Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/003—Transfer printing
• • 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
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/506—Intermediate layers
• • 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
• • 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
• • 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
• • 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
  • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants

Definitions

• the present invention relates to an ink jet printable material.
• customer-selected graphics typically are commercially available products tailored for that specific end-use and are printed on a release or transfer paper. They are applied to the article of clothing by means of heat and pressure, after which the release or transfer paper is removed.
• the preparation of such graphics may involve the use of colored crayons made from a heat-transferable material.
• crayons have been made available in kit form, which also includes an unspecified heat transfer sheet having an outlined pattern thereon.
• the transferable pattern is created from a manifold of a heat transfer sheet and a reverse or lift-type copy sheet having a pressure transferable coating of heat transferable material thereon.
• a heat transferable mirror image pattern is created on the rear surface of the transfer sheet by pressure transfer from the copy sheet. The heat transferable mirror image then can be applied to a T-shirt or other article by heat transfer.
• the creation of personalized, creative designs or images on a fabric such as a T-shirt or the like through the use of a personal computer system has been described.
• the method involves electronically generating an image, electronically transferring the image to a printer, printing the image with the aid of the printer on an obverse surface of a transfer sheet which has a final or top coating consisting essentially of Singapore Dammar Resin, positioning the obverse face of the transfer sheet against the fabric, and applying energy to the rear of the transfer sheet to transfer the image to the fabric.
• the transfer sheet can be any commercially available transfer sheet, the heat-transferable coating of which has been coated with an overcoating of Singapore Dammar Resin.
• the use of abrasive particles in the Singapore Dammar Resin coating also has been described. The abrasive particles serve to enhance the receptivity of the transfer sheet to various inks and wax-based crayons.
• a cellulosic base sheet has an image-receptive coating containing from about 15 to about 80 percent of a film-forming binder and from about 85 to about 20 percent by weight of a powdered polymer consisting of particles having diameters from about 2 to about 50 ⁇ m.
• the binder typically is a latex.
• a cellulosic base sheet has an image-receptive coating which typically is formed by melt extrusion or by laminating a film to the base sheet. The surface of the coating or film then is roughened by, for example, passing the coated base sheet through an embossing roll.
• Some effort also has been directed at generally improving the transfer of an image-bearing laminate to a substrate.
• an improved release has been described, in which upon transfer the release splits from a carrier and forms a protective coating over the transferred image.
• the release is applied as a solution and contains a montan wax, a rosin ester or hydrocarbon resin, a solvent, and an ethylene-vinyl acetate copolymer having a low vinyl acetate content.
• ink jet inks are aqueous-based systems. That is, the dyes employed in such inks are soluble in water. Thus, substrates printed with ink jet inks have a pronounced proclivity to run or even lose an image in the presence of moisture or water.
• ink jet inks often have a tendency to spread after being placed on a substrate, a phenomenon referred to in the art as bleeding, thereby adversely affecting the sharpness or resolution of the image.
• customer-selected graphics produced by desk-top publishing software and printed by ink jet printers result in graphics which in general are not transferred satisfactorily by known heat transfer papers. This is particularly true when transfer is attempted with a hand-held iron.
• the present invention addresses some of the difficulties and problems discussed above by providing a print enhancement coating which includes from 0 to 100 percent by weight of a polyvalent metal ion salt, from 0 to 100 percent by weight of a cationic polymer, and from 0 to 100 percent by weight of a viscosity modifier, all based on the total dry weight of the coating.
• the coating also may include a nonionic or cationic surfactant.
• the surfactant may be a nonionic surfactant.
• the ink viscosity modifier may be a poly(ethylene oxide) having a weight-average molecular weight of from about 10,000 to about 200,000.
• the poly(ethylene oxide) may have a weight-average molecular weight of from about 20,000 to about 100,000.
• the ink viscosity modifier may be a low to medium viscosity poly(vinyl alcohol) having a degree of hydrolysis of less than about 90 percent.
• the print enhancement coating may include from about 4 to about 90 percent by weight of a polyvalent metal ion salt and from about 96 to about 10 percent by weight of a cationic polymer.
• the coating also may include a nonionic or cationic surfactant.
• the surfactant may be a nonionic surfactant.
• the coating also may include an ink viscosity modifier.
• the ink viscosity modifier may be a poly(ethylene oxide) having a weight-average molecular weight of from about 10,000 to about 200,000.
• the poly(ethylene oxide) may have a weight-average molecular weight of from about 20,000 to about 100,000.
• the ink viscosity modifier may be a low to medium viscosity poly(vinyl alcohol) having a degree of hydrolysis of less than about 90 percent.
• the present invention also provides a printable material which includes a first layer having a first side and a second side, a second layer overlaying the first surface of the first layer; and a third layer overlaying the second layer.
• the second layer includes particles of a thermoplastic polymer having largest dimensions of less than about 50 ⁇ m and from about 10 to about 50 weight percent of a film-forming binder, based on the weight of the thermoplastic polymer.
• the third layer includes from 0 to 100 percent by weight of a polyvalent metal ion salt, from 0 to 100 percent by weight of a cationic polymer, and from 0 to 100 percent by weight of a viscosity modifier, all based on the total weight of the third layer.
• print enhancement refers to the prevention or reduction of bleeding in images printed by an ink jet printer.
• polyvalent metal ion salt means an organic or inorganic salt of a polyvalent metal ion.
• polyvalent metal includes metals in Groups 2-13 of the Periodic Table of the Elements (new notation).
• the polyvalent metal may be a metal of Groups 2, 12, and 13.
• the metal may be magnesium, calcium, zinc, or aluminum.
• the polyvalent metal ion salt will be an inorganic salt.
• the term cationic polymer means a polymer containing a plurality of cationic groups.
• the cationic polymer may be an amide-epichlorohydrin polymer, polyacrylamides with cationic functional groups, polyethyleneimines, polydiallylamines, polyacrylates and polymethacrylates in which the ester portions contain quaternary ammonium groups, and the like.
• the cationic polymer will be a polyacrylate or a polymethacrylate in which the ester portion is a tetraalkylammonium group.
• the print enhancement coating provided by the present invention includes from 0 to 100 percent by weight of a polyvalent metal ion salt, from 0 to 100 percent by weight of a cationic polymer, and from 0 to 100 percent by weight of a viscosity modifier, all based on the total dry weight of the coating.
• the print enhancement coating may include from about 4 to about 90 percent by weight of a polyvalent metal ion salt and from about 96 to about 10 percent by weight of a cationic polymer, all based on the total dry weight of the coating.
• the print enhancement coating may include a nonionic or cationic surfactant.
• nonionic surfactants include, by way of illustration only, alkyl poly-ethoxylates, polyethoxylated alkylphenols, fatty acid ethanol amides, complex polymers of ethylene oxide, propylene oxide, and alcohols, and polysiloxane polyethers.
• Cationic surfactants include, again by way of illustration, tallow trimethylammonium chloride. Desirably, the surfactant will be a nonionic surfactant.
• the ink viscosity modifier may be a poly(ethylene oxide) having a weight-average molecular weight of from about 10,000 to about 200,000.
• the poly(ethylene oxide) may have a weight-average molecular weight of from about 20,000 to about 100,000.
• the ink viscosity modifier may be a low to medium viscosity poly(vinyl alcohol) having a degree of hydrolysis of less than about 90 percent.
• the present invention also provides a printable material which includes a first layer having a first side and a second side, a second layer overlaying the first surface of the first layer; and a third layer overlaying the second layer.
• the second layer includes particles of a thermoplastic polymer having largest dimensions of less than about 50 ⁇ m and from about 10 to about 50 weight percent of a film-forming binder, based on the weight of the thermoplastic polymer.
• the first layer can be any material adapted for the end-use desired.
• the first layer typically will be a sheet material, more typically a flexible sheet material.
• flexible sheet materials include films, papers, nonwoven and woven webs, foils, and the like.
• the first layer When the printable material is intended for use as a heat-transfer material, the first layer often will be a film or a paper.
• An example of a suitable film is a biaxially oriented film having a typical thickness of about 76 ⁇ m (3 mils). This type of film typically is used to make transparencies for overhead projectors.
• the thickness of the paper desirably will be from about 76 to about 152 ⁇ m (from about 3 to about 6 mils).
• An especially useful paper is a label paper having what is referred to in the art as a print coating on one side.
• the print coating typically is a latex binder containing clay and starch, as is also well known in the art.
• the second layer usually is applied to the side of the paper not having the print coating, although the paper may have a print coating on both sides. While thinner or thicker papers may be used, the paper should have sufficient strength for handling, coating, sheeting, and other operations associated with its manufacture, and for removal after transferring an image. Other papers which may be used are latex-saturated papers.
• the second layer includes particles of a thermoplastic polymer having largest dimensions of less than about 50 ⁇ m. Desirably, the particles will have largest dimensions of less than about 20 ⁇ m.
• the thermoplastic polymer can be any thermoplastic polymer which meets the criteria set forth herein.
• the powdered thermoplastic polymer may be a polyolefin, polyester, polyamide, copolyamide, or ethylene-vinyl acetate copolymer.
• the second layer also includes from about 10 to about 50 weight-percent of a film-forming binder, based on the weight of the thermoplastic polymer. Desirably, the amount of binder will be from about 10 to about 30 weight percent. In general, any film-forming binder may be employed which meets the criteria set forth herein. Suitable binders include polyacrylates, polyethylenes, and ethylene-vinyl acetate copolymers. The binder desirably will be heat softenable at temperatures of about 120° Celsius or lower.
• the basis weight of the second layer may vary from about 5 to about 30 grams per square meter (g/m 2 ). Desirably, the basis weight will be from about 10 to about 20 g/m 2 .
• the second layer can be applied to the first layer, either directly or over a third or other layer, by means well known to those having ordinary skill in the art. For example, the layer may be applied by Meyer rod, air knife, and gravure coating, by way of illustration only.
• the second layer will have a melting point of from about 65 to about 180° Celsius.
• the term "melts" and variations thereof are used herein only in a qualitative sense and are not meant to refer to any particular test procedure. Reference herein to a melting temperature or range is meant only to indicate an approximate temperature or range at which a polymer or binder melts and flows under the conditions of a melt-transfer process to result in a substantially smooth film.
• melt behavior of polymers or binders correlate with the melting requirements described herein. It should be noted, however, that either a true melting point or a softening point may be given, depending on the nature of the material. For example, materials such a polyolefins and waxes, being composed mainly of linear polymeric molecules, generally melt over a relatively narrow temperature range since they are somewhat crystalline below the melting point.
• Melting points if not provided by the manufacturer, are readily determined by known methods such as differential scanning calorimetry. Many polymers, and especially copolymers, are amorphous because of branching in the polymer chains or the side-chain constituents. These materials begin to soften and flow more gradually as the temperature is increased. It is believed that the ring and ball softening point of such materials, as determined by ASTM E-28, is useful in predicting their behavior in the present invention. Moreover, the melting points or softening points described are better indicators of performance in this invention than the chemical nature of the polymer or binder.
• the third layer is the print enhancement coating described hereinbefore.
• the print enhancement coating or the third layer will have a basis weight of from about 0.1 to about 5 g/m 2 .
• the printable material desirably with have an additional layer which may be, for example, a release layer or a melt-transfer film layer. Additional layers may be included, if desired. Such additional layer or layers, if used, typically will be located between the first layer and the second layer.
• a melt-transfer film layer typically comprises a film-forming binder, as already described, or other polymer.
• the layer desirably is applied by extrusion coating, but other methods also may be used.
• the melt-transfer film layer desirably is formed from a polyethylene or a copolymer of ethylene with acrylic acid, methacrylic acid, vinyl acetate, or acrylic acid esters such as ethyl acrylate.
• the polymer desirably will have a melt flow rate of at least about 30 grams per 10 minutes (g/10 minutes), as determined in accordance with ASTM Method D-1238), although the melt flow rate may be as high as about 4,000 g/10 minutes.
• the melt flow rate of the polymer will be from about 300 to about 700 g/10 minutes.
• the basis weight of the melt-transfer film layer desirably will be from about 10 to about 50 grams per square meter (g/m 2 ), with a basis weight of from about 30 to about 50 being more desired.
• a release layer may be included, either in place of or in addition to the melt-transfer film layer.
• the release layer will be placed between the first layer and the second layer.
• the release layer will be placed between the first layer and the melt-transfer film layer.
• the latter is particularly desired when heat transfer will be accomplished by means of a hand-held iron.
• the release layer desirably will be a low molecular weight ethylene-acrylic acid copolymer applied from an aqueous dispersion.
• the melt flow rate of the ethylene-acrylic acid copolymer desirably will be at least about 200 g/10 minutes, more desirably from about 800 to about 1,200 g/10 minutes.
• Such dispersion also may contain a paraffin wax, which is mixed as an emulsion with the ethylene-acrylic acid copolymer dispersion.
• the paraffin wax emulsion can be any of those which are commercially available, such as Chemawax® 40 (Chematron, Inc., Charlotte, North Carolina).
• the ratio of paraffin wax to the copolymer may vary from 0 to about 4, with a ratio of about 1 being more desirable.
• the basis weight of the release layer desirably will be from about 2 to about 20 g/m 2 , more desirably from about 6 to about 10 g/m 2 .
• the release coating as described melts easily and provides easy release from the first layer for hand ironing of images onto a fabric; such characteristic is especially useful if heating of the image is irregular, which is not atypical of hand-ironing techniques.
• the second and any additional desired layers are formed by known coating techniques, such as by roll, blade, and air-knife coating procedures.
• the resulting material then is dried by means of, for example, steam-heated drums, air impingement, radiant heating, or some combination thereof. Some care must be exercised, however, to assure that drying temperatures are sufficiently low so that the particles of thermoplastic polymer present in the second layer do not melt during the drying process. Air impingement for 5 minutes or more at 80° Celsius was used successfully.
• Heat transfer of an image printed on the printable material of the present invention may be by any known means, such as by a hand-held iron or a heat transfer press. The latter is desired, however.
• the transfer temperature typically will be from about 120° to about 205° Celsius, for from about 5 seconds to about 2 minutes. A temperature of about 160° Celsius for about 15 seconds generally works well.
• the first layer in the examples was a commercially available print-coated heat transfer paper.
• the base paper was coated first by melt extrusion with an about 46- ⁇ m (1.8-mil) layer of a 500 melt index ethylene-methacrylic acid copolymer (Nucrel® 599).
• This melt-extruded layer then was coated with a layer composed of about 75 weight-percent of polyamide particles (Orgasol® 3501 EXD NAT1, a 10- ⁇ m average particle size copolymer of ⁇ -caprolactam and laurolactam, having a melting point of 160°C and available from Elf Atochem, France), about 19 weight-percent of an ethylene-acrylic acid copolymer (Michem® Prime 4983), and about 4 weight-percent of a polyethoxylated octylphenol nonionic surfactant (Triton® X-100, Rohm & Haas Co., St. Louis, Missouri).
• polyamide particles Orgasol® 3501 EXD NAT1, a 10- ⁇ m average particle size copolymer of ⁇ -caprolactam and laurolactam, having a melting point of 160°C and available from Elf Atochem, France
• an ethylene-acrylic acid copolymer Mochem® Prime 4983
• Michem® Prime 4983 was a 25 percent solids dispersion of Primacor® 5983 made by Dow Chemical Company.
• the polymer contained 20 percent acrylic acid and 80 percent ethylene.
• the copolymer had a Vicat softening point of 43°C and a ring and ball softening point of 100°C.
• the melt flow rate of the copolymer was 500 g/10 minutes.
• the basis weight of the coating was about 14 g/m 2 .
• Print testing was carried out with a Canon BJ 4200 printer with the BC 22 photo ink cartridge.
• the cartridge enables the user to select color photo graphics.
• the test print employed in the examples was an image having a woman's face as well as colored squares of cyan, yellow, magenta, red, blue, green, and black. Heat transfers, when done, were to a 100 percent cotton T-shirt material. Wash tests, when done, were in a home laundry using commercial detergent on the warm/warm cycle. The heat transfer press conditions were 177° C for 20 seconds.
• EXIV A 10 weight-percent total solids blend of Airvol® 523, Alcostat® 567 and Triton® X-100 in a 1/1/0.2 weight ratio, 3 g/m 2 .
• EXV Calcium chloride tetrahydrate 1.5 g/m 2 .
• EXVI Magnesium acetate hexahydrate and Triton® X-100 1/0.2/ 1.5 g/m 2 .
• EXVII Zinc acetate dihydrate, 1.5 g/m 2 .
• EXVIII 2.2 g/m 2 , 2/1/0.2 weight ratio of hydrated calcium chloride/Alcostat® 5667, Triton® X-100.
• EXIX 3 g/m 2 1/1/0.1 weight ratio of hydrated calcium chloride/ Alcostat® 567, Triton® X-100.
• EXX 2.2 g/m 2 1/1/0.1/0.02 weight ratio of Alcostat® 567, Airvol® 523, zinc acetate dihydrate, and Triton® X-100.
• EXXI 3 g/m 2 1/1/0.3/0.15 weight ratio of Alcostat® 567, Airvol® 523, zinc acetate dihydrate and Triton® X-100.
• EXXII 1.5 g/m 2 1/0.1 weight ratio of Alcostat® 567 and Triton® X-100.
• EXXIII 1.5 g/m 2 , 1/0.6 weight ratio of aluminum sulfate hexadecahydrate and Alcostat® 567.
• CEI This is a comparative example without an overcoat.
• the paper was extrusion coated with about 18 ⁇ m (0.7 mil) of Nucrel® 599.
• the print coat was a 100/10/10/5 blend of dispersed Orgasol® 3501 EXD NAT I, Airvol® 523, Alcostat 567 and Triton® X-100. This was applied at 25% total solids to give a coating weight of 14 g/m 2 . Note that the coating does not contain Michem® 4983 binder.
• CEII This comparative example was like CEII, except that the Nucrel® 599 film was about 38 ⁇ m (1.5 mils) thick.
• Print, Transfer, and Wash Test Results Example Print Resolution Print Color Color Shift Transfer Wash Test Control Very poor Greyish Green Good ---- EI Poor Greyish Green Good Good EII Fair Greyish Green Good Good EIII Poor Greyish green Good Good EIV Fair Greyish Green Good Good EV Good Good Good Green Good Good EVI Good Good Green Good Good EVII Good Reddish Green Good Good Good EVIII Good Good Green Good EIX Fair Greyish Yellow Good Good EX Excellent Good Yellow Good Good Good EXI Fair Good Very slight yellow Good Good EXII Good Good Very slight yellow Good Good Good EXIII Very Good Good Very slight yellow Good Good Good EXIV Very good Good Very slight yellow Good Very Good EXV Blue None Good Poor EXVI Poor Good ---- Very poor ---- EXVII Note Good Less yellow Poor Good EXVIII Good Blue Green Good Fair EXIX Excellent Blue Slight green Good Excellent EXX Good Good Good
• the paper was coated on the front side with a 100/25/5/5 parts by weight blend of Orgasol® 3501 EXD NAT 1, Michem® Prime 4983, Airvol® 523, and SMA 1440H (a styrene-maleic anhydride copolymer dispersant from Elf Atochem).
• the coating basis weight was about 16 g/m 2 .
• the coating total solids content was 27 weight-percent.
• a second coating was applied, utilizing a solution of a 100/100/5 parts by weight ratio of Alcostat® 567, Airvol® 523, and Tergitol® 15-S-9, a secondary alcohol polyethoxylate.
• the resulting material was printed, then fused, using a 0.5 Mylar polyester film on the print side and a release paper on the backside, in a Hix heat transfer press at about 132°C for 30 seconds.
• the image was the same as the one used for Examples I-XXIII and Comparative Examples I and II.
• the image was glossy, water resistant, and looked much like a glossy photograph.

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Cited By (8)

Citations (8)

• 1997
  • 1997-11-13 EP EP97119914A patent/EP0842786A1/de not_active Withdrawn
  • 1997-11-17 JP JP9315056A patent/JPH10166721A/ja active Pending

Patent Citations (8)

Non-Patent Citations (1)

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