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
  • G03C8/24—Photosensitive materials characterised by the image-receiving section
  • G03C8/26—Image-receiving layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/12—Homopolymers or copolymers of unsaturated ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/02—Condensation polymers of aldehydes or ketones only
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners
  • G03C1/307—Macromolecular substances
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/142—Dye mordant

Definitions

• This invention relates to photography and more particularly to novel products and processes.
• One object of this invention is to provide an improved image-receiving element for color diffusion transfer processes, in which a polymeric image-receiving layer has been hardened by the hereinafter specified class of hardening agents.
• Another object of this invention is to provide a process for hardening polymer-containing image-receiving layers for use in color diffusion transfer processes.
• Still another object of this invention is to provide novel color diffusion transfer processes utilizing said image-receiving layers.
• the invention accordingly comprises the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the product possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
• the present invention is particularly related to color diffusion transfer processes.
• a sheet of photosensitive material is exposed to create therein a latent image.
• the latent image is developed and, concurrent with and under the control of this development, an imagewise distribution of diffusible color-providing materials is formed. At least a portion of these diffusible color-providing materials is transferred by means of an alkaline aqueous processing liquid to a superposed imagereceiving layer to form a color image thereon.
• an alkaline aqueous processing liquid to a superposed imagereceiving layer to form a color image thereon.
• dye developers i.e., dyes containing a silver halide developing function and capable of developing exposed silver halide
• dye developers are the color-providing materials
• the image-receiving elements used in such processes generally comprise an opaque or transparent support coated with an image-receiving layer of a dyeable material which is permeable to the alkaline aqueous processing solution.
• filmforming materials such as polyvinyl alcohol, and nylons, such as N-methoxy-methyl-polyhexamethylene adipamide, as the dyeable materials.
• a preferred image-receiving element utilizes poly-4-vinylpyridine and, more preferably, a mixture of poly-4-vinylpyridine and polyvinyl alcohol, such as is disclosed in U.S. Pat. No. 3,148,061, issued Sept. 8, 1964, to Howard C. Haas.
• Dye developers are compounds which contain in the same molecule both the chromophoric system of a dye and also a silver halide developing function. They may be further defined as dyes which are silver halide developing agents.
• a silver halide developing function is meant a radical capable of developing an exposed silver halide image.
• Particularly useful dye developers are those in which the silver halide developing function is provided by the presence of a benzenoid developing radical.
• a preferred benzenoid developing radical in such compounds is a hydroquinonyl radical. Examples of representative dye developers are given in the previously mentioned U.S. Pat. No. 2,983,606, and in applications to which crossreference is made therein.
• an exposed silver halide emulsion is developed in the presence of the dye developer and, as a result of this development, the dye developer in the developed areas is oxidized and substantially immobilized. At least a portion of the immobilization is believed to be due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions.
• the dye developer is unreacted and diffusible, and thus provides an imagewise distribution of unoxidized dye developer, dissolved in the liquid processing composition, as a function of the point to-point degree of exposure of the silver halide emulsion.
• At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
• the imagereceiving element receives a depthwise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive color image of the developed image.
• water-sensitive film-forming materials in the image-receiving element often results in swelling of the film during processing with a resulting distortion of the image.
• Such water sensitivity can be minimized or eliminated by hardening or cross-linking the polymer, prior to photographic processing, with aldehydes such as glyoxal as is disclosed in U.S. Pat. No. 3,033,872, issued Oct. 10, 1961 to Elkan R. Blout et al.
• aldehydes such as glyoxal
• such materials may also introduce photographically adverse side effects, such as loss of gloss, reduced image density, and adhesion of the processing composition to the receiving layer.
• an additional coating or layer may be applied, but this so-called strip coat, as well as introducing an additional step into the fabrication of the image-receiving sheet, may also interfere with the transfer of dye developers to the re DCving sheet, as do some of the hardening or cross-linking agents, resulting in an over-all diminution of positive image quality.
• a class of compounds has now been found that unexpectedly meet most if not all the problems above enumerated, in that (a) the polymer in the receiving element is readily hardened with the desired degree of water insensitivity and without loss of gloss, and (b) the receiving element can be stripped cleanly from its superposed position with no adhesion thereto of the processing composition, without the necessity of an additional strip coat on the receiving sheet, and without an adverse effect on the stability of the transfer dye image.
• acrolein condensates suitable as hardening agents within the scope of this invention comprise a condensate of acrolein and a lower alkylmonoaldehyde or a tetraloweralkoxypropane.
• the condensates are low molecular weight materials, preferably having an average molecular weight within the range of about 120 to 600 and the lower alkyl and lower alkoxy radicals of the monoaldehyde and propane, respectively, comprise three or less carbon atoms.
• Acrolein condensation reactions are well known to those skilled in the art; see, for example, US. Pats. Nos. 3,080,281, issued Mar. 5, 1963, and 3,183,054, issued May 11, 1965, to Rudolph F. Fisher et al.
• Such a reaction may be carried out by mixing, in an acidic medium, in varying mole ratios, acrolein and the aldehyde or propane identified above.
• the product may then be diluted, e.g., to a 50% aqueous solution by weight for ease of handling, or used directly in hardening the receiving layers without dilution.
• EXAMPLE 1 11.2 gm. of acrolein, 15.2 gm. of 1,l,3,3-tetramethoxypropane and 1 drop of phosphoric acid were mixed in a beaker. 26.4 gm. of water was then added to provide a 50% aqueous solution by weight.
• Aldocryl Resin X-12 a trade name for a low molecular weight condensate of acrolein and formaldehyde sold by Shell Chemical Company, New York, N.Y.
• Aldocryl Resin X-l2 is described as a storage stable, pale yellow, 50% by weight aqueous solution with a mildly irritating odor and has the following average properties: an average molecular weight of 180-200; a viscosity at 20 C. of 6.65 centipoises; a density at 20 C. of 1.135 gm./ml.; a pH of 4 to 5; a carbonyl value of approximately 1.20 equivalents per gm. of solution and a complete solubility in water and ether.
• acrolein as used herein, is intended to include not only CH CHCHO, propenal (acrolein), but also acrolein dimer, both in its monomeric and polymeric form, as well.
• polymers suitable for use with the hardening agents of this invention mention may be made of polyvinyl alcohol, gelatin, partial acetals of polyvinyl alcohol, such as those disclosed in US. Pat. No. 3,239,337, issued Mar. 8, 1966 to Howard C. Haas, cellulose, cellulosic derivatives and other carbohydrate polymers.
• novel hardening agents of this invention are water soluble and can therefore be easily incorporated into the receiving element by adding an aqueous solution of the hardening agent to the polymer solution just prior to casting the polymeric layer on the receiving element.
• the hardening agent is preferably used in a 50% aqueous solution by weight although said hardening agent may also be used without dilution.
• the quantity of hardening agent to be used is based on the amount of OH, NH or SH groups in the polymer.
• the polymeric receiving layer may first be cast into a film and then hardened by treating said film with a solution of the hardening agent, i.e., by spreading, spraying or flowing said solution over said film or by immersing said film in a solution of the hardening agent.
• the degree of hardening desired is also a factor in determining the amount of hardener to be used. It can be readily seen, therefore, that the amount of hardening agent used is not critical and may be varied at the option of the operator depending upon the particular characteristics desired in the image-receiving layer.
• the receiving sheet comprises a mixture of polyvinyl alcohol and poly-4-vinylpyridine in a 2:1 ratio by weight
• about 5% of the 50% aqueous solution of hardening agent based on the weight of polyvinyl alcohol is used.
• the hardening agents may be used in treating polymeric receiving layers either in diluted form or full strength. As stated above, for ease of handling, the hardening agents are generally used in a. 50% aqueous solution.
• EXAMPLE 2 To an aqueous solution comprising 100 gm. of polyvinyl alcohol and 50 gm. of poly-4-vinylpyridine, on a dry weight basis, was added 10 gm. of the aforesaid Aldocryl Resin X-12. The solution was then cast on a subcoated film support to form a receiving layer.
• EXAMPLE 3 To an aqueous solution comprising 100 gm. of polyvinyl alcohol and 50 gm. of poly-4-vinylpyridine, on a dry weight basis, was added gm. of a 50% aqueous solution, by weight, of the acrolein condensate prepared by the reaction, on a 2 to 1 molar ratio, of acrolein and 1,l,3,3-tetramethoxypropane. The solution was then cast on a subcoated film support to form a receiving layer.
• novel hardening agents of this invention have ben found to provide particularly good results when the alkaline aqueous processing composition is thickened with a cellulosic material, for example, carboxymethyl cellulose or hydroxyethyl cellulose.
• the image-receiving layers to be employed in the diffusion transfer process are required to possess certain critical features if photographic images of excellent quality are to be formed therein.
• the imagereceiving layer upon contact with an alkaline processing composition used in diffusion transfer processes, is desired to slightly swell to allow the admittance within the imagereceiving layer of the diffusing image-forming material. This slight swelling should be to such a degree that most if not all of the diffusing image-forming material from the exposed photosensitive sheet may enter and be locked within the image-receiving layer so that a print having the highest image density is formed.
• the swelling should not be to such an extent that the gloss of the final print is destroyed or that the processing composition is induced to adhere to the final print. Extensive swelling of the image-receiving layer can also cause distortion of the formed image. It is within this area that the present invention provides its unusual results in that the process of the present invention provides hardened polymeric receiving layers which are hardened within the desired degree of swellability necessary to provide quality images without loss of gloss or dimensional stability and, most important, while providing an image-receiving layer to which processing composition does not tend to adhere.
• the superior qualities of the hardening agents of this invention are demonstrated by a simple test which utilizes the above-described stripping characteristics.
• the development of an exposed silver halide emulsion is carried out by superimposing said silver halide emulsion on the image-receiving element and spreading therebetween an alkaline aqueous processing composition by inserting the thus-formed sandwich between a set of pressure-applying rollers having a predetermined gap.
• Hardening agents are not considered acceptable unless the imagereceiving sheet can be stripped without adhesion of the processing composition to said image-receiving layer.
• image-receiving layers which have been treated with hardening agents are processed at roller gaps greatly in excess of what is considered standard and then evaluated for stripping qualities. The thicker the gap, the more likely it is that portions of the processing solution will adhere to the image-receiving layer.
• Image-receiving elements prepared in accordanc with this invention, and particularly those prepared in Examples 2 and 3 above, gave excellent results when employed with multilayer negatives containing dye developers similar to those described in the aforementioned US. Pat. No. 2,983,606.
• Th image-receiving elements prepared by the novel process of this invention are especially useful in composite film units intended for use in a Polaroid Land Camera made by Polaroid Corporation, Cambridge, Mass, or a similar camera structure such, for example, as the camera forming the subject matter of US. Pat. No. 2,435,717, issued to Edwin H. Land on Feb. 10, 1948.
• such composite film units comprise a photosensitive element, an image-receiving element and a rupturable pod containing an alkaline aqueous processing solution.
• the elements and pod are so associated with each other that, upon processing, the photosensitive element may be superposed on the image-receiving element and the pod may be ruptured to spread the alkaline aqueous processing solution between the superposed elements.
• the nature and construction of the pods used in such rolls are well known to the art. See, for example, US. Pats. Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.
• said imagereceiving layer comprises about a 2 to 1 mixture of polyvinyl alcohol and poly-4-vinylpyridine and said harden ing agent is a condensate of acrolein and 1,l,3,3-tetramethoxypropane.
• said image-receiving layer comprises about a 2 to 1 mixture of polyvinyl alcohol and poly-4-vinyl pyridine and said hardening agent is a condensate of acrolein and formaldehyde.

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• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Color Printing (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (1)

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ID=26923040

Family Applications (1)

Country Status (5)

Cited By (4)

• 0
  • NL NL128127D patent/NL128127C/xx active
  • BE BE638344D patent/BE638344A/xx unknown
  • NL NL298876D patent/NL298876A/xx unknown
• 1963
  • 1963-10-01 GB GB38630/63A patent/GB1056860A/en not_active Expired
  • 1963-10-04 DE DEJ24517A patent/DE1182526B/de active Pending
• 1966
  • 1966-12-30 US US605971A patent/US3586503A/en not_active Expired - Lifetime

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