/de active Pending

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