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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
  • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
  • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
  • G03C8/14—Oxidation of the chromogenic substances
  • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment

Definitions

• the present invention relates to a color photographic diffusion transfer process and more particularly it relates to an improved color photographic diffusion transfer process for color photographic materials containing dye developers.
• a photosensitive element having a silver halide emulsion and a dye developer is ex posed and a liquid processing composition is applied to the photosensitive element by, for instance, immersing, coating, spraying, etc.
• a liquid processing composition is applied to the photosensitive element by, for instance, immersing, coating, spraying, etc.
• the photosensitive element is superposed on an image-receiving element which can be dyed with the dye developer.
• the photosensitive element contains the dye developer in a layer adjacent to the side of a silver halide emulsion layer away from the incident light.
• the silver halide emulsion layer of the photosensitive element is placed on the image-receiving layer of the image-receiving element and a liquid processing composition is spread as a thin layer between the two layers.
• the liquid processing composition diffuses into the silver halide emulsion layer and the dye developer-containing layer to develope the developable silver halide and the dye developer thus developed the silver halide is immobilized.
• This immobilization is apparently due, at least in part, to the reduction is mobility or solubility of the oxidation product of the dye developer as compared with that of the unoxidized dye developer.
• the immobilization may be also due, at least in part, to the localized reduction of alkali concentration as a function of development.
• each silver halide emulsion layer is associated with each dye developer which has substantially a complementary color to the main sensitive region of the silver halide emulsion, that is to say, when a silver halide emulsion having sensitivity to red light is associated with a cyan dye developer, a silver halide emulsion having sensitivity to green light with a magenta dye developer, and a silver halide emulsion having sensitivity to blue light with a yellow dye developer, each dye developer is oxidized and immobilized in the developed region or area of each associated silver halide emulsion layer.
• the dye developers in the nondeveloped portions of the silver halide emulsion layers diffuse and are transferred to the image-receiving element superposed on the photosensitive element.
• cyan dye developers as 1,4-bis-(a-methyl- ,B-hydroxynonylpropylamino)-5,8-dihydroxyanthraquinone, etc.
• magenta dye developers as 4-propoxy-2-[p- (Bhydroquinonylethyl)-phenylazo]-1-naphthol, etc.
• yellow dye developers as l-phenyl-3N-nhexylcarboxyamido4-[p-2',5'-dih.ydroxyphenethyl) phenylazo]-5-pyrazolone, etc.
• the desired maximum density, gradation, and sensitivity cannot be obtained. Since the immobilization of the dye developers occurs as a function of the development of silver halide emulsion layers, the transferred image obtained in the diffusion transfer process shows undesirably high minimum density, low maximum density, and low contrast in the highlight regions.
• a silver halide emulsion layer is developed not only by the dye developer having substantially complementary color to the main sensitive region of the silver halide emulsion but also by other dye developers associated with other silver halide emulsion layers.
• a magenta dye developer which is associated with a green-sensitive silver halide emulsion layer diffuses partially into a blue-sensitive emulsion layer and a redsensitive emulsion layer to initiate development and is immobilized there, which results in forming a transferred image containing less magenta dye.
• a color diffusion transfer process comprising imagewise exposing a color photographic material having at least one silver halide emulsion layer and a dye developer disposed adjacent to the silver halide in the silver halide emulsion layer and processing the exposed material with an alkaline processing solution in a superposed relation with an image receiving material to immobilize the dye developer at the exposed portions of the silver halide emulsion layer and transfer by diffusion to the image receiving material the dye developer at the unexposed portions of the silver halide emulsion layer, and conducting the processing with the alkaline processing solution in the presence of 6,6, 7,7- tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'- spirocumarone.
• auxiliary developing agent for the purpose of distinguishing it from the dye developers.
• the auxiliary developing agent can be present in the processing composition or in the image receiving element but it is preferable that the auxiliary developing agent be present in the negative photosensitive element containing the dye developers.
• various methods can be employed for incorporating the auxiliary developing agent in a hydrophilic colloid layer of the negative photosensitive element.
• the auxiliary developing agent used in this invention is dissolved in a substantially water-insoluble high boiling organic solvent and after finely dispersing the solution in aqueous solution of a hydrophilic colloid, the dispersion thus containing the auxiliary developing agent is coated.
• the auxiliary developing agent is dissolved in an alkaline aqueous solution and after mixing the solution with an aqueous solution of a hydrophilic colloid, the mixture is coated.
• the auxiliary developing agent is dissolved in a low-boiling organic solvent such as methanol or ethyl acetate and after mixing the solution with aqueous solution of a hydrophilic colloid,
• the mixture is coated.
• the multilayer-type diffusion transfer color photographic material used in this invention has desirably, as a layer structure, on a support a red-sensitive emulsion layer, a green-sensitive emulsion layer and a bluesensitive emulsion layer in this order and the emulsion layers have associated therewith a cyan dye developer, a magenta dye developer and a yellow dye developer, respectively.
• the color photographic material can have a yellow filter layer, an antihalation layer, intermediate layers, and a protective layer.
• the silver halide emulsion used in the present invention is a colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide or silver chloroiodobromide or a mixture thereof.
• the composition of the halide is selected depending on the purpose to which the element is to be applied and treatment conditions of the sensitive material. Particularly, a silver iodobromide or chloroiodobromide emulsion consisting of l 10 mol percent of iodide, less than 30 mol percent of chloride and a balance of bromide is preferred.
• the mean particle size of the emulsion is usefully within a range of about 0.1 to about 2 microns and a uniform particle size is desirable depending on the end use purpose of sensitive material. Particles are of a cubic, an octahedral or a mixed crystal system. These silver halide emulsion can be prepared using conventional techniques, for example, as disclosed in P. Glafkides: Chimie Photographique, Chap. 18-23, 2nd edition, 1957, Paul Moncle, Paris.
• a soluble silver salt such as silver nitrate and a water soluble halide such as potassium bromide are reacted in a solution of a protective colloid such as gelatin and the crys tal growth accomplished in the presence of an excess of halide or a solvent for silver halide, such as ammonia.
• a precipitation method such as the single or double jet method or pAg controldouble jet method can be used.
• the removal of the soluble salts from the emulsion is by washing a cooled and coagulated emulsion with water, dialysis thereof, or settlement by adding a precipitating agent such as an anionic polymer or a surface active agent having sulfon, sulfuric acid ester or carboxylic group and controlling the pH or by using an acylated protein such as phthaloyl gelatin as the protective colloid and controlling the pH.
• a precipitating agent such as an anionic polymer or a surface active agent having sulfon, sulfuric acid ester or carboxylic group and controlling the pH or by using an acylated protein such as phthaloyl gelatin as the protective colloid and controlling the pH.
• the silver halide emulsion used in the present invention is desirably sensitized by subjecting the emulsion to a heat treatment in conjunction with sensitizers naturally contained in gelatin, a sulfur sensitizer such as sodium thiosulfate or N,N,N-trimethyl thiourea, a gold sensitizer such as thiocyanate or the thiosulfate complex salt of monovalent gold, or a reducing sensitizer such as stannous chloride or hexamethylenetetramine (for example, as described in U.S. Pat. Nos. 1,623,499; 2,399,083; 3,297,447; and 3,297,446).
• a sulfur sensitizer such as sodium thiosulfate or N,N,N-trimethyl thiourea
• a gold sensitizer such as thiocyanate or the thiosulfate complex salt of monovalent gold
• a reducing sensitizer such as stannous chlor
• the silver halide emulsion used in the present invention can be stabilized with an additive such as 4-hydroxy'6-methy1-1 ,3 ,3a, 7-tetrazaindene, 5- nitrobenzimidazole, 1-phenyl-5-mercaptotetrazo1e, 8- chloromercuriquinoline, benzenesulfinic acid and pyrocatechin.
• an additive such as 4-hydroxy'6-methy1-1 ,3 ,3a, 7-tetrazaindene, 5- nitrobenzimidazole, 1-phenyl-5-mercaptotetrazo1e, 8- chloromercuriquinoline, benzenesulfinic acid and pyrocatechin.
• inorganic compounds such as cadmium and mercury salts, and the complex salts of platinum group elements, such as the chlorine complex salt of palladium, are useful for the stabilization of the sensitive material according to the present invention.
• the silver halide emu1- sion used in the present invention can contain a sensitizing compound such as polyethylene oxide compound (for example, as described in U.S. Pat. Nos. 3,046,134; 2,944,900; and 3,294,540).
• a sensitizing compound such as polyethylene oxide compound (for example, as described in U.S. Pat. Nos. 3,046,134; 2,944,900; and 3,294,540).
• the silver halide emulsion used in the present invention can have its color sensitivity extended with an optical sensitizing dye.
• optical sensitizers there are mentioned the cyanines, merocyanines, homopolar cyanines, styryls, hemicyanines, oxanoles, hemioxanoles and the like. Examples of these optical sensitizers are described in by P. Glaflddes, supra (chap. 35 41) and F. M. Hamer: The Cyanine Dyes and Related Compounds (lnterscience).
• cyanines in which the nitrogen atom in the nucleus is substituted by an aliphatic radical having a hydroxyl, carboxyl or sulfo group, as described in U.S. Pat. Nos. 2,503,766; 3,459,553; 3,177,210; 3,384,486; 2,526,632; 2,493,748; 2,912,329 and 3,397,060, are useful in the present invention.
• the dye developer is ordinarily dissolved in a solvent or a solvent mixture under heating, the solution of the dye developer is added to an aqueous solutionof a hydrohilic colloid such as gelatin and after passing through a colloid mill suitable number of times, the mixture is directly coated or is coated after cooling, solidifying, cutting, washing, and melting. Or, alternatively, the solution of the dye developer is added to a silver halide emulsion and the mixture is coated.
• Preferred examples of the solvents used for the purpose are described in, for instance, the specifications of Japanese Patent Publication No. 13,837/1968 and U.S. Pat. No. 2,322,027.
• the color developer used in the present invention can be dispersed using various methods in a hydrophilic colloid as a carrier corresponding to the type of developer.
• a compound such as diffusion dyereleasing coupler having a dissociating group such as a sulfo or carboxyl group can be dissolved in water or alkaline aqueous solution and then added to a hydrophilic colloid solution.
• Color developers, which are difficult to dissolve in aqueous medium and easily dissolved in an organic solvent, are dissolved in an organic solvent, the resulting solution is then added to a hydrophilic colloid solution and dispersed as fine particles by agitation.
• suitable solvents there are mentioned ethyl acetate, tetrahydrofuran, methyl ethyl ketone, cy-
• high-boiling solvents suitable for the purpose there are mentioned the triglycerides of higher fatty acids, aliphatic esters such as dioctyl adipate, phthalic acid esters such as di n-butyl phthalate, phosphoric acid esters such as tn ocresyl phosphate and tri-n-hexyl phosphate, amides such as N,N-diethy1 lauryl amide, hydroxy compounds such as 2,4-di-n-amy1 phenol and the like. Further, to stabilize the dispersion of the color developer and promote the course of color image formation, it is advantageous to add a solvent-phile polymer together with color developer to the sensitive element.
• aliphatic esters such as dioctyl adipate
• phthalic acid esters such as di n-butyl phthalate
• phosphoric acid esters such as tn ocresyl phosphate and tri-n-hexyl
• solventphile polymers suitable for the purpose there are men tioned shellac, phenol-formaldehyde condensates, poly-n-butyl acrylate, the copolymer of n butyl acrylate and acrylic acid, the copolymer of n butyl acrylate, styrene and methacryl amide, and the like.
• These polymers can be dissolved together with the color developer in an organic solvent and then dispersed in a hydrophilic colloid, or a hydrosol of the polymer, prepared by emulsion polymerization, can be added to the hydrophillic colloid dispersion of the color developer.
• thedispersion of the color developer can be attained effectively in the presence of large shearing stress.
• a high speed rotating mixer for example, a high speed rotating mixer, a colloid mill, a high pressure milk homogenizer, the high pressure homogenizer disclosed in the British Pat. No. 1,304,264, and a supersonic emulsifier are useful.
• the dispersion of the color developer is promoted by using a surface active agent as an emulsion assistant.
• surface active agents which are useful for the dispersion of the color developer used in the present invention, there are mentioned sodium triisopropylnaphthalenesulfonate, sodium dinonylnaphthalenesulfonate, so dium p-dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, sodium cetylsulfate and anionic surface active agents disclosed in the Japanese Patent Pub1ication 4293/64; as described in U.S. Pat. No. 3,676,141, the combination of these anionic agents and higher fatty acid esters of anhydrohexitol shows an especially good emulsifying ability. Additionally, those disclosed in U.S. Pat. Nos. 3,287,133; 3,384,483; 2,992,104; 3,043,;692; 3,044,873; 3,061,453; 3,069,263; 3,069,264; 3,121,011 etc. are suitable.
• dye developers used in this invention are the compounds described in the specifications of U.S. Pat. Nos. 3,255,001; 3,320,063;
• Examples of specifically useful dye developers are 4-[p-(2,5'-dihydroxyphenyl)-phenylazo]-5- acetamidol -naphthol, 4-[p-( 2,5 dihydroxyphenethyl )-phenylazo]--benzamidol naphthol, 1-phenyl-3-methyl-4-[p-(2,5- dihydroxyphenethyl)-phenylazo]-5-pyrazolone, 2-[p- (2 ,5 '-dihyd roxyphenethyl )-phenylazo -4-acetamidol-naphthol, 2-[p-( 2,5 '-dihydroxyphenethyl phenylazo1-4-methoxy- 1 -naphthol, 2-[p-( 2,5 dihydroxyphenethyl)-phenylazo]-4-ethoxyl -naphthol, 1-phenyl-3-N-n-butyl
• the color of the cyan dye developer changes into magenta and when both amino nitrogen atoms of it are acylated, the color thereof changes into orange-yellow.
• the colors of the dye developers can be changed.
• the structure or the color of the dye developer can be changed by a development reaction, e.g., hydrolysis, that is to say, the color of the dye developer present in the photosensitive element can be changed when it is transferred to an image receiving element.
• a leuco compound such as 1-phenyl-3-methyl-4-( 2 -methyl-4-diethylamino)anilino-S-pyrazolone which does not give light filtering action to the emulsion layer under the layer containing it, which is immobilized at the developed portions, which diffuses imagewise from the undeveloped portions to an image receiving element, and which is oxidized therein into a colored image can be also used.
• the dye developer is disposed adjacent to the silver halide of a silver halide emulsion layer in the photosensitive element. That is to say, the dye developer or dye developers are incorporated in one or more emulsion layers and are preferably incorporated in silver halide emulsion layers or hydrophilic organic colloid layers under the corresponding silver halide emulsion layers.
• the dye developer in the layer under the silver halide emulsion layer having the main light-sensitive region which is a complementary color to the color of the dye developer.
• the dye developer can be incorporated in the silver halide emulsion layer which is associated with the dye developer or in the layer adjacent to the silver halide emulsion layer.
• the dye developer in a mixed packet in the colloid surrounding particles or fine grains containing silver halide particles. Such a mixed packet system is disclosed in US. Pat. Nos. 2,800,457; 2,800,458; 2,907,682, 3,466,662; and 3,276,869.
• the auxiliary developing agent be incorporated in a silver halide emulsion layer, a dye developer-containing layer, an intermediate layer, a protective layer, etc., of the photosensitive element. It is most preferred that the auxiliary developing agent be incorporated in one or more layers of the photosensitive element as a dispersion in an aqueous solution of an organic colloid such as gelatin as a solution thereof in a high-boiling organic solvent having a boiling point higher than about 175C.
• these high-boiling organic solvents are phthalic acid alkyl esters of which the alkyl group has, preferably, less than 6 carbon atoms, such as methyl phthalate, ethyl phthalate, propyl phthalate, n-butyl phthalate, di-n-butyl phthalate, amyl phthalate, isoamyl phthalate, and dioctyl phthalate; phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, and diphenyl mono-p-tertiary butylphenyl phosphate; alkyl amides; and acetanilide such as N-nbutylacetanilide and N-methyl-p-methylacetanilide.
• the high-boiling solvents may be also used as mixtures with other solvents having boiling points lower than these high-boiling solvents by at least 25C, to aid the solubility of the auxiliary developer and to permit then films, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, ethyl propionate, secondary-butyl alcohol, carbon tetrachloride, chloroform, benzyl alcohol, 2,3-methylcyclohexanone, and 2,4-methylcyclohexanone or solvents which are more soluble in water than the above-described high-boiling solvents and have a solubility of at least 2 parts thereof per parts of water, such as methyl isobutyl ketone, B-ethoxyethyl acetate, B-butoxy-B-ethoxyethyl acetate, tetrahydrofurfuryl adipate
• the amount of the auxiliary developing agent used in this invention depends on the amount and the kind of the dye developers used, the amount and the kind of silver halide, the layer structure of the photosensitive element, and the like but the amount thereof is usually 0.01 10 times, more generally 0.1 2 times the molar amount of the dye developer used. Also the amount is suitably 0.01 0.5 times the amount of the photosensitive silver halide.
• the amount generally used when the auxiliary developing agent is present in the processing solution is about 2 to 4 times the amount present when it is used in the photosensitive element.
• the silver halide coating amount generally is from about 0.4 to 4 X 10 mol/ 100 cm about 0.3 to 3 mol/ 100 cm and about 0.3 to 3 mol/ 100 cm for the red sensitive layer the green sensitive layer and the blue sensitive layer, respectively, for a total amount of about 1 to 10 X 10 mol/lOO cm
• the amount is, however, not limited to these ranges and amounts outsides these ranges can be used to achieve the objects desired.
• Layers used in the present invention which are permeable to treating solutions, such as a silver halide emulsion layer, a layer containing a color developer, auxiliary layers such as a protective layer or an intermediate layer, contain a hydrophilic polymer as a binder.
• gelatin casein, gelatin modified with acylating agents etc., gelatin grafted with vinyl polymer, proteins such as albumin; cellulose derivatives such as hydroxyethylcellulose, methylcellulose and carboxymethylcellulose; partial hydrolysates of polyvinyl alcohol or polyvinyl acetate, high molecular weight nonelectrolytes such as polyvinyl pyrrolidone or polyacrylamide; polyacrylic acid, the partial hydrolysate of polyacrylamide, anionic synthetic polymers such as the copolymer of vinyl methyl ether and maleic acid, further amphoteric synthetic polymer such as the copolymer of N-vinyl imidazole, acrylic acid and acrylamide or the polyacrylamide subjected to the Hofmann reaction.
• hydrophilic polymers are used either alone or in as admixtures thereof. Further, these hydrophilic polymer layers can contain a polymer latex dispersion of hydrophobic monomer such as an alkyl acrylate or methacrylate etc. These hydrophilic polymers, above all the polymers having a functional group such as an amino, hydroxyl and carboxyl group, can be rendered non-soluble with many kinds of cross-linking agents without losing the permeability to the treating solution.
• aldehyde compounds such as formaldehyde, glyoxal, glutaraldehyde, mucochloric acid or the oligomer or acrolein
• aziridines such as triethylene phosphamide as described in the Japanese Patent Publication 8790/62
• epoxy compounds such as l,4-bis(2',3'- epoxypropoxy)diethyl ether as described in the Japanese Patent Publication 7133/59
• active halogen compounds such as the sodium salt of 2-hydroxyl-4,6- dichloro-s-triazine as described in the U.S. Pat. No.
• hydrophilic polymer layers can contain a cross-linking promotor such as carbonates or resorcine other than the cross-linking agent.
• An image receiving element which is dyed by the dye developers from the negative photosensitive element can be suitably selected.
• the dyeable materials suitable for the image receiving layer of the image receiving element there are gelatin, polyvinyl pyrrolidone, poly-4-vinylpyridine, polyvinyl acetate, polyvinyl alcohol, cellulose acetate, polyvinyl salicylate, partially hydrolyzed polyvinyl acetate, methyl cellulose, and mix- 7 tures of them.
• the typical examples of the supports used for the image receiving elements and for the photosensitive elements are cellulose nitrate films, cellulose acetate films, polyvinyl acetal films, polystyrene films, polyethylene terephthalate films, polyethylene films, polypropylene films, papers, polyethylene-coated papers, glass, etc.
• the multilayer-type negative photosensitive element can be used as the support for the image receiving element.
• the support can be transparent or opaque according to the purposes.
• the image re DCV be associated with an acid polymer or an acid compound derivative which provides an acid material with a definite rate.
• an acid material is incorporated in the layer under the image receiving layer of the image receiving element. The acid material contributes to neutralize the alkali in the liquid processing composition on the image-receiving layer.
• the diffusion transfer photographic film unit according to the present invention preferably possesses a function for neutralizing alkalis brought from the treating compositions.
• a high pH-value i.e., more than 10, preferably more than 11, sufficient to promote the course of image formation which comprises the development of the silver halide emulsion, the formation of the diffusing color image and the diffusion thereof
• the treating composition contains an alkali.
• the pH-value in the film unit is neutralized to approximately neutral, i.e., below 9, preferably below 8, to stop practically further'image formation and prevent the change of image tone with the lapse of time.
• a neutralizing layer containing a sufficient amount of an acid substance to neutralize the alkali in the treating solution up to the pH-value as described above, i.e., an acid substance in a surface concentration more than equivalent to the alkali in the spread treating solution, to the film unit.
• Preferred acid substances are those containing an acid group having a pKa value of less than 9, above all carboxyl or sulfonic acid group, or such a precursor that can provide such an acid group by hydrolysis.
• oleic acid As specific examples, there are mentioned more preferably higher fatty acids such as oleic acid, as described in U.S. Pat. No. 2,983,606, as well as polymers of acrylic, methacrylic or maleic acid, or the partial esters or anhydrides thereof as described in U.S. Pat. No. 3,362,819.
• high molecular acid substances there are mentioned copolymers of maleic anhydride and a vinyl monomer such as ethylene vinyl acetate, vinyl methyl ether etc. and the nbutyl half-ester, the copolymer of butyl acrylate and acrylic acid, cellulose acetate, acid phthalate and the like.
• the neutralizing layer can contain polymers such as cellulose nitrate and polyvinyl acetate, and further plasticizers as de scribed in U.S. Pat. No. 3,557,237.
• the neutralizing layer further can be cured by cross-linking by means of polyfunctional azilysine compounds and epoxycom pounds.
• the layer is placed in the image-receiving element and/or sensitive element. Especially, it is advantageous to place the layer between the support for the image-receiving element and the image-receiving layer.
• the acid substance can be encapsulated as microcapsules to join to the film unit.
• the neutralizing layer or acid substance-containing layer used in the present invention is separated desirably from the treating solution layer to be spread by means of the neutralization controlling layer.
• the neutralization controlling layer serves to prevent undesirable reduction of the transferred image concentration due to the too rapid reduction of the pl-l-value of the treating solution by the neutralizing layer before the development of a given silver halide emulsion layer and the formation of the diffusion transfer image, so that the reduction of the pH-value can be retarded until after the given development and transfer.
• the image-receiving member comprises a multi-layer system: support neutralizing layer neutralization controlling layer mordant layer (image-receiving layer).
• the neutralization controlling layer comprises mainly a polymer such as gelatin, polyvinyl alcohol, polyvinyl propyl ether, polyacrylamide, hydroxypropylmethyl cellulose, isopropyl cellulose, partial polyvinyl butylal, partially hydrolyzed polyvinyl acetate, the copolymer of B-hydroxyethyl methacrylate and ethyl acrylate, and the like.
• These polymers are cured usefully by crosslinking by means of aldehyde compounds such as formaldehyde or N-methylol compounds.
• the neutralization controlling layer has a thickness of about 2 microns.
• a spacer layer between the image receiving layer and the acid material-containing layer can be disposed a spacer layer, as disclosed in U.S. Pat. Nos. 3,362,819 and 3,362,821, for controlling the release of the acid material can be disposed.
• the image receiving element can further contain a development inhibitor such as mercaptotetrazole and iodine as disclosed in U.S. Pat. No. 3,265,498.
• the image-receiving element used in the present invention fixes the color image-forming substance, such as diffusing dye, being released with the distribution of image from color developer in conjunction with silver halide emulsion.
• the color image-forming substance is an anionic material such as a color developer having a hydroquinonyl group or coupling dye having a water-soluble acid group
• the image-receiving element contains advantageously a basic polymer or a basic surface active agent.
• basic polymers those containing tertiary or quaternary nitrogen atoms are preferred: e.g., poly-4-vinyl pyridine; polymer of aminoguanidine derivative of vinyl methyl ketone described in U.S. Pat. No.
• onium groupings such as ammonium, sulfonium or phosphonium and hydrophobic residues such as long chain alkyl radicals are preferred: e.g., N-lauryl pyridinium bromide, cetyl trimethyl ammonium bromide, methyl tri-n-lauryl ammonium p-toluene sulfonate, methylethylcetyl sulfonium iodide, benzidine triphenyl phosphorium chloride etc.
• compounds of polyvalent metals such as thorium, aluminium or zirconium have also a fixing action for the anionic color image forming substance.
• these compounds are formed in the form of a film together with a polymer such as gelatin (preferably, acid-treated gelatin), polyvinyl alcohol, polyacrylamide, polyvinyl methyl ether, hydroxyethyl cellulose, N-methoxy methyl polyhexylmethylene adipamide, polyvinyl pyrrolidone and the like.
• a polymer such as gelatin (preferably, acid-treated gelatin), polyvinyl alcohol, polyacrylamide, polyvinyl methyl ether, hydroxyethyl cellulose, N-methoxy methyl polyhexylmethylene adipamide, polyvinyl pyrrolidone and the like.
• the liquid processing composition for initiating the development of the exposed portions of the photosensitive element is an strongly alkaline solution and, in general, is a solution having a pH above 12 or containing an OH ion concentration larger than 0.01 N.
• a compound capable of providing strong a1- kalinity such as potassium hydroxide, sodium hydroxide, and sodium carbonate can be used.
• a film-forming material capable of increasing the viscosity of the processing composition and forming a comparatively hard and stable film of the processing composition when the composition is spread and dried can be added to the alkaline processing composition.
• a film-forming material which is not substantially influenced in regard to the reduction in viscosity can be used.
• Preferred film-forming materials are watersoluble high molecular weight polymers inert to the alkaline processing solution, such as hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide and other viscosity increasing agents, as disclosed in U.S. Pat. Nos. 3,351,465 and 3,362,822, etc.
• onium compounds are quaternary ammonium compounds, quaternary phosphonium compounds, and quaternary sulfonium compounds.
• the specific examples of the particularly useful onium compounds include 1 -benzyl-2-picoliniurn bromide, 1-( 3- bromopropyl )-2-picolinium-p-toluenesulfonic acid, l-phenethyl-Z-picolinium bromide, 2,4-dimethyl 1 phenethylpyridinium bromide, a-picoline-B- naphthoylmethyl bromide, N,N-diethylpiperidinium bromide, phenethyltrimethyl phosphonium bromide, dodecyldimethylsulfonium-p-toluenesulfonium, etc.
• the onium compound is preferably incorporated in the alkaline processing composition. It is most preferred that the amount of the onium compound used be 2 15 percent by weight of the total processing composition. By conducting the development processing in the presence of the onium compound, the quality of the transferred images increases greatly. Other examples of the onium compounds and other examples of the manner of using them are described in the specifications of U.S. Pat. Nos. 3,411,904 and 3,173,786.
• the alkaline processing solution may contain a development inhibitor such as benzotriazole.
• the processing solution can further contain a shading agent such as titanium dioxide and carbon black.
• the auxiliary developing agent of this invention can be incorporated in the alkaline processing solution.
• the color photographic diffusion transfer process of this invention can also be applied to a film unit in which a photo-sensitive element is combined in a body with an image receiving element.
• a film unit is described in the specifications of US. Patent Nos. 3,415,644; 3,415,645 and 3,415,646.
• the dye developer will be oxidized during development and immobilized as the result of the reaction with the oxidation product of the auxiliary developing agent.
• the auxiliary developing agent is oxidized by the development of the exposed silver halide.
• the oxidized auxiliary developing agent is further caused to react with the unoxidized dye developer to regenerate the auxiliary developing agent for further reaction with the exposed silver halide. It is further believed that by using the auxiliary developing agent, at least a part of the auxiliary developing agent gives, as the result of such a reaction, a transferred image having improved image density, improved color separation and less color mixing.
• the auxiliary developing agent used in this invention can be prepared by, for instance, the following manner.
• EXAMPLE 1 The following layers were coated successively on a cellulose triacetate support to give Film A.
• l-phenyl-3-N-nhexylcarbox yamido-4-[p-( 2 ',5 -dihydroxyphenethyl phenylazol-S-pyrazolone was dissolved in a mixture of 10 cc of N-n-butylacetanilide and 25 cc of cyclohexanone and the solution was dispersed by emulsification in cc of a 10 percent aqueous gelatin solution containing 8 cc of an 8 percent aqueous solution of sodium n-dodecylbenzenesulfonate.
• the emulsion thus prepared was mixed with 5 cc of an 2 percent aqueous solution of 2-hydroxy-4,6-dichloro-S-triazine sodium salt and further water was added thereto to make the total volume 300 cc.
• the mixture was coated on the support in a dry thickness of 2.0 microns.
• a silver iodobromide emulsion (containing 5 mol percent silver iodide) containing 3.5 X 10 mols of silver and 6.5 g of gelatin per 100 g of emulsion was coated on the dye developer layer in a dry thickness of 1.5 microns.
• a coating composition of 100 cc of a 5 percent aqueous gelatin solution containing 2 cc of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate and 5 cc of 2 percent mucochloric acid was coated on the silver halide emulsion layer in a dry thickness of 1.5 microns.
• the photosensitive silver halide emulsion coating composition contained additionally 20 g of an emulsion prepared by dissolving 5 g of 1'phenyl-3-pyrazoli-done in a mixture of 10 cc of tri-o-cresyl phosphate and 10 cc of ethyl acetate and dispersing the solution in 50 cc of a 10 percent aqueous gelatin solution.
• Each of the Films A, B, and C thus prepared was exposed through a step wedge and treated in superposed relation with the image receiving element as shown below with the following processing composition to conduct the transfer development.
• the processing composition was spread between the film and the image receiving element in a ratio of 1.8 cc per 100 cm of the image receiving element.
• the composition of the processing solution used above was as follows:
• the image recieving element used above was prepared by coating on a baryta-paper a solution of 2 g of poly-4-vinyl-pyridine (mordant) and 0.1 g of l-phenyl-5-mercaptotetrazole in 100 g of a 10 percent aqueous gelatin solution in a dry thickness of 10 microns.
• the photosensitive element was stripped from the image receiving element and then the blue filter reflective density of the yellow image thus transferred to the image receiving element was measured.
• the minimum transfer density and the maximum transfer density are shown in the following table.
• a red-sensitive silver iodobromide emulsion (containing 1 mol percent silver iodide) containing 5.5 X mols of silver and 5.0 g of gelatin per 100 g of emulsion was coated on the cyan dye developer layer in a dry thickness of 3.5 microns.
• a green-sensitive silver iodobromide emulsion (containing 2 mol percent silver iodide) containing 4.7 X 10' mols of silver and 6.2 g of gelatin per 100 g of emulsion was coated in a dry thickness of 1.8 microns.
• cc of a 5 percent aqueous gelatin solution containing 1.5 cc of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate was coated on the silver halide emulsion layer in a dry thickness of 1.0 micron.
• a blue-sensitive silver iodobromide emulsion (containing 7 mol percent silver iodide) containing 3.5 X 10 mols and 6.5 g of gelatin per 100 g of emulsion was coated in a dry thickness of 1.5 microns.
• a 4 percent aqueous gelatin solution containing 2 cc of a 5 percent aqueous solution of 5 percent sodium n-dodecylbenzenesulfonate and 5 cc of a 2 percent aqueous mucochloric acid solution was coated in a dry thickness of 1 micron.
• Film E The same procedure as was used in the case of preparing Film D was followed except that 100 cc of the coating composition for the protective layer of Film D was mixed with 50 g of an emulsion prepared by dispersing by emulsification in 50 cc of a 10 percent aqueous gelatin solution a solution of 5 g of 1-phenyl-3- pyrazolidone in a mixture of 10 cc of tri-o-cresyl phosphate and 10 cc of ethyl acetate and the mixture was coated in a dry thickness of 1 micron.
• Each of Films D, E, and F prepared was exposed through step wedge to white light and then was treated in superposed relationship with the image receiving element as described in Example 1 with the processing composition as described in Example 1 to conduct transfer development for one minute.
• the processing composition was spread with a ratio of 1.5 cc per 100 cm of the image receiving element.
• the reflective densities of the color images thus transferred were measured using red, green, and blue filters respectively. The minimum transfer density and the maximum transfer density of each case are shown in the following table.
• Example 3 Film D prepared as described in Example 2 was exposed through a step wedge and was treated in superposed relation with the image receiving element as shown below with the processing composition as shown below.
• Processing Composition Auxiliary Developing Agent shown in the following table
• Auxiliary Developing Agent Amount Composi (a) None (control) tion do. (b) l-Phenyl-3-pyrazolidone 1.0 g do. (c) 4-Methylphenyl Hydroquinone 1.0 g do. (d) 4-Methylcatechol 1.0 g do. (e) Compound of This Invention 1.0 g do. (f) Compound of This Invention 10.0 g
• a color photographic diffusion transfer process comprising imagewise exposing a photographic material having at least one silver halide emulsion layer and a dye developer present adjacent to the silver halide in said silver halide emulsion layer and treating said photographic material in superposed relation with an image receiving material with an alkaline processing solution whereby the dye developer at the exposed portions of the silver halide emulsion layer is immobilized and the dye developer at the unexposed portions of the silver halide emulsion layer is transferred by diffusion to the image receiving material, said treatment with said alkaline processing solution being in the presence of 6,6,7,7-tetrahydroxy-4,4,4,4-tetramethyl-bis- 2,2-spirocumarone.
• said photographic material is a multi-layer photographic material having in order on a support, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and wherein said 6,6, 7,7'-tetrahydroxy-4,4,4',4'- tetramethyl-bis-2,2-spirocumarone is present in one of said silver halide emulsion layers.

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• Physics & Mathematics (AREA)
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• Photosensitive Polymer And Photoresist Processing (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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• 1972
  • 1972-08-17 JP JP47082274A patent/JPS5234376B2/ja not_active Expired
• 1973
  • 1973-08-15 US US00388670A patent/US3849131A/en not_active Expired - Lifetime
  • 1973-08-17 GB GB3910973A patent/GB1437126A/en not_active Expired
  • 1973-08-17 DE DE19732341786 patent/DE2341786A1/de active Pending

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