Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
  • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
  • G03G7/002—Organic components thereof
  • G03G7/0026—Organic components thereof being macromolecular
  • G03G7/0046—Organic components thereof being macromolecular obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44F—SPECIAL DESIGNS OR PICTURES
  • B44F1/00—Designs or pictures characterised by special or unusual light effects
  • B44F1/06—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings
  • B44F1/066—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings comprising at least two transparent elements, e.g. sheets, layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
  • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
  • G03G7/002—Organic components thereof
  • G03G7/0026—Organic components thereof being macromolecular
  • G03G7/004—Organic components thereof being macromolecular obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• This invention relates to multilayer laminates in which at least one of the layers includes an ink-bearing surface.
• the invention features an article that includes (a) a first polymeric substrate having a major surface; (b) a second polymeric substrate having a major surface; and (c) a thermoplastic, heat-sealing adhesive bonding the major surface of the first polymeric substrate to the major surface of the second polymeric substrate such that the peel strength between the polymeric substrates is at least 6 N/cm.
• At least one of the major surfaces includes an ink-bearing image. It is also possible for the major surfaces of both substrates to include an ink- bearing image.
• the ink preferably is an electrophotographic ink.
• the ink includes a polymer having a Tg no greater than about 30°C, while in other embodiments the ink includes a polymer having a Tg greater than about 30°C.
• An example of a suitable ink is derived from gel organosol-containing, liquid toner compositions described, e.g., in Baker et al., U.S. 5,652,282 and Baker et al., U.S. 5,698,616, both of which are hereby incorporated by reference.
• toners include (a) a carrier liquid (e.g., an aliphatic hydrocarbon carrier liquid having a Kauri-Butanol number less than 30) and (b) a (co)polymeric steric stabilizer having a molecular weight greater than or equal to 50,000 Daltons and a polydispersity less than 15 covalently bonded to a thermoplastic (co)polymeric core that is insoluble in the carrier liquid.
• the core preferably has a Tg no greater than about 30°C.
• the toner may further include a colorant and a charge director.
• non-gel organosol-containing liquid toner compositions described, for example, in Baker et al., U.S. 5,886,067.
• a suitable ink is derived from liquid toners described in Landa et al., U.S. 4,794,651; Landa et al., U.S. 4,842,974; Landa et al., U.S. 5,047,306; Landa et al., U.S. 5,047,307; Landa et al., U.S. 5,192,638; Landa et al., U.S. 5,208,130; Landa et al., U.S. 5,225,306; Landa et al., U.S. 5,264,313; Landa et al., U.S.
• ink jet inks and lithographic inks are also useful. Any of these inks may be used alone or in combination with each other.
• the ink-bearing surface may include electrophotographically printed areas featuring an electrophotographic ink and offset printed areas featuring a lithographic ink. Preferably, however, all the printed areas of the article are electrophotographically printed areas featuring electrophotographic ink.
• the adhesive is preferably selected from thermoplastic heat-sealing adhesive compositions which, when interposed between the major surfaces of the first and second polymeric substrates and laminated together between a pair of lamination rollers using a line speed of about 0.2-10 inch/sec, a temperature of about 65-150°C, and a nip pressure of about 15-110 lbs/in. to bond the first and second polymeric substrates together, achieve a peel strength of at least 6 N/cm within a period of no greater than about 1 hour following lamination.
• thermoplastic heat-sealing adhesive compositions include polyurethanes (e.g., polyester-based polyurethanes), polyesters, and ethylene-vinyl acetate copolymers.
• the polymers may be provided with functional groups such as anhydride or carboxy groups.
• Blends of two or more polymers may also be used (e.g., blends of polyesters and polyurethanes; polyesters, polyurethanes, and ethylene-vinyl acetate copolymers; or polyurethanes and ethylene-vinyl acetate copolymers).
• multilayer adhesives may be used, for example (a) a first layer comprising a polyurethane; and (b) a second layer comprising a polyester.
• the polymeric substrates may be the same as, or different from, each other. A number of polymeric substrates may be used.
• the first polymeric substrate features a rigid core layer and the second polymeric substrate features a flexible overlay film.
• at least one of the substrates is substantially transparent to permit viewing of the printed image on the ink-bearing substrate surface.
• suitable polymeric substrates are selected from the group consisting of polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyesters, polyolefins, polycarbonates, and combinations thereof.
• microporous substrates such as that commercially available under the trade designation TESLIN films available from PPG, Inc. of Pittsburgh, PA.
• One preferred construction includes a polyvinyl chloride substrate adhesively bonded to a substantially transparent polyester overlay film.
• the article may include more than two substrates.
• the article may include a core substrate having a pair of opposed major surfaces, each of which is bonded to a separate overlay film. Such constructions are particularly useful for articles having printed images on two different surfaces.
• the invention features a process for preparing an article that includes: (a) combining the first polymeric substrate and a second polymeric substrate having a major surface with a thermoplastic heat-sealing adhesive such that the adhesive is intermediate the major surfaces of the polymeric substrates, where at least one of the substrates includes an ink-bearing image on its major surface in contact with the adhesive; and (b) laminating the major surfaces of the first and second substrates together through the adhesive to form an article in which the peel strength between the first and second substrates of at least 6 N/cm.
• the ink-bearing image is preferably formed according to an electrophotographic process that includes:
• the toner preferably is a liquid toner.
• the liquid toner in turn, preferably includes a film-forming polymer.
• the film-forming polymer has a Tg no greater than about 30°C, while in other embodiments the film-forming polymer has a Tg greater than about 30°C.
• the article may be subjected to a number of operations, including slitting, cutting, hole punching and drilling, foil stamping, sewing and grommeting, foil stamping, perforation, folding, surface texturing, and the like.
• the black, positive-acting, film-forming, electrophotographic ink used in the examples was prepared at an organosol/pigment ratio of 6 following the procedure described in Example 40 of U.S. 5,652,282 modified as follows.
• the gel organosol prepared according to the procedure of Example 22 of U.S. 5,652,282 was mixed using a Silverson mixer (Model L2R, Silverson Machines, Ltd.) operated at the lowest speed setting. After mixing for five minutes, 1912 g of the homogenized organosol at 16.14% (w/w) solids in
• NORPAR 12 were combined with 1031 g of ORPAR 12 (Exxon Chemical Co., Houston, TX), 51 g of MONARCH 120 carbon black (Cabot Corp., Billerica, MA), and 6.08 g of Zirconium HEX-CEM (OMG Chemical Company, Cleveland, OH) in a 4.0 liter polyethylene container. This mixture was then milled in ten vertical bead mills, each having a capacity of 0.5 liter (Model 6TSG-1/4, Aimex Co. Ltd., Tokyo, Japan) by placing 300 g of millbase and 390 g of 1.3 mm diameter Potters glass beads (Potters Industries, Inc., Parsippany, NJ) in each mill. Each mill was operated at 2,000 rpm for 1.5 hours without cooling water circulating through the cooling jacket of the milling chamber.
• This 3% toner was tested on the toner plating apparatus described in U.S. 5,652,282.
• the reflection optical density (ROD) was greater than 1.47 at plating voltages greater than 400 volts.
• Example 1 An adhesive-coated polyester film was prepared by solution coating
• Desmocoll 8634 polyurethane resin solution (15 wt. % in methyl ethyl ketone, available from Bayer Chemical Co.) onto Mellinex 454 polyester film (0.92 mil, available from Dupont) at a wet coating coverage of approximately 375 g/square meter, followed by drying to give an adhesive-coated film.
• the dry thickness of the adhesive layer was 1.0 mil.
• the adhesive portion of the film was area printed using a liquid toner- based, black, positive-acting, film-forming, electrophotographic ink (prepared as described above) to a net optical density of 1.6.
• the net optical density is equal to the white light optical density minus the white light optical density of unprinted film, measured in reflectance mode with a Macbeth densitometer.
• the net optical density corresponded to an ink net optical density of 1.3 for a paper substrate printed under identical conditions.
• the adhesive-coated film was laminated to a white polyvinyl chloride substrate.
• the article was cut into strips measuring one inch wide and the 180 degree peel force required to cause delamination was measured 15 minutes after the lamination using an Instron Tester (Model 5542).
• the crosshead speed was 12 inches/minute.
• unprinted adhesive-coated polyester film was laminated to an identical white polyvinyl chloride substrate in an identical manner. The peel force was determined to be approximately 12 pounds/inch (21 N/cm), which resulted in tearing of the polyester film.
• An adhesive-coated polyester film was prepared by solution coating Airflex 7200 ethylene vinyl acetate copolymer dispersion (72 wt. % in water, available from Air Products Chemical Co.) onto Mellinex 454 polyester film (0.92 mil, available from Dupont) at a wet coating coverage of approximately 75 g/square meter, followed by drying to give an adhesive-coated film.
• the dry thickness of the adhesive layer was 2 mil.
• the adhesive portion of the film was area printed using a liquid toner- based, black, positive-acting, film-forming, electrophotographic ink (prepared as described above) to a net optical density of 1.6 and then laminated to a white polyvinyl chloride substrate following the procedure described in Example 1.
• the peel strength, measured as described in Example 1, was determined to be 4.5 pounds/inch (7.9 N/cm).
• unprinted adhesive film was laminated to an identical white polyvinyl chloride substrate in an identical manner.
• the peel force was determined to be approximately 5.0 pounds/inch (8.8 N/cm).
• a laminated construction was prepared by laminating a sheet of Bynel E418 anhydride-modified ethylene vinyl acetate polymer adhesive (5.0 mil thick, available from Dupont Chemical Co.) between a white polyvinyl chloride substrate and the coated side of a sheet of coated polyester film (Mylar 50RL31, available from Dupont Chemical Co.). Lamination was accomplished following the procedure described in Example 1. The resulting laminate had a peel strength, measured as described in Example 1, of 6 pounds/inch (10.5 N/cm).
• a substrate was prepared by forming a primer layer and then a subbing layer on 4 mil thick polyvinylidene chloride primed polyester film (available from 3M Company).
• the primer layer was prepared by coating (to a wet thickness of 12.5 microns) an aqueous dispersion containing 250 ppm by weight colloidal vanadium oxide (added as a 1% dispersion in water, available from 3M Company), 2500 ppm by weight of hydrolyzed glycidoxypropyl trimethoxy silane (hydrolyzed in water at 5% concentration using 50 ppm HC1 as a catalyst 18 hours before addition to the primer layer coating solution), 500 ppm by weight Triton X-100 surfactant (available from Rohm and Haas), and 2.5 % by weight Eastek 2400 polymer (available as a 40% dispersion from Eastman Chemical Co.), followed by drying.
• the subbing layer was prepared by coating (to a wet thickness of 9 microns) the coating solution of Example LA. of U.S. Patent 5,204,219 onto the primer layer, followed by drying.
• the subbing layer of the resulting film was area printed using a liquid toner-based, black, positive-acting, film-forming, electrophotographic ink (prepared as described above) to an optical density of 1.2.
• E418 adhesive to the ink was determined by laminating a 5.0 mil thick sheet of the adhesive between the printed surface of the subbing layer of the polyester film and the coated side of Mylar 50RL31 film following the procedure described in Example 1.
• the peel strength of the resulting laminate was measured according to the procedure described in Example 1. Separation between the Bynel E418 and the printed surface occurred at a peel force of 3.5 pounds/inch (6.1 N/cm). Separation of Bynel E418 adhesive from the Mylar 50RL31 film did not occur in the peel testing.
• Example 3 The procedure of Example 3 was followed except that 2 mil thick Bynel 11E554 film (available from Dupont Chemical Co. and described as a modified ethylene vinyl acetate) was used in place of Bynel E418. Peeling of the adhesive from bare polyvinyl chloride resulted in a peel force of 5 pounds/inch (8.8 N/cm). Peeling of the adhesive from the electrophotographic ink resulted in a peel force of 6 pounds/inch (10 N/cm). Separation of Bynel 11E554 adhesive from the Mylar 50RL31 film did not occur in the peel testing.
• 2 mil thick Bynel 11E554 film available from Dupont Chemical Co. and described as a modified ethylene vinyl acetate
• Example 5 The procedure of Example 4 was followed except that a polyester film coated withBostik Vitel 3554 adhesive (an amorphous, thermoplastic, high molecular weight, linear, saturated, polyester resin) was used in place of Bynel E418.
• the adhesive-coated film was prepared by solution coating a 40% solids solution of Bostik Vitel 3554 polyester adhesive onto Mellinex 454 polyester film (0.92 mil, available from DuPont) at a wet coating coverage of approximately 125 g/square meter, followed by drying to give an adhesive-coated film.
• the dry thickness of the adhesive layer was 2.0 mil. Lamination to a white polyvinyl chloride substrate yielded an article having a peel strength greater than 10 pounds/inch (18 N/cm).
• Example 6 The procedure of Example 4 was followed except that a polyester film coated with a mixture of Desmocoll 8634 semi-crystalline polyurethane resin solution (Bayer Chemical Co.) and Bostik Vitel 3554 amorphous polyester resin was used in place of Bynel E418.
• the adhesive-coated film was prepared by solution coating a solution containing a mixture of 7.5% solids Desmocoll 8634 and 7.5% solids Bostik Vitel 3554 40% onto Mellinex 454 polyester film (0.92 mil, available from DuPont) at a wet coating coverage of approximately 170 g/square meter, followed by drying to give an adhesive-coated film.
• the dry thickness of the adhesive layer was 1.0 mil. Lamination to a white polyvinyl chloride substrate yielded an article having a peel strength greater than 10 pounds/inch (18 N/cm).
• the adhesion of the Desmocoll 8634/Bostik was prepared by solution coating a solution containing a mixture of 7.
• Vitel 3554 mixture to an electrophotographic ink was tested following the procedure of Example 4. Peeling of the adhesive-coated polyester film from the electrophotographic ink resulted in a peel force of 4 pounds/inch (7.1 N/cm).
• the laminate was also peeled at 90 degrees, resulting in smooth peel at a peel force of 2.5 pounds/inch (4.4 N/cm), compared to a zipper-like peel observed for a laminate construction featuring only the Desmocoll 8634 adhesive.
• the adhesive-coated film had a solid, non-tacky surface, compared to a tacky surface observed for adhesive compositions containing Bostik 3554 alone.
• Example 4 The procedure of Example 4 was followed except that a polyester film coated with a two-layer adhesive composition was used in place of Bynel E418.
• the adhesive-coated film was prepared by first solution coating a 6.5% solids aqueous dispersion of Airflex 7200 ethylene-vinyl acetate copolymer dispersion (Air Products Chemical Co.) onto Mellinex 454 polyester film (0.92 mil, available from DuPont) at a wet coating coverage of approximately 40 g/square meter, followed by drying to give an adhesive-coated film having a dry thickness of 1.0 mil.
• a second adhesive layer was added by solution coating a 15% solids solution of Desmocoll 8634 on top of the Airflex 7200 layer at a wet coating coverage of 85 g/square meter, followed by drying to yield a layer having a dry thickness of 0.5 mil.
• the total thickness of the resulting two-layer adhesive was 1.5 mil. Lamination to a white polyvinyl chloride substrate yielded an article having a peel strength of 7 pounds/inch (11 N/cm).
• the laminate was also peeled at 90 degrees, resulting in smooth peel at a peel force of 6.7 pounds/inch (4.4 N/cm), compared to a zipper-like peel observed for a laminate construction featuring only the Desmocoll 8634 adhesive.
• the adhesive-coated film had a solid, non-tacky surface, compared to a tacky surface observed for adhesive compositions containing Bostik 3554 alone.
• Example 8 The procedure of Example 2 was followed except that the polyester film was coated with a mixture of Desmocoll 8634 polyurethane resin solution (Bayer Chemical Co.) and Airflex 7200 ethylene-vinyl acetate copolymer dispersion (Air Products Chemical Co.).
• the adhesive-coated film was prepared by solution coating a mixture of equal amounts of 15 wt.% Desmocoll 8634 and 15 wt.% ethylene-vinyl acetate copolymer in methyl ethyl ketone (prepared by mixing
• the adhesive portion of the film was area printed using a liquid toner- based, black, positive-acting, film-forming, electrophotographic ink (prepared as described above) to a net optical density of 1.6 and then laminated to a white polyvinyl chloride substrate following the procedure described in Example 1.
• the peel strength measured as described in Example 1 with the exception that the measurement was made 5 minutes after lamination, was determined to be 4.6 pounds/inch (8.1 N/cm).
• the chamber was maintained at 60°C and 95% relative humidity.
• the sample was removed and stored in a dessicator at room temperature for another 14 days. Its 180 degree peel force was then measured as described in Example 1 and determined to be 5.8 pounds/inch (10.2 N/cm).
• unprinted adhesive-coated polyester film was laminated to an identical white polyvinyl chloride substrate in an identical manner.
• the peel force measured 5 minutes following lamination, was determined to be 8.6 pounds/inch (15 N/cm).
• Two additional laminated samples were subjected to high humidity and heat (60°C/95% relative humidity) for 14 days, as described above.
• the 180 degree peel force of one of the samples was measured 5 minutes following removal from the Thermotron chamber and determined to be 5.4 pounds/inch (9.5 N/cm).
• the other sample was placed in a dessicator at room temperature for 14 days. Following removal from the dessicator, its peel strength was measured and determined to be 5.1 pounds/inch (9.0 N/cm).
• the unprinted adhesive-coated film was held at 40°C for a period of one week. It was then laminated to an identical white polyvinyl chloride substrate in an identical manner. The peel strength, measured 5 minutes after lamination, was determined to be 10.6 pounds/inch (19 N/cm).
• Example 8 The procedure of Example 8 was followed except that the adhesive coating solution was prepared by combining one part of the 15 wt.% ethylene-vinyl acetate solution with two parts of a 15 wt.% solution of Q-Thane QA3781 polyurethane resin (available from K. J. Quinn and Co. of Seabrook, NH).
• the adhesive coating solution was prepared by combining one part of the 15 wt.% ethylene-vinyl acetate solution with two parts of a 15 wt.% solution of Q-Thane QA3781 polyurethane resin (available from K. J. Quinn and Co. of Seabrook, NH).
• the adhesive-coated film was area-printed and laminated to a white polyvinyl chloride substrate, as described in Example 8.
• the peel strength of the laminate measured 5 minutes after lamination, was determined to be 5.6 pounds/inch (9.9 N/cm).
• Two additional laminated samples were subjected to high humidity and heat (60°C/95% relative humidity) for 14 days, as described above.
• the 180 degree peel force of one of the samples was measured 5 minutes following removal from the Thermotron chamber and determined to be 5.3 pounds/inch (9.5 N/cm).
• the other sample was placed in a dessicator at room temperature for 14 days. Following removal from the dessicator, its peel strength was measured and determined to be 8.5 pounds/inch (15 N/cm).
• the unprinted adhesive-coated film was held at 40°C for a period of one week. It was then laminated to an identical white polyvinyl chloride substrate in an identical manner. The peel strength, measured 5 minutes after lamination, was determined to be 7.5 pounds/inch (13.2 N/cm).
• Example 10 The procedure of Example 8 was followed except that the adhesive coating solution was prepared by combining one part of the 15 wt.% ethylene-vinyl acetate solution, two parts of the 15 wt.% solution of Q-Thane QA3781 polyurethane resin, and one part of a 15 wt.% amorphous polyester resin (Vitel B3554 from Bostik Co. of Middleton, MA).
• the adhesive-coated film was area-printed and laminated to a white polyvinyl chloride substrate, as described in Example 8.
• the peel strength of an identical laminate measured after a 14 day exposure to high humidity and heat (60°C and 95% relative humidity), followed by a 14 day dessication at room temperature, was 7.8 pounds/inch (13.8 N/cm).
• Two additional laminated samples were subjected to high humidity and heat (60°C/95% relative humidity) for 14 days, as described above.
• the 180 degree peel force of one of the samples was measured 5 minutes following removal from the Thermotron chamber and determined to be 5.8 pounds/inch (10.2 N/cm).
• the other sample was placed in a dessicator at room temperature for 14 days. Following removal from the dessicator, its peel strength was measured and determined to be 6.8 pounds/inch (12 N/cm).
• the unprinted adhesive-coated film was held at 40°C for a period of one week. It was then laminated to an identical white polyvinyl chloride substrate in an identical manner. The peel strength, measured 5 minutes after lamination, was determined to be 5.4 pounds/inch (9.5 N/cm). Other embodiments are within the following claims.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Laminated Bodies (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)

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• 1999
  • 1999-09-09 KR KR1020017003111A patent/KR20010088801A/ko not_active Application Discontinuation
  • 1999-09-09 WO PCT/US1999/020611 patent/WO2000016165A1/en not_active Application Discontinuation
  • 1999-09-09 JP JP2000570640A patent/JP2002525654A/ja active Pending

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