CA2265543A1 - Thermal transfer printing incorporating a coating for printable plastic films - Google Patents
Thermal transfer printing incorporating a coating for printable plastic films Download PDFInfo
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- CA2265543A1 CA2265543A1 CA002265543A CA2265543A CA2265543A1 CA 2265543 A1 CA2265543 A1 CA 2265543A1 CA 002265543 A CA002265543 A CA 002265543A CA 2265543 A CA2265543 A CA 2265543A CA 2265543 A1 CA2265543 A1 CA 2265543A1
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- coating
- thermal transfer
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
Abstract
A process for thermal transfer printing on plastic films incorporating a coating composition is provided. The process includes providing plastic film having a coating composition including a binder of a polymer and/or copolymer of carboxylic acid containing vinylic unsaturation, at least one finely divided particulate filler, and a surface active agent. A thermographic element such as a ribbon which includes a dye layer is then heated in the form of an image to be printed onto the plastic film, with the heating causing the dye layer to melt in the form of the image. The plastic film coated with the coating composition is contacted with the thermographic ribbon, and the dye layer is transferred from the ribbon to the plastic film. Such thermal transfer printing on coated plastic films provides for a multitude of uses such as plastic labels for outdoor use.
Description
?10152025CA 02265543 l999-03- 10WO 98/10938 PCT/US97/ 13394-1-THERMAL TRANSFER PRINTING INCORPORATING A COATINGFOR PRINTABLE PLASTIC FILMSThis invention relates to a coating composition which enhances the printability ofplastic surfaces, particularly plastic ?lms. More particularly, the present invention relatesto a method of thermal transfer printing which incorporates the use of a coatingcomposition to improve such printing on plastic ?lms.Thermal transfer printing processes have been developed to satisfy âonâdemandâtype printing requirements. Thermal transfer printing, however, has also typically beenlimited to print surfaces composed of paper as opposed to plastic surfaces. This isprimarily due to the poor print quality and poor durability of plastic surfaces in thermaltransfer printing processes. In thermal transfer printing processes, a print surfacesubstrate is provided for printing thereon, and a themial element in the fonn of a printinghead is provided for transferring the image to the substrate. A therrnographic ribbonwhich includes a solid ink thereon is disposed between the print surface substrate and theprint head. The print head includes a plurality of heating elements which can beindividually heated in the desired image for printing. In operation, the thermographicribbon is sandwiched between the print head and the print surface substrate, causing theprint head to contact the thermographic ribbon which in turn contacts the print surfacesubstrate. The individual heating elements of the print heat are heated in the imagedesired to be printed. Such sandwiching and heating simultaneously applies pressure andheat to the therrnographic ribbon, which causes the solid ink contained on thethermographic ribbon to be melted or lique?ed at the portions of the print head which arebeing heated. Since the therrnographic ribbon is in contact with the print surfacesubstrate, the melted ink is transferred from the thennographic ribbon to the print surfacesubstrate in the form of the image desired.While thermal transfer printing processes have become popular, such processeshave traditionally been used mainly with paper substrates, due to the di?iculty in printingon plastic ?lms and the high cost associated with such ?lms. For example, commercialproducts such as product numbers 01-180 and 01-181 marketed by Madico GraphicFilms, Wobum, Mass., and Kimdura K-100 marketed by Kimberly Clark are printablepolymer ?lms useful in thermal transfer printing processes. While such ?lms have proved?1015202530CA 02265543 l999-03- 10WO 98/10938 PCT/US97/13394-2-to be use?il alternatives to paper, they are signi?cantly more expensive than paper, andare therefore inef?cient in âon-demandâ type printing use due to cost considerations.U. S. Patent No. 5,233,924 to Ohba et al. describes a âsynthetic paperâ typeproduct which is an example of an alternative substrate described as use?il in thermaltransfer printin processes. This patent discloses a ?nely porous opaque polyole?n ?lmlayer incorporating an inorganic ?ne powder, with an ethylene-vinyl alcohol copolymer?lm layer on one or both sides of the polyole?n ?lm layer, and ?irther including a coatlayer such as an inorganic material. While such ?lms have proven to provide adequateprint quality in thermal transfer printing, the high cost of these materials results in asigni?cant downside to their use. Additionally, the smooth surface of the ethylene-vinylalcohol copolymer appears to be a hinderance in many printing applications.The invention is directed to a printable coating composition which comprises anacrylic-based emulsion which includes inorganic particulates and a surfactant. In oneembodiment, the invention includes an ultra violet light stabilizer additive. The specialcoating formulation of this invention overcomes prior dif?culties in the printing,especially lithographic and thennal transfer printing, of plastic ?lms.The acrylic binder contemplated comprises a thennoplastic polymer or copolymerof a carboxylic acid containing vinylic unsaturation such as acrylic acid or methacrylicacid or ester of those acids. The acrylates contemplated contain lower alkyl groups suchas those ranging from about 1 to about 16 carbon atoms, speci?c examples includemethyl, ethyl, butyl, lauryl and stearyl. Use?il acrylic resins may be modi?ed with non-acrylic monomers such as acrylonitrile, butadiene and/or styrene.Acrylic polymer binders are well known in the art and are described in U.S. PatentNos. 3,753,769; 4,058,645 and 4,749,616.A particularly useful thermoplastic copolymer is ethylene-acrylic acid availablecommercially under the trade name Michem, particularly Michem-4983, by MichelmanCorporation. Ethyleneâacrylic acid is, typically, produced by high pressurecopolymerization of ethylene and acrylic acid. When ethylene is copolymerized withacrylic acid, the molecular structure is signi?cantly altered by the random inclusion ofbulky carboxylic acid groups along the backbone and side chains of the copolymer. Thecarboxyl groups are free to form bonds and interact with any poly substrate.?1015202530W0 98/10938CA 02265543 l999-03- 10PCT/U S97/ 13394-3-Commercially available ethylene-acrylic acid copolymers are Primacor 4983 sold by DowChemical Co., an aqueous dispersion having 25% solids content and obtained from areaction between 15 mole % acrylic and 85 mol % ethylene. Other acrylic emulsions thatmay be employed are those sold under the name of Acrylic, particularly Acrylic79XW318A, 89XWO55 and 90XW067 by Valspar Corporation.The total amount of the binder can range from about 20% to about 80%,speci?cally about 30% to about 60% by weight based on the entire weight of the coatingcomposition.The binder can be entirely acrylic polymer or it can be entirely ethylene-acrylicacid copolymer. For some applications a combination of acrylic polymer and ethylene-acrylic copolymer is preferred. Usually, when there is no acrylic polymer, pigmentdispersion is poor and so is adhesion of the coating to the substrate. If there is noethylene-acrylic acid copolymer, the coating tends to be moisture sensitive. Thus, abalance between the acrylic polymer and the ethylene-acrylic acid copolymer is preferred.When a combination is employed, the preferred amount is 5 to 50% by weight of acrylicpolymer and 95 to 50% by weight of ethylene-acrylic acid copolymer. A typicalformulation includes 5 to 20 wt. % acrylic polymer and 95 to 80 wt. % ethylene-acrylicacid copolymer based on the entire weight of the combination.Another component of the formulation comprises at least one ink receptivityenhancing particulate additive.The particulate additive, often referred to as ?ller, comprises ?nely dividedinorganic solid materials such as silica, including fumed silica, talc, diatomaceous earth,calcium silicate, bentonite and clay. The amount of ?ller comprises a substantialpercentage of the weight of the coating, typically, about 20% to about 80%, speci?callyfrom about 30% to about 60% based on the entire weight of the coating. Theparticulates are generally small in size, typically ranging from about 1/.tm to about l0um,speci?cally from about 3 ,urn to about 7 um. Speci?c examples of ?llers include kaolin,silica (also known for antiblocking properties), aluminum silicates, clay and talc. Pulpmay also be employed.Opacity enhancing particulates which will possibly enhance the ink receptivity ofthe coating may also be employed. These are relatively inert substances. Calcium?1015202530W0 98/ 10938CA 02265543 l999-03- 10PCT/US97/13394-4-carbonate is extensively used in therrnoplastics, it is relatively inexpensive and easy touse. It can be used in its natural form but âprecipitated calcium carbonateâ which isprepared by chemical precesses can be employed. Sometimes, particulates of calciumcarbonate are coated with a resin to reduce plasticizer absorption and this fonn can alsobe employed.Particulates which provide pigmentation may also be used. Pigmentscontemplated are organic and inorganic substances with particle sizes which are rarelyless than 1 micron in diameter. Typical pigments include carbon black and titaniumdioxide. Calcium carbonate can also act as a pigment. Other pigments not to beexcluded by this invention are metallic pigments such as particles of aluminum, copper,gold, bronze or zinc. These pigments are usually ?ake shaped particles which re?ect lightwhen incorporated into the coating vehicle.The ink absorbing material, opacifying particulates and/or pigment are usuallyused in combination, depending upon the desired degree of translucency or opacity.Typically the opacifying particulates and /or pigment concentration ranges form about 5%to about 70% of the total particulate concentration of the coating, specifically about 10%to about 45% of the total particulate concentration of the coating.Further speci?c examples of particulates which may be employed in addition tothose noted above include acetylene black, alpha cellulose, aluminum silicates, bariumsulfate, calcium silicate, calcium sulphate, cellulose, clays, diatomite, glass ?ake, keratin,lignin, lithophone, mica, microballoons, molybdenum disul?de, nepheline syonite, paper,pulp, quartz, shell ?our, talc, vermiculite and wood.The invention further comprises an optional ultra violet stabilizer additive. This isa chemical agent which absorbs or screens out radiation beyond the violet end of thespectmm of visible radiations to prevent radiation catalyzed reactions which degradeplastic. Typical UV absorbers are bezophenone, benzotriazoles, includinghydroxyphenyl-benzotriazole, substituted acrylonitriles, salicylic derivatives and nickelcomplexes. Care must be taken with certain UV stabilizers, such as benzophenone,which may act as a thickening agent. A contemplated UV stabilizer is commerciallyavailable benzotriazole âTinuven 1130" available from Ciba-Geigy, âUV54l 1" availablefrom Cytec, and âMixxim BB/200" available from Fairmont. Commercially available?1015202530CA 02265543 l999-03- 10W0 98/ 10938 PCT/US97/ 13394-5-benzophenone can be obtained from BASF under the name âUvinul 3048" or from GreatLakes Chemical under the name âSyntase 230". Another commercially available UVabsorber is an oxalanilide sold under the name âVP Sanduvor VSUâ by Sandoz. The UVabsorber is, typically, used in combination with a free-radical scavenger which halts anyUV catalyst reactions. Typical free-radical scavengers include hindered amines includinghindered aminoether light stabilizers. Contemplated commercially available hinderedamines include âTinuven 123" sold by Ciba-Geigy, âUvasil 299" sold by Enichem andâBLS 1770" sold by Mayzo. Commercially prepared UV absorber/free radical scavengerpackages are available such as âVP Sanduvor 3225 " sold by Sandoz. Typically, whenusing a UV absorber and a free-radical scavenger in combination, the concentration offree-radical scavenger ranges from about 10% to about 60%, preferably about 20% toabout 40% by weight based on the entire amount of UV stabilizer additive employed.The total amount of UV stabilizer additive package that is useful in the coatingcompositions of this invention comprises about 1 to 15%, speci?cally 2 to 8% by weightof the entire coating composition. Usually, the UV stabilizers are blended in anhydrocarbon solvent, speci?cally, alcohol solvent which is miscible with water. Typically,the amount of alcohol employed is su?icient to solubilize the UV stabilizer additives, theamount ranging from about 0.5% to about 5% by weight based on the entire weight ofthe coating.The coating composition further comprises, in relatively minor amounts, a surfaceactive agent which facilitates dispersion of the particulates. This component is especiallyimportant to disperse the UV stabilizer. Any suitable surface active agent whichpromotes coating stability can be employed. Anionic emulsi?ers are contemplated. Theyinclude alkali metal and ammonium salts of the sulfates of alcohols having from 8 to 18carbon atoms such as sodium lauryl sulfate, alkali metal and ammonium salts of aromaticsulfonic acids such as dodecane-1-sulfonic acid and octadiene 1-sulfonic acid,aralkylsulfonates such as sodium isopropyl benzene sulfonate, sodium dodecyl benzenesulfonate and sodium isobutyl naphthalene sulfonate, alkali metal and ammonium salts ofsulfonated dicarboxylic acid esters such as sodium dioctyl sulfosuccinate and disodium N-octadecylsulfosuccinamate, alkali metal or ammonium salts of free acids of complexorganic mono and diphosphate esters, and the like. Non-ionic emulsi?ers such as octyl or?1015202530CA 02265543 l999-03- 10wo 93/10933 PCT/US97/13394-6-nonylphenyl polyethoxyethanol, and the like, may also be used. Mixtures of the forgoingare also contemplated. A speci?c emulsi?er is the disodium ethoxylated alcohol (C1,,-Cu)half ester of sulfosuccinic acid available from American Cyanamide Company sold underthe tradename Aerosol A-102 or the disodium ethoxylated nonylphenol half esters ofsulfosuccinic acid (Aerosol A-103). Another speci?c emulsi?er is the sodium salt of analkylaryl polyether sulfonate available from Rohm and Haas Company under thetradename âTriton X-200" or âTriton X-405" an ethylene oxide derivative. Anotheruse?rl emulsi?er is âTergitol 15-5-9".An effective amount of surface active agent, su?icient to disperse the UVstabilizer and particulates may be used. This amount can range from about 0.5 wt. % toabout 10 wt. % of the total weight of the coating, speci?cally about 1 wt. % to about 7wt. % of the total weight of the coating.Traditional coating additives can also be included in the coating of this invention.Typically such materials include modi?ers to improve the coefficient of ?iction, surfaceslip and antiblocking properties. Speci?c examples of such modi?ers include naturalwaxes such as paraffin wax, microcrystalline wax, beeswax, camauba wax, montan wax(lignite wax), etc. and synthetic waxes such as hydrogenated castor oil, chlorinatedhydrocarbon waxes, long chain fatty acid amides and the like. Other modi?ers that canbe added to the coating mixture include one or more wetting agents, crosslinking agents,stabilizers, catalysts, plasticizers, defoamers, slip agents, anti-static agents andantioxidants.The coating is made by combining all the ingredients sequentially or at the sametime and mixing or blending them at room temperature and atmospheric pressureconditions in a conventional mixing apparatus. Typically, the coating is in an aqueousmedia having a solid content of about 10 to 80%, typically 25 to 60% based on the entireweight of the ?nal coating composition.Typically the ?lm to be treated with the coating of this inventions is formed byextruding a polyole?n resin, such as polypropylene, through a ?at sheet extruder die at atemperature ranging from between about 200 to about 250°C, casting the ?lm onto acooling drum and quenching the ?lm. The sheet is then stretched about 3 to 7 times inthe machine direction (MD) orienter followed by stretching about 5 to about 10 times in?1015202530W0 98/10938CA 02265543 l999-03- 10PCT/US97/ 13394-7-the transverse direction (TD) orienter.The ?lm to be treated with the coating of this invention can include any single ormulti-layer thermoplastic material that can be formed into a thin ?lm. Contemplatedmaterials include any polyole?n such as polypropylene, polyethylene, polybutene,polystyrene, polyvinyl chloride, copolymers and blends thereof. Other ?lm materialscontemplated include polyethyleneterephthalate and nylon. In multilayer ?lms there areone or more skin layers located on at least one surface of the thennoplastic core layer.The skin layer can comprise polyethylene, including medium and high densitypolyethylene, polypropylene, copolymer or terpolymer of C2-C, alpha ole?ns or blendsthereof. At least one side of the ?lm can comprise a heat seal or pressure seal surface.Typical heat seal materials comprise ethylene and propylene homopolymers, copolymersor terpolymers such as ethylene-propylene, ethylene-propylene-butene-1, andpolyvinyldichloride polymers. Any of the materials can contain inorganic particulatessuch as titanium dioxide to enhance the whiteness or color of the substrate or to enhanceantiblocking properties.A primer enhances binding of the coating of this invention to the uncoated ?lm.Typical primers are polymers with good adhesion to the uncoated ?lms such aspolyethyleneimine and epoxy resins.In one embodiment of the invention, the ?nal printed ?lm is adhered to an object.Any conventional glue can be employed to adhere the ?lm. Glues contemplated arepressure scalable, hot melt or water-based. The coating of this invention will notinterfere with the adhesive. Thus, the adhesive can be applied to the print side of the ?lmso that the printed surface will face the object to which it is applied. This is useful whenit is desirable to read the print through the object, e. g. a glass window or a clear plasticcontainer.Typically, prior to coating the ?lm with the ?nal formulated composition of thisinvention, the ?lm surface is treated to create a high energy surface environmentsu?icient for the adhesion of a primer or other coating such as by ?ame or coronatreatment or other method which can oxidize the ?lm surfaces. Corona treatment isaccomplished by exposing the ?lm surface to a high voltage corona discharge whilepassing the ?lm between spaced electrodes. A?er electronic treatment of the ?lm?1015202530W0 98/ 10938CA 02265543 l999-03- 10PCT/US97/ 13394surface, the coating can be applied.Alternatively, the coating can be applied o?â-line, by any conventional method.For example, the ?lm can be coated by roller coating, spray coating, slot coating orimmersion coating. Gravure roll coating or reverse direct gravure coating are acceptablemethods. The excess coating solution can be removed by squeeze rolls or doctor knives.Regardless of the method by which the coating is applied, the amount should besuch that upon drying a smooth, evenly distributed layer is obtained. A preferred coatingweight ranges from about 3 to 9 g/mâ.The substrate can be of any desired thickness, although thicknesses will typicallyrange from about 20 to about 100 microns for high speed equipment.In one aspect of the invention, the coating is employed on labels for stretch wrappackaging film.In any event, the coating composition of this invention may be applied to bothsurfaces of the ?lm. Alternatively, one surface may have another coating compositionapplied to it or a substrate such as another polymer ?lm or laminate, a metal foil such asaluminum foil, cellulosic webs, paper, spunbonded polyole?n ?ber, a suitable adhesivesuch as a hot melt or room temperature sealable adhesive or water based adhesive.Thus, the present invention contemplates a method for forming a thermal transferprint image. Typically, thermal transfer printing has been used to print onto papersubstrates, due to the di?iculty in providing an image having clear resolution onto aplastic film using thermal transfer printing processes. By incorporating the coatingcomposition of the present invention, a method for forming a thermal transfer print imageon a plastic substrate can be easily accomplished.The present invention can be used for thennal transfer printing processes in anumber of applications, including âon-demandâ type digital printing, and is particularlyuse?il for pressure-sensitive decals, bar coding, point application identi?cation labelingsuch as airline luggage tags, visitor identi?cation badges and the like. Since the presentinvention accomplishes thennal transfer printing onto plastic ?lms, a variety ofapplications are contemplated which are not limited by the previously shortcomings inusing paper as a printing surface. For example, water resistant substrates for outdoor useare contemplated by the present invention.?1015202530CA 02265543 l999-03- 10W0 98/10938 PCT/US97ll3394-9-The present invention contemplates the use of any known process foraccomplishing thermal transfer printing. A typical thermal transfer printing process isdiscussed in âMaterials for Thermal Transfer Printingâ by Anczurowski and Sanders inthe Journal of Imaging Technology 13: 97-102 (1987).In preferred processes, a therrnographic element such as a therrnographic ribbonis provided, including a support having a dye or ink layer thereon. The ink layer has amelting temperature below that of the ribbon substrate and compatible with the heatingtemperature of the print head. When the print head is heated, the ink layer should becapable of melting on the ribbon, without causing degradation of the ribbon support.Preferably, the ink layer has a melting temperature from about 60 °C to about 80 °C.Altemately, a sublirninal-type dye or ink can be used. An example of a commerciallyavailable therrnographic ribbon is 4065-manufactured by Sony. The thermographicribbon is disposed between the thermoplastic substrate having the coating compositionthereon and a print head containing a plurality of thermal heating elements. The heatingelements of the print head can be image-wise heated, such that speci?c elements of theprint head are individually heated in the desired image for printing. The image-wiseheating of the thermographic ribbon melts the solid ink component of the therrnographicribbon in the form of the desired image. The thus-melted ink is transferred to thethermoplastic substrate having the coating thereon. Since the thennographic ribbon isimage-wise heated, only the solid ink on that portion of the therrnographic element whichis being heated in the image is caused to melt.In dye sublimation-type thermal transfer printing processes, it is not necessary todirectly contact the substrate surface with the therrnographic element in order to transferthe image. Instead, the thermographic ribbon includes a subliminal dye thereon. Whenthe print head heats the thennographic ribbon according to the image desired, thesubliminal dye sublimes into a gas. The printing surface substrate having the coatingcomposition coated thereon is positioned adjacent the therrnographic ribbon, and ismaintained at a temperature below that of the therrnographic element. The dye which hasbeen sublimed into a gas transfers to the cold substrate where it condenses and the dye istransferred to the print surface substrate in the form of the image transferred from thethennographic ribbon.?1015202530W0 98/ 10938CA 02265543 l999-03- 10PCT/US97/ 13394-10-Color printing onto plastic ?lms using thennal transfer printing processesaccording to the present invention incorporating coating compositions for the plastic?lms is also contemplated by the present invention.ExamplesThe following Examples 1-3 compare uncoated polypropylene ?lm and prior artsynthetic paper with polypropylene ?lm coated with various coating compositionsaccording to the present invention, for use in thermal transfer printing processes.Example 1This Example represents a plastic ?lm known in the art, without any coatingcomposition according to the present invention. The ?lm consists of a biaxially orientedpolypropylene ?lm, sold commercially as 16OLL302 by Mobil Chemical Company.Example 2This Example represents an expensive synthetic paper product of the prior art,sold commercially under the name Kimdura by Kimberly Clark. The Kimdura product isa biaxially oriented polypropylene ?lm having mineral ?lled skins, and a clay-based topcoating. The ?lm is believed to be produced in accordance with Process (4) disclosed inU.S. Patent No. 5,233,924. The ?lm is believed to be a ?nely porous polyole?n typesynthetic paper coated on either side with an ethylene-vinyl alcohol copolymer, having aclay ?lled top coating thereover.Example 3This Example represents a plastic ?lm incorporating the coating composition ofthe present invention to provide a high quality, low cost thermal transfer print surface.A print enhancing coating is prepared by combining 19.9% ethylene-acrylic acidco-polymer, 10.3% acrylic polymer, 32.4% clay, 25.8% talc, 6.4% titanium dioxide and5.2% commercial antistatic, suspension aid and defoamer additives in aqueous solution.The mixture is prepared to a solids concentration of 46-48%.A biaxially oriented polypropylene ?lm sold commercially as 260LLG202 byMobil Chemical Company is treated to a dyne level of 38 dynes/cm. The ?lm is coatedwith a polyethyleneimine primer sold by Daubert Chemical, which contains 1.9%polyethyleneimine, 0.5% hexocellosolve and 97.6% water. The print enhancing coatingis applied to the primed surface using a reverse gravure coater to a coat weight of 3.75?1015WO 98/10938CA 02265543 1999-03-10PC TIU S97/ 1 3394.11.g/mâ. The coating composition is air dried at a temperature of 93 ° C.The print surface substrates can be printed using a Zebra l40Xi printermanufactured by Zebra Corp., incorporating the following ribbons:IIIIHIVI-21 ribbon manufactured by Iimak Corp., representing a ribbonincorporating a hard wax carrier.I-28 ribbon manufactured by Iimak Corp., representing a ribbonincorporating a fast wax canier.R2 Prime ribbon manufactured by Iimak Corp., representing a ribbonincorporating a resin canier.SP33O ribbon manufactured by Iimak Corp., representing a ribbonincorporating a resin carrier.PM260 ribbon manufactured by Iimak Corp., representing a ribbonincorporating a premium resin carrier.4065 ribbon manufactured by Sony Corp., representing a ribbonincorporating a wax/resin carrier.4075 ribbon manufactured by Sony Corp., representing a ribbonincorporating a resin carrier.4080 ribbon manufactured by Sony Corp., representing a ribbonincorporating a wax/resin carrier.
Claims (10)
1. A method for forming a thermal transfer print image comprising:
(a) providing a thermoplastic substrate having a coating composition on at leastone surface thereof, said coating comprising:
(i) about 20 to about 80 weight percent, based on the entire weight of the coating of at least one binder selected from the group consisting of a polymer of carboxylic acid containing vinylic unsaturation, a copolymer of carboxylic acid containing vinylic unsaturation and mixtures thereof;
(ii) about 20 to about 80 weight percent, based on the entire weight of the coating of at least one finely divided particulate filler; and (iii) about 0. 5 to about 10 weight percent, based on the entire weight of the coating, of a surface active agent;
(b) imagewise-heating a thermographic element comprising a support including a dye layer, and (c) transferring a dye image to said surface of said substrate having said coating thereon.
(a) providing a thermoplastic substrate having a coating composition on at leastone surface thereof, said coating comprising:
(i) about 20 to about 80 weight percent, based on the entire weight of the coating of at least one binder selected from the group consisting of a polymer of carboxylic acid containing vinylic unsaturation, a copolymer of carboxylic acid containing vinylic unsaturation and mixtures thereof;
(ii) about 20 to about 80 weight percent, based on the entire weight of the coating of at least one finely divided particulate filler; and (iii) about 0. 5 to about 10 weight percent, based on the entire weight of the coating, of a surface active agent;
(b) imagewise-heating a thermographic element comprising a support including a dye layer, and (c) transferring a dye image to said surface of said substrate having said coating thereon.
2. A method as in claim 1, wherein said image-wise heating step (b) causes said dye layer to melt and said transferring step (c) is accomplished by directly contacting said print surface with said thermographic element including said melted dye layer.
3. A method as in claim 1, wherein said image-wise heating step (b) causes said dye layer to sublime, and said transferring step (c) is accomplished by positioning said print surface adjacent said thermographic element, thereby causing said sublimated dye-layer to condense on said print surface.
4. A method as in claim 1, wherein said polymer of carboxylic acid is derived from acrylic acid, methacrylic acid or ester thereof.
5. A method as in claim 1, wherein said copolymer of carboxylic acid is ethylene acrylic acid copolymer.
6. A method as in claim 1, wherein said binder comprises a mixture of about 5 toabout 50% by weight acrylic polymer and about 95 to about 50% by weight ethyleneacrylic acid copolymer based on the entire weight of the mixture.
7. A method as in claim 1, wherein said surface active agent is an anionic emulsifier or a non-ionic emulsifier.
8. A method as in claim 7, wherein said surface active agent is selected from the group consisting of sodium salt of an alkylaryl polyether sulfonate, ethylene oxide derivative and mixtures thereof.
9. A method as in claim 1, wherein said particulate filler is selected from the group consisting of silica, talc, diatomaceous earth, calcium silicate, bentonite, clay and mixtures thereof.
10. A thermal transfer print image comprising:
a polyolefin substrate treated on at least one surface with a coating composition comprising:
(a) about 20 to about 80 weight percent, based on the entire weight of the coating of at least one binder selected from the group consisting of a polymer of carboxylic acid containing vinylic unsaturation, a copolymer of carboxylic acid containing vinylic unsaturation and mixtures thereof, (b) about 20 to about 80 weight percent, based on the entire weight of the coating, of at least one finely divided particulate filler, and (c) about 0.5 to about 10 weight percent, based on the entire weight of the coating, of a surface active agent; and a thermal transfer dye image on said surface coated with said composition, said dye image transferred to said polyolefin substrate by thermal transfer printing.
a polyolefin substrate treated on at least one surface with a coating composition comprising:
(a) about 20 to about 80 weight percent, based on the entire weight of the coating of at least one binder selected from the group consisting of a polymer of carboxylic acid containing vinylic unsaturation, a copolymer of carboxylic acid containing vinylic unsaturation and mixtures thereof, (b) about 20 to about 80 weight percent, based on the entire weight of the coating, of at least one finely divided particulate filler, and (c) about 0.5 to about 10 weight percent, based on the entire weight of the coating, of a surface active agent; and a thermal transfer dye image on said surface coated with said composition, said dye image transferred to said polyolefin substrate by thermal transfer printing.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/705,349 | 1996-09-11 | ||
US08/705,349 US5891552A (en) | 1996-01-04 | 1996-09-11 | Printed plastic films and method of thermal transfer printing |
PCT/US1997/013394 WO1998010938A1 (en) | 1996-09-11 | 1997-07-29 | Thermal transfer printing incorporating a coating for printable plastic films |
Publications (1)
Publication Number | Publication Date |
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CA2265543A1 true CA2265543A1 (en) | 1998-03-19 |
Family
ID=24833066
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002265543A Abandoned CA2265543A1 (en) | 1996-09-11 | 1997-07-29 | Thermal transfer printing incorporating a coating for printable plastic films |
Country Status (14)
Country | Link |
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US (1) | US5891552A (en) |
EP (1) | EP0925192B1 (en) |
JP (1) | JP2001500807A (en) |
KR (1) | KR20000036043A (en) |
CN (1) | CN1232428A (en) |
AR (1) | AR009745A1 (en) |
AU (1) | AU713188B2 (en) |
BR (1) | BR9711760A (en) |
CA (1) | CA2265543A1 (en) |
DE (1) | DE69715889T2 (en) |
ES (1) | ES2184125T3 (en) |
ID (1) | ID19374A (en) |
TW (1) | TW345545B (en) |
WO (1) | WO1998010938A1 (en) |
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- 1996-09-11 US US08/705,349 patent/US5891552A/en not_active Expired - Fee Related
-
1997
- 1997-07-29 JP JP10513642A patent/JP2001500807A/en active Pending
- 1997-07-29 KR KR1019997002034A patent/KR20000036043A/en not_active Application Discontinuation
- 1997-07-29 WO PCT/US1997/013394 patent/WO1998010938A1/en active IP Right Grant
- 1997-07-29 AU AU38201/97A patent/AU713188B2/en not_active Ceased
- 1997-07-29 EP EP97935209A patent/EP0925192B1/en not_active Expired - Lifetime
- 1997-07-29 CA CA002265543A patent/CA2265543A1/en not_active Abandoned
- 1997-07-29 ES ES97935209T patent/ES2184125T3/en not_active Expired - Lifetime
- 1997-07-29 CN CN97198530A patent/CN1232428A/en active Pending
- 1997-07-29 DE DE69715889T patent/DE69715889T2/en not_active Expired - Fee Related
- 1997-07-29 BR BR9711760-9A patent/BR9711760A/en not_active Application Discontinuation
- 1997-08-11 TW TW086111468A patent/TW345545B/en active
- 1997-09-10 AR ARP970104153A patent/AR009745A1/en unknown
- 1997-09-11 ID IDP973150A patent/ID19374A/en unknown
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JP2001500807A (en) | 2001-01-23 |
TW345545B (en) | 1998-11-21 |
AU3820197A (en) | 1998-04-02 |
AR009745A1 (en) | 2000-05-03 |
DE69715889D1 (en) | 2002-10-31 |
BR9711760A (en) | 2002-03-05 |
CN1232428A (en) | 1999-10-20 |
ID19374A (en) | 1998-07-02 |
KR20000036043A (en) | 2000-06-26 |
WO1998010938A1 (en) | 1998-03-19 |
EP0925192A4 (en) | 1999-11-10 |
DE69715889T2 (en) | 2003-02-20 |
EP0925192B1 (en) | 2002-09-25 |
AU713188B2 (en) | 1999-11-25 |
EP0925192A1 (en) | 1999-06-30 |
ES2184125T3 (en) | 2003-04-01 |
US5891552A (en) | 1999-04-06 |
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