US3239337A - Photographic products and processes - Google Patents

Photographic products and processes Download PDF

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Publication number
US3239337A
US3239337A US71424A US7142460A US3239337A US 3239337 A US3239337 A US 3239337A US 71424 A US71424 A US 71424A US 7142460 A US7142460 A US 7142460A US 3239337 A US3239337 A US 3239337A
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US
United States
Prior art keywords
image
dye developer
benzaldehyde
processes
receiving layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US71424A
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English (en)
Inventor
Howard C Haas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polaroid Corp
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Polaroid Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE607371D priority Critical patent/BE607371A/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US71424A priority patent/US3239337A/en
Priority to GB30110/61A priority patent/GB927520A/en
Priority to FR871238A priority patent/FR1305534A/fr
Priority to DEJ20440A priority patent/DE1133977B/de
Application granted granted Critical
Publication of US3239337A publication Critical patent/US3239337A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • G03C8/56—Mordant layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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

  • One object of this invention is to provide novel imagereceiving elements for use in color diffusion transfer processes.
  • Another object of this invention is to provide novel color diffusion transfer processes utilizing said imagereceiving elements.
  • the invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure,
  • 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 color-providing materials is formed. At least a portion of these color-providing materials is transferred by means of an alkaline aqueous processing liquid to a superposed image-receiving layer to form a colored positive image thereon.
  • dye developers i.e., dyes containing a silver halide developing function and capable of developing exposed silver halide
  • 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 adi amide as the dyeable materials.
  • an image-receiving layer comprising a partial acetal of polyvinyl alcohol and a trialkylammonium benzaldehyde quaternary salt, i.e., a partial acetal prepared from polyvinyl alcohol and a trialkylammonium benzaldehyde quaternary salt,
  • X is an acid anion and each R is an alkyl group; said Rs together comprising not more than 8 carbon atoms.
  • 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 developers.
  • 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 previously mentioned US. Patent No. 2,983,606. Additional useful dye developers are described in the following copending US. applications:
  • a latent silver halide image in a photosensitive element is developed in the presence of the dye developer and, as a result of this development, the dye developer in the exposed areas is oxidized and substantially immobilized. At least a portion of the immobilization is believed to be at least due, 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 dilfusible, 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 image wise 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 image-receiving 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.
  • the acetals for use in this invention may be prepared by known methods. In general, they may be prepared by condensing a trialkylammonium benzaldehyde quaternary salt with polyvinyl alcohol.
  • the polyvinyl alcohols for use in the synthesis may be selected from the various polyvinyl alcohols which are commercially available.
  • suitable polyvinyl alcohols mention may be made of Elvanol 72-60 (trade name of E. I. du Pont de Nemours & Co., Wilmington, Delaware), and Gelvatol 1-75 (trade name of Shawinigan Products Corp, New York, N.Y.).
  • the degree of acetalization can be varied over a. considerable range.
  • the water sensitivity of the acetals and especially of the acetals wherein the trialkyl substituents are lower alkyls, e.g., methyl will increase with increasing acetalization.
  • This water sensitivity which is sometimes undesirable, may be reduced by lowering the degree of acetalization. It can also be reduced by using polyvinyl alcohols which are not completely hydrolyzed. Particularly useful results have been obtained by using acetals wherein about 19% of the hydroxy groups of the polyvinyl alcohol are acetalyzed. This degree of acetalization has been found especially useful for the trimethyl-substituted acetals.
  • the anionic portion of the quaternary salt appears to have little to no effect on the ability of the acetals to function as mordants and may be selected from the various acid anions, e.g., sulfonates, etc. Especially useful results have been obtained using the toluenesulfonate salts.
  • the trialkylammonium substituent is preferably para to the aldehyde group.
  • the metaand orthosubstituted compounds may be used.
  • trialkylammonium benzaldehyde quaternary salts mention may be made of p-trimethylammonium benzaldehyde p-toluenesulfonate, p-triethylammonium benzaldehyde ptoluenesulfonate, p-dimethylbutylammonium benzaldehyde p-toluenesulfonate, p-diethylbutylammonium benzaldehyde p-toluenesulfonate and p-methylethylbutylammonium benzaldehyde p-toluenesulfonate.
  • An acetal suitable for use in the image-receiving elements of this invention may be prepared, for example, by dissolving about 0.2 mole of polyvinyl alcohol in about 50 mls. of water and reacting it in the presence of about 0.03 cc. of concentrated sulfuric acid with about 0.033 mole of a trialkylammonium benzaldehyde quaternary salt for about 17 hours at 60 C.
  • the polymer may be purified by making the above reaction mixture alkaline, using about 1.4 gms. of a 50% sodium hydroxide solution dissolved in mls. of water and dialyzing. The polymer may be isolated by freeze drying.
  • Example I 76 gms. (0.398 ml.) of p-(N-methyl-N-butylamino) benzaldehyde (prepared by processes described in Organic Syntheses, Volume 1, Gilman, page 208) were dissolved in 250 mls. of ether containing 75 gms. (0.405 ml.) of methyl p-toluenesulfonate. The mixture was heated at reflux overnight and then 4 hours at 100 C., upon removing the ether. The resulting p-butyldimethylamino benzaldehyde quaternary ammonium salt, (melting point 158 C.-160 C.), was crystallized from tetrahydrofuran and dried.
  • novel image-receiving elements may be prepared by coating a sheet of a suitable film support such as cellulose acetate, cellulose acetate-coated baryta paper, etc., which may be suitably subcoated for proper adhesion, with a solution, preferably a 3% to 10% solution, comprising the acetal.
  • a suitable film support such as cellulose acetate, cellulose acetate-coated baryta paper, etc.
  • a solution preferably a 3% to 10% solution, comprising the acetal.
  • the polymers are water soluble and can be coated from aqueous solutions.
  • the coating and drying operations involved may be carried out by methods commonly employed in the art.
  • the acetal polymers may comprise the sole dyeable film-forming material in the image-receiving layer, or it may be added to other image-receiving materials, e.g., gelatin, polyvinyl alcohol, N-methoxymethyl polyhexamethylene adipamide, etc. Especially useful results have been obtained when the acetals are used in combination with polyvinyl alcohol.
  • the ratio of the acetal polymer to the other image-receiving materials may be varied to suit particular needs. Especially good results have been obtained if the acetal polymers comprise 10% to 100% by weight of the film-forming materials.
  • Example 2 A subcoated film support was coated with an aqueous coating solution comprising:
  • Example 4 A subcoated film support was coated with a coating solution comprising:
  • Example 5 A subcoated baryta paper was coated with a coating solution comprising:
  • a control for comparison with the above image-receiving sheets was prepared in the following manner:
  • Example 6 A subcoated film support was coated with a methanol- Water solution (1 to 9 by volume) comprising:
  • the photosensitive elements comprised a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum; said emulsions having disposed in separate alkali-permeable layers behind them, respectively, a cyan dye developer, 21 magenta dye developer and a yellow dye developer.
  • the particular dye developers employed in the photosensitive elements were (1) 1,4 bis [a methyl ⁇ 3 (2,5' dihydroxyphenyl) ethylamino]-anthraquinone (a cyan dye developer), (2) 2- [p (2,5 dihydroxyphenethyl) phenylazo] 4 propoxy-l-naphthol (a magenta dye developer) and (3) 1- phenyl 3 N n hexyl carboxamido 4 [p (hydroquinonylethyl) -phenylazo] -5-pyrazolone (a yellow dye developer).
  • IMAGE-RECEIVING ELEMENT OF EXAMPLE 4 IMAGERECEIVING ELEMENT OF EXAMPLE 5 [Density] Exposure Red Green Blue Filter Filter Filter Blue and Green 1. 33 0.63 0. 55 Red and Blue 0. 10 1. 04 0.77 Red and Green 0.05 0. 18 1. 22 Total Exposure 0.07 0. 14 0.32 No Exposure 1.16 1.31 1. 58
  • the stability of the dye developers on the image-receiving elements of this invention was measured by dyeing (l) films comprising 90% polyvinyl alcohol and 10% of a p-trimethylammonium benzaldehyde quaternary salt partial acetal of polyvinyl alcohol; (2) films of polyvinyl alcohol; (3) films of gelatin, and (4) films of N-methoxymethyl polyhexamethylene adipamide with (a) 1,4-b1S-[ocmethyl B (2,5' dihydroxyphenyl) ethylamino] anthraquinone; (b) 2-[p-(2,5'-dihydroxyphenethyl)-phenylazo]-4-propoxy-1-naphthol, and (c) 1-phenyl-3-N-n-l1exyl carboxamido 4 [p (hydroquinonylethyl) phenylazo]-5-pyrazolone.
  • the density of the films was measured and then the films were exposed to a battery of 250 watt sunlamps for periods up to 168 hours.
  • the stability of the dye developers of the image-receiving elements of this invention was comparable to that on polyvinyl alcohol and superior to that on gelatin and N-methoxymethyl polyhexamethylene adipamide.
  • reagents such as hardeners, cross-linking agents, and other reagents which will reduce the water sensitivity of the resulting layer.
  • the image-receiving elements of this invention are especially useful in composite film units intended for use in a Polaroid Land camera, made by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for example, as the camera forming the subject matter of US. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948.
  • such composite film units comprise a photosensitive element, an image-receiving element and a rupturable pod containing an aqueous alkaline 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 aqueous alkaline 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. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.
  • a latent image contained in an exposed silver halide emulsion is developed in the presence of an aqueous alkaline processing solution comprising a dye developer to provide an imagewise distribution of unoxidized dye developer and wherein at least a portion of said distribution of said unoxidized dye developer is transferred, by imbibition, to an image-receiving layer in superposed relationship with said photosensitive element to impart to said image-receiving layer a transfer image
  • the step of transferring said imagewise distribution of unoxidized dye developer to an image-receiving layer comprising a partial acetal of polyvinyl alcohol with a trialkylammonium benzaldehyde quaternary salt, the trialkyl substituents of said quaternary salt comprising together not more than 8 carbon atoms.
  • trialkylammonium benzaldehyde quaternary salt is a para-trialkylammonium benzaldehyde quaternary salt.
  • a process as defined in claim 1 wherein said partial acetal comprises 10 to by weight of the film-forming materials in said image-receiving layer.
  • said imagereceiving layer comprises polyvinyl alcohol in addition to said partial acetal.
  • said dye developer is an anthraquinone dye developer.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US71424A 1960-11-25 1960-11-25 Photographic products and processes Expired - Lifetime US3239337A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE607371D BE607371A (en)van) 1960-11-25
US71424A US3239337A (en) 1960-11-25 1960-11-25 Photographic products and processes
GB30110/61A GB927520A (en) 1960-11-25 1961-08-21 Photographic products and processes for colour diffusion transfer
FR871238A FR1305534A (fr) 1960-11-25 1961-08-21 Nouveau procédé et nouveaux produits photographiques
DEJ20440A DE1133977B (de) 1960-11-25 1961-08-22 Bildempfangsmaterial fuer das Farbdiffusionsuebertragungsverfahren, insbesondere unter Verwendung von Mehrschichtenfilmen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US71424A US3239337A (en) 1960-11-25 1960-11-25 Photographic products and processes

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GB (1) GB927520A (en)van)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3316089A (en) * 1963-07-03 1967-04-25 Polaroid Corp Photographic products and processes utilizing cross-linking agents containing intralinear quaternary nitrogen atoms
US3770439A (en) * 1972-01-03 1973-11-06 Polaroid Corp Polymeric mordant in color diffusion transfer image receiving layer
US4124388A (en) * 1977-05-02 1978-11-07 Polaroid Corporation Ammonium mordants for photographic dyes
US5387491A (en) * 1993-08-25 1995-02-07 Nippon Paper Industries, Co., Ltd. Photosensitive transfer sheet

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2358836A (en) * 1942-05-26 1944-09-26 Eastman Kodak Co Water-soluble polyvinyl acetals
US2818403A (en) * 1954-07-26 1957-12-31 Du Pont Polyvinyl acetals of aldehydes containing a betaine group
GB804971A (en) * 1954-03-09 1958-11-26 Polaroid Corp Improvements in or relating to photography
US2909430A (en) * 1958-10-08 1959-10-20 Polaroid Corp Photographic processes
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US2996956A (en) * 1958-03-27 1961-08-22 Polaroid Corp Light-polarizing film material and the process of preparation
US2997390A (en) * 1956-09-04 1961-08-22 Polaroid Corp Novel color processes and products
US3015989A (en) * 1958-01-27 1962-01-09 Polaroid Corp Light-polarizing film materials and process of preparation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2358836A (en) * 1942-05-26 1944-09-26 Eastman Kodak Co Water-soluble polyvinyl acetals
GB804971A (en) * 1954-03-09 1958-11-26 Polaroid Corp Improvements in or relating to photography
US2818403A (en) * 1954-07-26 1957-12-31 Du Pont Polyvinyl acetals of aldehydes containing a betaine group
US2997390A (en) * 1956-09-04 1961-08-22 Polaroid Corp Novel color processes and products
US3015989A (en) * 1958-01-27 1962-01-09 Polaroid Corp Light-polarizing film materials and process of preparation
US2996956A (en) * 1958-03-27 1961-08-22 Polaroid Corp Light-polarizing film material and the process of preparation
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US2909430A (en) * 1958-10-08 1959-10-20 Polaroid Corp Photographic processes

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3316089A (en) * 1963-07-03 1967-04-25 Polaroid Corp Photographic products and processes utilizing cross-linking agents containing intralinear quaternary nitrogen atoms
US3770439A (en) * 1972-01-03 1973-11-06 Polaroid Corp Polymeric mordant in color diffusion transfer image receiving layer
US4124388A (en) * 1977-05-02 1978-11-07 Polaroid Corporation Ammonium mordants for photographic dyes
US5387491A (en) * 1993-08-25 1995-02-07 Nippon Paper Industries, Co., Ltd. Photosensitive transfer sheet

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GB927520A (en) 1963-05-29
BE607371A (en)van)
DE1133977B (de) 1962-07-26

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