US2798004A - Film lacquer - Google Patents
Film lacquer Download PDFInfo
- Publication number
- US2798004A US2798004A US406345A US40634554A US2798004A US 2798004 A US2798004 A US 2798004A US 406345 A US406345 A US 406345A US 40634554 A US40634554 A US 40634554A US 2798004 A US2798004 A US 2798004A
- Authority
- US
- United States
- Prior art keywords
- film
- lacquer
- photographic
- water
- polyvinyl phthalate
- 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
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- 239000004922 lacquer Substances 0.000 title description 36
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- -1 FATTY ALCOHOL SULPHATES Chemical class 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000008199 coating composition Substances 0.000 claims description 5
- 239000011253 protective coating Substances 0.000 claims description 5
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 5
- 229930182490 saponin Natural products 0.000 claims description 5
- 150000007949 saponins Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- NOJNFULGOQGBKB-UHFFFAOYSA-M sodium;3-[3-tert-butylsulfanyl-1-[[4-(6-ethoxypyridin-3-yl)phenyl]methyl]-5-[(5-methylpyridin-2-yl)methoxy]indol-2-yl]-2,2-dimethylpropanoate Chemical compound [Na+].C1=NC(OCC)=CC=C1C(C=C1)=CC=C1CN1C2=CC=C(OCC=3N=CC(C)=CC=3)C=C2C(SC(C)(C)C)=C1CC(C)(C)C([O-])=O NOJNFULGOQGBKB-UHFFFAOYSA-M 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 150000003863 ammonium salts Chemical class 0.000 description 9
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 125000002877 alkyl aryl group Chemical group 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000003716 rejuvenation Effects 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- JADVWWSKYZXRGX-UHFFFAOYSA-M thioflavine T Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C1=[N+](C)C2=CC=C(C)C=C2S1 JADVWWSKYZXRGX-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
- G03C11/00—Auxiliary processes in photography
- G03C11/08—Varnishing, e.g. application of protective layers on finished photographic prints
-
- 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
- Y10S430/162—Protective or antiabrasion layer
Definitions
- This invention concerns a film lacquer for photographic film, more particularly a water-soluble film lacquer comprising the ammonium salt of polyvinyl phthalate and certain compatible constituents which have the property of drying to a water-resistant protective layer.
- lacquers have not met the need for a lacquer that can be applied simply, from non toxic, non-flammable solvents, at various stages of aqueous film treatments without intermediate drying and handling, which is compatible with photographic emulsions, and which can be removed readily and a fresh coating applied whenever the original lacquer has become excessively damaged.
- a film can be produced by using the ammonium salt of polyvinyl phthalate which is water soluble, but which forms a water-insoluble coating on the film. It is removable in the alkaline developing bath commonly used in developing photographic film as well as in other mildly alkaline aqueous solutions.
- One object of this invention is to provide a transparent protective layer for photographic elements such as film, paper, glass and the like which may be applied from a water solution. Another object of this invention is to provide a water-insoluble lacquer for photographic elements removable in alkaline developing solutions. A further object of this invention is to provide a transparent protective layer which can resist abrasions, fingerprints, etc. without permitting the photographic image itself to be damaged. Another object is to provide such a protective layer which is readily removable so that when it has become undesirably damaged it can be removed and replaced with a fresh protective layer. Another object is to provide a smooth, transparent layer which can be applied to already scratched and abraded photographic film, in order to minimize the etfect of such damage.
- Another object is to provide a process of applying a protective coating to photographic film which can be economically integrated with the usual operations of photographic film manufacture, processing, and the like.
- a further object is to provide a water-insoluble coating which can be a vehicle for ultraviolet absorbers.
- a further object is to provide a transparent protective layer which will have desirable slip and scratch resistance.
- Another object is to provide a protective layer which will shield the photographic image from the attack of fungi and other micro-organisms, and which will keep dust, dirt, and contaminants physically separated from the delicate photographic image.
- polyvinyl phthalate which is water-soluble
- This polyvinyl phthalate is the major film-forming material in my lacquer which also contains materials which insure proper wetting of the film, provide slip and scratch resistance, impart fungicidal properties, and when desirable perform other functions such as absorption and screening of ultraviolet light.
- this lacquer may be made to photographic elements which are dry, or in various degrees of wetness so long as the surface water is not so plentiful as to dilute the lacquer excessively; these applications to moist or wet photographic elements are particularly advantageous.
- the lacquer will be applied to photographic elements after processing, between the washing operation that removes final traces of processing chemicals and the drying operation.
- processing might be done on a processing machine, with a lacquer-containing tank at the end following the wash tank into which the film would be dipped before transport into the drying section.
- the film would be immersed in a tray of the lacquer after washing and before drying.
- motion picture film the photographic processing will usually be done on a continuous machine and the lacquer may be applied after washing.
- a still further embodiment is the application of this lacquer to unexposed and/or unprocessed films for protection of the emulsion surface; such a protective coating would automatically be removed in the develop: ing solutions, permitting normal development of the lightsensitive emulsion.
- a still further embodiment is the treating of scratched films by reprocessing, through photographic developing and fixing solutions (which has a cleaning action in removing surface dirt and dirt imbedded in scratches), washing, and applicating the lacquer as above in order to minimize the seriousness of the scratches and damage.
- Photographic elements which have been lacquered may be cleaned by the removal of the lacquer in dilute alkali, facilitating the reapplication of an unblemished lacquer coat.
- This use of a water-soluble lacquer is especially desirable in simplifying the rejuvenation of dirty and scratched films because more efficient cleaning of the film surface is provided by aqueous cleaning agents, and subsequent lacquer application can be made with a minimum of further treatment.
- the polyvinyl phthalate in my lacquer must be chosen so that it meets certain requirements.
- the phthalyl content must be in such a range as to insure a water-soluble ammonium salt, produced in dilute ammonia solutions and it must have a high enough phthalyl content to avoid the gummy nature of the lower polyvinyl phthalates; usually this will require a phthalyl content between 50-75%.
- CarboWax 4000 is the trade name for a solid polyethylene glycol composition made by polymerizing ethylene oxide. It imparts increased scratch resistance and increased slip to the lacquer coating.
- a suitable Wetting agent which insures the lacquer flowing evenly over the film surface at the time of coating may be a detergent which contains ethylene glycol and an alkyl aryl polyether alcohol.
- this composition may be substituted by certain other detergents, such as Triton 770, Triton X301, Triton X200, Triton X100, glycerol, saponin, Duponol ME or 1,5-naphthalene disulfonic acid (sodium salt).
- Triton 770 is an aqueous solution 30% sodium salt of an alkyl aryl polyether sulphate and 30% isopropyl alcohol.
- Triton X301 is the same as Triton 770, but in the form of a aqueous paste without isopropyl alcohol.
- Triton X200 is similar to Triton X301 except that the active ingredient of the paste is a sulphonate.
- Triton X100 is an alkyl aryl polyether alcohol. Saponin is composed of a group of amorphous glucosides.
- Duponol MB is composed of fatty alcohol sulphates.
- the amount of ammonia in my lacquer is only so much as to take the polyvinyl phthalate into solution.
- Methyl or ethyl alcohol may be substituted for water.
- the pentachlorophenol is a well known fungicide and preservative, which aids in attaining high resistance to microbiological organism in the final lacquer coatings.
- Various mercurials, copper naphthenates, and other fungicides and preservatives may be substituted when desired, so long as they are compatible.
- Polyvinyl phthalate renders a coating superior to some other compounds in that it is unafiected by carbon tetrachloride, a common film cleaning material which dissolves many other film lacquers. Also polyvinyl phthalate in the ammonium salt is applied from water, not from toxic and/or inflammable solvents, and being water-soluble, it may be applied immediately following the last wash on a processing machine when the lacquer is applied as a protective coating for the developed film. No specialized equipment is required (such as a lacquering machine); therefore, extra operations with extra handling are eliminated.
- the insolubilization of the lacquer is a time-temperature relationship and proceeds more rapidly as the temperature is increased.
- the bulk of the ammonia is lost readily as the water first evaporates from the lacquer, and then retained ammonia is lost more slowly over a period of several hours to several days, depending upon conditions such as temperature, air flow, etc.
- normal motion picture film drying is sufficient to remove most of the combined ammonia, and this drying plus the normal interval between processing and use renders the lacquer insoluble in water and secures its final desirable physical qualities.
- Fig. 1 shows a film base carrying a photographic image and superimposed thereon a coating containing the ammonium salt of polyvinyl phthalate. It will be understood, of course, that when this coating dries, the ammonia evaporates leaving water insoluble polyvinyl phthalate.
- Fig. 2 is a flow diagram showing that the ammonium salt of polyvinyl phthalate, a wetting agent, pentachlorophenol, water-soluble polyethylene glycol and water (or similar material) are admixed to form the coating composition which is then coated on the processed photographic film using a suitable coating technique such as the hopper method illustrated.
- polyvinyl phthalate may be coated out of organic solvents, such as cellosolve, lower aliphatic alcohols such as methyl, ethyl, isopropyl, isobutyl and the like, aromatic hydrocarbons such as benzene toluene, xylene or mixtures of organic solvents which are compatible.
- organic solvents such as cellosolve, lower aliphatic alcohols such as methyl, ethyl, isopropyl, isobutyl and the like, aromatic hydrocarbons such as benzene toluene, xylene or mixtures of organic solvents which are compatible.
- the properties of the hardened lacquer appear to be comparable whether coated out of organic solvents or out of water. Tests run on samples of photographic film indicate that the treated films are considerably superior to untreated film in their resistance to abrasive action. For instance, strips were run through a rapid type printer and compared with uncoated check strips which showed greater damage as a result of the printing operation. In further tests, larger samples of photographic films were subjected to a modified ASTM Falling Carborundum Test. Haze measurements indicate quite definitely that the lacquered materials were more resistant to abrasion than untreated controls.
- the treated film is found resistant to fingerprinting; usually the fingerprint is removable by wiping with a dry cloth or a cloth moistened with carbon tetrachloride or other film cleaning solvent; in severe cases the lacquer can be removed by reprocessing the film through normal alkaline developer, or rinsing in dilute alkali of pH between 8.0 and 12.0, followed by a water rinse, and reapplication of the lacquer this renewal is almost invariably sufficient to eliminate the most stubborn fingerprints. Tests of microbiological resistance wherein treated film is exposed to conditions of high humidity etc.
- Ultraviolet absorbers which may be used depend upon their compatibility and solubility in the desired solvents. Such compounds include 2,2-dihydroxy-4,4-dimethoxybenzophenone, 2,2'-dihydroxy-benzophenone, sodium-(aphenylhydrazone)-a,;3-diketobutyrate, Thioflavine S, derivatives of oc-methyl-a-phenyl hydrazine, and the like.
- a photographic product comprising a support member carrying a photographic image produced by exposing and processing a light-sensitive photographic emulsion and superimposed upon the photographic image, a protective coating of polyvinyl phthalate produced from a coating composition containing 1.0 to 10.0% polyvinyl phthalate having a phthalyl content between 50-75% dissolved in an amount of ammonium hydroxide suificient to form a stoichiometric equivalent to the polyvinyl phthalate, about 0.24% of a Wetting agent selected from the group consisting of saponin, fatty alcohol sulphates, alkyl aryl polyether alcohol, and the sodium salt of 1,5- naphthalene disulfonic acid, and from .05 to .5% solid water-soluble polyethylene glycol.
- a process for protecting processed photographic film from scratches and similar abrasions comprising coating the processed film with a water-soluble coating composition comprising from about 1.0 to 10.0% polyvinyl phthalate having a phthalyl content between 5075% in an amount of ammonium hydroxide sufiicient to form a stoichiometric equivalent to the polyvinyl phthalate, about 0.24% of a wetting agent selected from the group consisting of tsaponin, fatty alcohol sulphates, aryl polyether sulphate, alkyl aryl polyether alcohol, and the sodium salt of 1,5-naphthalene disulfonic acid, and from .05 to .5 solid water-soluble polyethylene glycol.
- a water-soluble coating composition comprising from about 1.0 to 10.0% polyvinyl phthalate having a phthalyl content between 5075% in an amount of ammonium hydroxide sufiicient to form a stoichiometric equivalent to the polyvinyl
- a process for rejuvenating soiled processed photo- 5 graphic film comprising coating said film with a coating composition comprising polyvinyl phthalate having a phthalyl content between 5075% in an amount of ammonium hydroxide suflicient to form a stoichiometric equivalent to the polyvinyl phthalate, about 0.24% of a wetting agent selected from the group consisting of saponin, fatty alcohol sulphates, 'aryl polyether sulphate, alkyl aryl polyether alcohol, and the sodium salt of 1,5- naphthalene 'disulfonic acid, and from .05 t0 .5 solid and recoating said film with the said coating.
- a coating composition comprising polyvinyl phthalate having a phthalyl content between 5075% in an amount of ammonium hydroxide suflicient to form a stoichiometric equivalent to the polyvinyl phthalate, about 0.24% of a wetting agent selected from the group consist
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Description
Uite States Patent Ofifice Patented July 2, 1957 FILM LACQUER Edward M. Weigel, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y. a corporation of New Jersey Application January 26, 1954, Serial No. 4%,345
3 Claims. (Cl. 117-2) This invention concerns a film lacquer for photographic film, more particularly a water-soluble film lacquer comprising the ammonium salt of polyvinyl phthalate and certain compatible constituents which have the property of drying to a water-resistant protective layer.
Due to the nature of photographic film and uses that are made of it, it has been found that handling tends to produce scratches and other abrasions. Moreover the photographic film is subject to fingerprinting, smudging from various lubricating oils, skin oils, etc. These are particularly noticeable in so-called miniature camera film which is passed through automatic printing devices, and in motion picture film which is caused to move through mechanical and manual devices, past foreign surfaces and over other portions of its own surface. A great many lacquers are known which may be applied to photographic films at various stages in their manufacture and use, more particularly following their processing and developing, which may render them protected to some extent against abrasions. However, these lacquers have not met the need for a lacquer that can be applied simply, from non toxic, non-flammable solvents, at various stages of aqueous film treatments without intermediate drying and handling, which is compatible with photographic emulsions, and which can be removed readily and a fresh coating applied whenever the original lacquer has become excessively damaged. I have discovered that such a film can be produced by using the ammonium salt of polyvinyl phthalate which is water soluble, but which forms a water-insoluble coating on the film. It is removable in the alkaline developing bath commonly used in developing photographic film as well as in other mildly alkaline aqueous solutions.
One object of this invention is to provide a transparent protective layer for photographic elements such as film, paper, glass and the like which may be applied from a water solution. Another object of this invention is to provide a water-insoluble lacquer for photographic elements removable in alkaline developing solutions. A further object of this invention is to provide a transparent protective layer which can resist abrasions, fingerprints, etc. without permitting the photographic image itself to be damaged. Another object is to provide such a protective layer which is readily removable so that when it has become undesirably damaged it can be removed and replaced with a fresh protective layer. Another object is to provide a smooth, transparent layer which can be applied to already scratched and abraded photographic film, in order to minimize the etfect of such damage. Another object is to provide a process of applying a protective coating to photographic film which can be economically integrated with the usual operations of photographic film manufacture, processing, and the like. A further object is to provide a water-insoluble coating which can be a vehicle for ultraviolet absorbers. A further object is to provide a transparent protective layer which will have desirable slip and scratch resistance. Another object is to provide a protective layer which will shield the photographic image from the attack of fungi and other micro-organisms, and which will keep dust, dirt, and contaminants physically separated from the delicate photographic image.
The above objects are carried out by combining polyvinyl phthalate with ammonium hydroxide in distilled water and incorporating in this mixture certain other constituents which will impart additional protective properties to the coating or facilitate the application of defectfree coatings.
To be more specific, I have found that the ammonium salt of polyvinyl phthalate, which is water-soluble, is not stable out of solution, and when dry breaks down to form polyvinyl phthalate which is water-insoluble, and free ammonia. This polyvinyl phthalate is the major film-forming material in my lacquer which also contains materials which insure proper wetting of the film, provide slip and scratch resistance, impart fungicidal properties, and when desirable perform other functions such as absorption and screening of ultraviolet light.
A typical lacquer formula which I have found to carry out the above objects and at the same time to be applicable by dipping and immersion of the film into the solution is as follows:
Polyvinyl phthalate 1.94 Distilled water 96.75
Applications of this lacquer may be made to photographic elements which are dry, or in various degrees of wetness so long as the surface water is not so plentiful as to dilute the lacquer excessively; these applications to moist or wet photographic elements are particularly advantageous.
In one embodiment of my invention the lacquer will be applied to photographic elements after processing, between the washing operation that removes final traces of processing chemicals and the drying operation. With miniature camera film or so-called roll films, for example, such processing might be done on a processing machine, with a lacquer-containing tank at the end following the wash tank into which the film would be dipped before transport into the drying section. During manual processing the film would be immersed in a tray of the lacquer after washing and before drying. With motion picture film the photographic processing will usually be done on a continuous machine and the lacquer may be applied after washing. Another embodiment is the application of this lacquer to unexposed and/or unprocessed films for protection of the emulsion surface; such a protective coating would automatically be removed in the develop: ing solutions, permitting normal development of the lightsensitive emulsion. A still further embodiment is the treating of scratched films by reprocessing, through photographic developing and fixing solutions (which has a cleaning action in removing surface dirt and dirt imbedded in scratches), washing, and applicating the lacquer as above in order to minimize the seriousness of the scratches and damage. Photographic elements which have been lacquered may be cleaned by the removal of the lacquer in dilute alkali, facilitating the reapplication of an unblemished lacquer coat. This use of a water-soluble lacquer is especially desirable in simplifying the rejuvenation of dirty and scratched films because more efficient cleaning of the film surface is provided by aqueous cleaning agents, and subsequent lacquer application can be made with a minimum of further treatment.
The polyvinyl phthalate in my lacquer must be chosen so that it meets certain requirements. The phthalyl content must be in such a range as to insure a water-soluble ammonium salt, produced in dilute ammonia solutions and it must have a high enough phthalyl content to avoid the gummy nature of the lower polyvinyl phthalates; usually this will require a phthalyl content between 50-75%.
I have found that the constituents used with the ammonium salt of polyvinyl phthalate may be substituted only with care in order to insure proper compatibility with each other, as well as compatibility with the photographic emulsions upon which they are to be coated.
CarboWax 4000 is the trade name for a solid polyethylene glycol composition made by polymerizing ethylene oxide. It imparts increased scratch resistance and increased slip to the lacquer coating.
A suitable Wetting agent which insures the lacquer flowing evenly over the film surface at the time of coating may be a detergent which contains ethylene glycol and an alkyl aryl polyether alcohol. However, this composition may be substituted by certain other detergents, such as Triton 770, Triton X301, Triton X200, Triton X100, glycerol, saponin, Duponol ME or 1,5-naphthalene disulfonic acid (sodium salt). Triton 770 is an aqueous solution 30% sodium salt of an alkyl aryl polyether sulphate and 30% isopropyl alcohol. Triton X301 is the same as Triton 770, but in the form of a aqueous paste without isopropyl alcohol. Triton X200 is similar to Triton X301 except that the active ingredient of the paste is a sulphonate. Triton X100 is an alkyl aryl polyether alcohol. Saponin is composed of a group of amorphous glucosides. Duponol MB is composed of fatty alcohol sulphates.
The amount of ammonia in my lacquer is only so much as to take the polyvinyl phthalate into solution. Methyl or ethyl alcohol may be substituted for water.
The pentachlorophenol is a well known fungicide and preservative, which aids in attaining high resistance to microbiological organism in the final lacquer coatings. Various mercurials, copper naphthenates, and other fungicides and preservatives may be substituted when desired, so long as they are compatible.
Polyvinyl phthalate renders a coating superior to some other compounds in that it is unafiected by carbon tetrachloride, a common film cleaning material which dissolves many other film lacquers. Also polyvinyl phthalate in the ammonium salt is applied from water, not from toxic and/or inflammable solvents, and being water-soluble, it may be applied immediately following the last wash on a processing machine when the lacquer is applied as a protective coating for the developed film. No specialized equipment is required (such as a lacquering machine); therefore, extra operations with extra handling are eliminated.
The insolubilization of the lacquer is a time-temperature relationship and proceeds more rapidly as the temperature is increased. The bulk of the ammonia is lost readily as the water first evaporates from the lacquer, and then retained ammonia is lost more slowly over a period of several hours to several days, depending upon conditions such as temperature, air flow, etc. However, it appears that normal motion picture film drying is sufficient to remove most of the combined ammonia, and this drying plus the normal interval between processing and use renders the lacquer insoluble in water and secures its final desirable physical qualities.
in the accompanying diagrammatic illustration, Fig. 1 shows a film base carrying a photographic image and superimposed thereon a coating containing the ammonium salt of polyvinyl phthalate. It will be understood, of course, that when this coating dries, the ammonia evaporates leaving water insoluble polyvinyl phthalate.
Fig. 2 is a flow diagram showing that the ammonium salt of polyvinyl phthalate, a wetting agent, pentachlorophenol, water-soluble polyethylene glycol and water (or similar material) are admixed to form the coating composition which is then coated on the processed photographic film using a suitable coating technique such as the hopper method illustrated.
Although our preferred embodiment comprises coating the ammonium salt out of water, polyvinyl phthalate may be coated out of organic solvents, such as cellosolve, lower aliphatic alcohols such as methyl, ethyl, isopropyl, isobutyl and the like, aromatic hydrocarbons such as benzene toluene, xylene or mixtures of organic solvents which are compatible.
The properties of the hardened lacquer appear to be comparable whether coated out of organic solvents or out of water. Tests run on samples of photographic film indicate that the treated films are considerably superior to untreated film in their resistance to abrasive action. For instance, strips were run through a rapid type printer and compared with uncoated check strips which showed greater damage as a result of the printing operation. In further tests, larger samples of photographic films were subjected to a modified ASTM Falling Carborundum Test. Haze measurements indicate quite definitely that the lacquered materials were more resistant to abrasion than untreated controls. The treated film is found resistant to fingerprinting; usually the fingerprint is removable by wiping with a dry cloth or a cloth moistened with carbon tetrachloride or other film cleaning solvent; in severe cases the lacquer can be removed by reprocessing the film through normal alkaline developer, or rinsing in dilute alkali of pH between 8.0 and 12.0, followed by a water rinse, and reapplication of the lacquer this renewal is almost invariably sufficient to eliminate the most stubborn fingerprints. Tests of microbiological resistance wherein treated film is exposed to conditions of high humidity etc. favoring the growth of micro-organisms in both accelerated tests and in tropic regions, have shown the treated film to resist solubilization of the photographic emulsion and obliteration or destruction of the photographic image under conditions in which untreated films are rendered useless in relatively short times.
Ultraviolet absorbers which may be used depend upon their compatibility and solubility in the desired solvents. Such compounds include 2,2-dihydroxy-4,4-dimethoxybenzophenone, 2,2'-dihydroxy-benzophenone, sodium-(aphenylhydrazone)-a,;3-diketobutyrate, Thioflavine S, derivatives of oc-methyl-a-phenyl hydrazine, and the like.
What I claim is:
1. A photographic product comprising a support member carrying a photographic image produced by exposing and processing a light-sensitive photographic emulsion and superimposed upon the photographic image, a protective coating of polyvinyl phthalate produced from a coating composition containing 1.0 to 10.0% polyvinyl phthalate having a phthalyl content between 50-75% dissolved in an amount of ammonium hydroxide suificient to form a stoichiometric equivalent to the polyvinyl phthalate, about 0.24% of a Wetting agent selected from the group consisting of saponin, fatty alcohol sulphates, alkyl aryl polyether alcohol, and the sodium salt of 1,5- naphthalene disulfonic acid, and from .05 to .5% solid water-soluble polyethylene glycol.
2. A process for protecting processed photographic film from scratches and similar abrasions comprising coating the processed film with a water-soluble coating composition comprising from about 1.0 to 10.0% polyvinyl phthalate having a phthalyl content between 5075% in an amount of ammonium hydroxide sufiicient to form a stoichiometric equivalent to the polyvinyl phthalate, about 0.24% of a wetting agent selected from the group consisting of tsaponin, fatty alcohol sulphates, aryl polyether sulphate, alkyl aryl polyether alcohol, and the sodium salt of 1,5-naphthalene disulfonic acid, and from .05 to .5 solid water-soluble polyethylene glycol.
3. A process for rejuvenating soiled processed photo- 5 graphic film comprising coating said film with a coating composition comprising polyvinyl phthalate having a phthalyl content between 5075% in an amount of ammonium hydroxide suflicient to form a stoichiometric equivalent to the polyvinyl phthalate, about 0.24% of a wetting agent selected from the group consisting of saponin, fatty alcohol sulphates, 'aryl polyether sulphate, alkyl aryl polyether alcohol, and the sodium salt of 1,5- naphthalene 'disulfonic acid, and from .05 t0 .5 solid and recoating said film with the said coating.
References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES 1O Carbowax Compounds and Polyethylene Glycols, Water-Soluble P y y E yfepreeessmg, Washlng published 1946 by Carbide and Carbon =Chemicals, page 7. (Copy in Division 50.)
Claims (1)
1. A PHOTOGRAPHIC PRODUCT COMPRISING A SUPPORT MEMBER CARRYING A PHOTOGRAPHIC IMAGE PRODUCED BY EXPOSING AND PROCESSING A LIGHT-SENSITIVE PHOTOGRAPHIC EMULSION AND SUPERIMPOSED UPON THE PHOTOGRAPHIC IMAGE, A PROTECTIVE COATING OF POLYVINYL PHTHALATE PRODUCED FROM A COATING COMPOSITION CONTAINING 1.0 TO 10.0% POLYVINYL PHTHALATE HAVING A PHTHALYL CONTENT BETWEEN 50-75% DISSOLVED IN AN AMOUNT OF AMMONIUM HYDROXIDE SUFFICIENT TO FORM A STOICHIOMETRIC EQUIVALENT TO THE POLYVINYL PHTHALATE, ABOUT 0.24% OF A WETTING AGENT SELECTED FROM THE GROUP CONSISTING OF SAPONIN, FATTY ALCOHOL SULPHATES, ALKYL ARYL POLYETHER ALCOHOL, AND THE SODIUM SALT OF 1,5NAPHTHALENE DISULFONIC ACID, AND FROM .05 TO .5% SOLID WATER-SOLUBLE POLYETHYLENE GLYCOL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US406345A US2798004A (en) | 1954-01-26 | 1954-01-26 | Film lacquer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US406345A US2798004A (en) | 1954-01-26 | 1954-01-26 | Film lacquer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2798004A true US2798004A (en) | 1957-07-02 |
Family
ID=23607580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US406345A Expired - Lifetime US2798004A (en) | 1954-01-26 | 1954-01-26 | Film lacquer |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2798004A (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3129096A (en) * | 1960-01-27 | 1964-04-14 | Du Pont | Photographic negatives and their preparation |
| US3473926A (en) * | 1964-05-04 | 1969-10-21 | Eastman Kodak Co | Negative material for converting from letterpress to lithography |
| US3642472A (en) * | 1967-08-30 | 1972-02-15 | Holotron Corp | Bleaching of holograms |
| US3931431A (en) * | 1973-01-18 | 1976-01-06 | Giorgi Lewis A | Photographs coated with a protective and finishing layer |
| US3947168A (en) * | 1967-05-04 | 1976-03-30 | Fuji Photo Film Co., Ltd. | Film casting apparatus for the purification of photographic materials |
| US4200463A (en) * | 1975-12-19 | 1980-04-29 | Motorola, Inc. | Semiconductor device manufacture using photoresist protective coating |
| US5853926A (en) * | 1997-07-23 | 1998-12-29 | Eastman Kodak Company | Pre-coated, fused plastic particles as a protective overcoat for color photographic prints |
| US5856051A (en) * | 1997-07-23 | 1999-01-05 | Eastman Kodak Company | Water-resistant protective overcoat for AgX photographic system |
| US5952130A (en) * | 1998-08-19 | 1999-09-14 | Eastman Kodak Company | Protective layer for gelatin based AGX photographic products |
| US5965304A (en) * | 1997-11-06 | 1999-10-12 | Eastman Kodak Company | Protecting layer for gelatin based AGX photographic products |
| US6077648A (en) * | 1999-01-22 | 2000-06-20 | Eastman Kodak Company | Protective overcoat for photographic elements |
| US6083676A (en) * | 1999-04-26 | 2000-07-04 | Eastman Kodak Company | Method for applying a protective overcoat to a photographic element using a fuser belt |
| US6171770B1 (en) | 1999-11-24 | 2001-01-09 | Jiann Chen | Method for applying a protective overcoat to a photographic element |
| US6187517B1 (en) | 2000-06-09 | 2001-02-13 | Eastman Kodak Company | Enzyme-activated water-resistant protective overcoat for a photographic element |
| US6197482B1 (en) | 1999-05-14 | 2001-03-06 | Eastman Kodak Company | Polymer overcoat for imaging elements |
| US6232049B1 (en) | 1999-01-22 | 2001-05-15 | Eastman Kodak Company | Protective overcoat for photographic elements |
| US6258517B1 (en) | 2000-06-06 | 2001-07-10 | Eastman Kodak Company | Imaged element with improved wet abrasion resistance |
| US6274298B1 (en) | 2000-06-07 | 2001-08-14 | Eastman Kodak Company | Protective overcoat comprising polyester ionomers for photographic elements |
| US6303184B1 (en) | 1999-05-14 | 2001-10-16 | Eastman Kodak Company | Method of forming a discontinuous polymer overcoat for imaging elements |
| US6426167B2 (en) | 1999-07-15 | 2002-07-30 | Eastman Kodak Company | Water-resistant protective overcoat for image recording materials |
| US6465165B2 (en) | 1999-05-14 | 2002-10-15 | Eastman Kodak Company | Scratch resistant-water resistant overcoat for photographic systems |
| US6573011B1 (en) | 2001-12-21 | 2003-06-03 | Eastman Kodak Company | Label with curl and moisture resistant protective layer |
| US6723402B2 (en) | 2001-12-21 | 2004-04-20 | Eastman Kodak Company | Protective layer for hydrophilic packaging material |
| US20050031982A1 (en) * | 2003-08-04 | 2005-02-10 | Eastman Kodak Company | Imaging material with improved scratch resistance |
| US20050031983A1 (en) * | 2003-08-04 | 2005-02-10 | Eastman Kodak Company | Imaging material with improved mechanical properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2131747A (en) * | 1937-10-13 | 1938-10-04 | Eastman Kodak Co | Antihalation backing for photographic film |
| US2184310A (en) * | 1937-06-10 | 1939-12-26 | Du Pont | Photographic and printing media |
| US2203767A (en) * | 1938-01-25 | 1940-06-11 | Du Pont Film Mfg Corp | Antihalation photographic element |
| US2548646A (en) * | 1946-01-02 | 1951-04-10 | Warren S D Co | Moldproofing mineral coated papers |
-
1954
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2184310A (en) * | 1937-06-10 | 1939-12-26 | Du Pont | Photographic and printing media |
| US2131747A (en) * | 1937-10-13 | 1938-10-04 | Eastman Kodak Co | Antihalation backing for photographic film |
| US2203767A (en) * | 1938-01-25 | 1940-06-11 | Du Pont Film Mfg Corp | Antihalation photographic element |
| US2548646A (en) * | 1946-01-02 | 1951-04-10 | Warren S D Co | Moldproofing mineral coated papers |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3129096A (en) * | 1960-01-27 | 1964-04-14 | Du Pont | Photographic negatives and their preparation |
| US3473926A (en) * | 1964-05-04 | 1969-10-21 | Eastman Kodak Co | Negative material for converting from letterpress to lithography |
| US3947168A (en) * | 1967-05-04 | 1976-03-30 | Fuji Photo Film Co., Ltd. | Film casting apparatus for the purification of photographic materials |
| US3642472A (en) * | 1967-08-30 | 1972-02-15 | Holotron Corp | Bleaching of holograms |
| US3931431A (en) * | 1973-01-18 | 1976-01-06 | Giorgi Lewis A | Photographs coated with a protective and finishing layer |
| US4200463A (en) * | 1975-12-19 | 1980-04-29 | Motorola, Inc. | Semiconductor device manufacture using photoresist protective coating |
| US5853926A (en) * | 1997-07-23 | 1998-12-29 | Eastman Kodak Company | Pre-coated, fused plastic particles as a protective overcoat for color photographic prints |
| US5856051A (en) * | 1997-07-23 | 1999-01-05 | Eastman Kodak Company | Water-resistant protective overcoat for AgX photographic system |
| US5965304A (en) * | 1997-11-06 | 1999-10-12 | Eastman Kodak Company | Protecting layer for gelatin based AGX photographic products |
| US5952130A (en) * | 1998-08-19 | 1999-09-14 | Eastman Kodak Company | Protective layer for gelatin based AGX photographic products |
| US6077648A (en) * | 1999-01-22 | 2000-06-20 | Eastman Kodak Company | Protective overcoat for photographic elements |
| US6153363A (en) * | 1999-01-22 | 2000-11-28 | Eastman Kodak Company | Protective overcoat comprising interpenetrating network for photographic elements |
| US6232049B1 (en) | 1999-01-22 | 2001-05-15 | Eastman Kodak Company | Protective overcoat for photographic elements |
| US6083676A (en) * | 1999-04-26 | 2000-07-04 | Eastman Kodak Company | Method for applying a protective overcoat to a photographic element using a fuser belt |
| US6465165B2 (en) | 1999-05-14 | 2002-10-15 | Eastman Kodak Company | Scratch resistant-water resistant overcoat for photographic systems |
| US6300045B2 (en) | 1999-05-14 | 2001-10-09 | Eastman Kodak Company | Polymer overcoat for imaging elements |
| US6197482B1 (en) | 1999-05-14 | 2001-03-06 | Eastman Kodak Company | Polymer overcoat for imaging elements |
| US6303184B1 (en) | 1999-05-14 | 2001-10-16 | Eastman Kodak Company | Method of forming a discontinuous polymer overcoat for imaging elements |
| US6426167B2 (en) | 1999-07-15 | 2002-07-30 | Eastman Kodak Company | Water-resistant protective overcoat for image recording materials |
| US6171770B1 (en) | 1999-11-24 | 2001-01-09 | Jiann Chen | Method for applying a protective overcoat to a photographic element |
| US6258517B1 (en) | 2000-06-06 | 2001-07-10 | Eastman Kodak Company | Imaged element with improved wet abrasion resistance |
| US6428948B2 (en) | 2000-06-06 | 2002-08-06 | Eastman Kodak Company | Imaged element with improved wet abrasion resistance |
| US6274298B1 (en) | 2000-06-07 | 2001-08-14 | Eastman Kodak Company | Protective overcoat comprising polyester ionomers for photographic elements |
| US6187517B1 (en) | 2000-06-09 | 2001-02-13 | Eastman Kodak Company | Enzyme-activated water-resistant protective overcoat for a photographic element |
| US6573011B1 (en) | 2001-12-21 | 2003-06-03 | Eastman Kodak Company | Label with curl and moisture resistant protective layer |
| US6723402B2 (en) | 2001-12-21 | 2004-04-20 | Eastman Kodak Company | Protective layer for hydrophilic packaging material |
| US20050031982A1 (en) * | 2003-08-04 | 2005-02-10 | Eastman Kodak Company | Imaging material with improved scratch resistance |
| US20050031983A1 (en) * | 2003-08-04 | 2005-02-10 | Eastman Kodak Company | Imaging material with improved mechanical properties |
| US6946240B2 (en) | 2003-08-04 | 2005-09-20 | Eastman Kodak Company | Imaging material with improved scratch resistance |
| US7074551B2 (en) | 2003-08-04 | 2006-07-11 | Eastman Kodak Company | Imaging material with improved mechanical properties |
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