Title:

Process for printing and molding a flocked article

Document Type and Number:

United States Patent 7413581

Abstract:

The processes and articles of the present invention use thermally stable and loft retentive polymers in sublimation printed flock fibers, which are particularly attractive for forming molded articles. A preferred polymer is poly(cyclohexylene-dimethylene terephthalate.

Inventors:

Abrams, Louis Brown (Fort Collins, CO, US)

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Application Number:

10/614340

Publication Date:

08/19/2008

Filing Date:

07/03/2003

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Export Citation:

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Assignee:

High Voltage Graphics, Inc. (Fort Collins, CO, US)

Primary Class:

428/90

Other Classes:

8/471

International Classes:

D06P5/00; D06P5/24; D06P5/28; D06P3/52

Field of Search:

428/90, 8/471

US Patent References:

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Primary Examiner:

Juska, Cheryl

Attorney, Agent or Firm:

Sheridan Ross P.C.

Parent Case Data:

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional Patent Application Nos. 60/393,362 filed Jul. 3, 2002; 60/416,098 filed Oct. 4, 2002; 60/422,206 filed Oct. 29, 2002; and 60/443,986 filed Jan. 30, 2003. The entire disclosure of the provisional applications is considered to be part of the disclosure of the accompanying application and is hereby incorporated by reference.

Claims:

What is claimed is:

1. A method for forming an article, comprising: providing a flock fiber-containing surface, wherein the fibers of the fiber-containing surface comprise at least about 25 wt. % of a terephthalate polymer or copolymer having a repeating unit having the formula: embedded image

where “R” represents hydrogen or independently a substituted or unsubstituted alkyl or aryl group and “S” is an aromatic or nonaromatic cyclic residue which can include one or more heteroatoms; and sublimation printing the fiber-containing surface to form a printed article, wherein the fibers are at least one of drawn and heat set at a temperature at or above the maximum fiber temperature during sublimation printing.

2. The method of claim 1, wherein the polymer has a glass transition temperature of at least about 75 degrees Celsius wherein the fibers are oriented transversely to an adhesive film contacting ends of the fibers, and wherein the fibers are free-standing.

3. The method of claim 1, wherein the fibers have a percent elongation of at least about 25%, a compression recovery (from 34.5 mPa) of at least about 30%, and a deflection temperature at 18.8 kg/square cm of at least about 215 degrees Celsius.

4. The method of claim 1, wherein the polymer is poly(cyclohexylene-dimethylene terephthalate).

5. The method of claim 1, wherein the fiber-containing surface comprises a release sheet, the plurality of fibers, and a release adhesive between the fibers and the release sheet.

6. The method of claim 1, wherein the fiber-containing surface comprises the plurality of fibers adhered to a hot melt adhesive.

7. The method of claim 1, wherein the fiber-containing surface comprises a plurality of fibers adhered to a thermoplastic backing film.

8. The method of claim 1, wherein the article comprises: a substrate; a permanent adhesive; and the flock fibers adhered by the permanent adhesive to the substrate, wherein the fibers are oriented transversely to the adjacent surface of the substrate, and wherein the fibers are heat set, and/or drawn at a temperature of at least about 180° C.

9. The method of claim 1, wherein the fibers are at least about 20% crystallized, wherein the fibers are perpendicular to a plane of the substrate, and wherein the fibers are free standing.

10. The method of claim 1, wherein the substrate is a thermoplastic backing film and wherein the fibers are at least substantially normal to the substrate.

11. The method of claim 1, wherein the fibers are heat set at a temperature at or above the maximum flock temperature during sublimation printing.

12. The method of claim 11, wherein the fibers have a softening point at least about 5% greater than a maximum temperature of the flock during the sublimation printing step and wherein the maximum temperature is at least about 340° F.

13. The method of claim 11, wherein the fibers have a melting point at least about 5% greater than a maximum temperature of the flock during the sublimation printing step and wherein the maximum temperature is at least about 340° F.

14. The method of claim 1, wherein the fibers have a melting point of at least about 265° C.

15. The method of claim 1, wherein the fibers have a shrinkage of less than about 1% in air at 190° C.

16. The method of claim 1, wherein the fibers are at least about 30% crystallized.

17. The method of claim 1, wherein at least one of a drawing temperature and heat set temperature of the flock is at least about 180° C.

18. The method of claim 11, wherein the fiber-containing surface comprises a thennosetting adhesive, wherein, before the sublimation printing step, the thermosetting adhesive is not thermoset, and wherein the thermosetting adhesive is thermoset during the sublimation printing step.

19. The method of claim 11, wherein the fiber-containing surface comprises a carrier sheet, a release adhesive engaging the carrier sheet and first ends of a plurality of fibers, and wherein second ends of the plurality of fibers are sublimation printed and further comprising: thereafter applying a first permanent adhesive layer to the second ends of the plurality of flock fibers, the first ends being opposed to the second ends.

20. The method of claim 19, further comprising: applying a barrier film to a second surface of the first permanent adhesive layer, wherein a first surface of the permanent adhesive layer contacts the fibers and wherein the first and second adhesive layer surfaces are in an opposed relationship.

21. The method of claim 20, further comprising: applying a second permanent adhesive layer to a second surface of the barrier film, wherein a second surface of the barrier film contacts the first permanent adhesive layer and wherein the first and second barrier film surfaces are in an opposed relationship.

22. The method of claim 1, wherein the fiber-containing surface comprises a carrier sheet, a sublimation dye on a first surface of the carrier sheet, a plurality of fibers, a release adhesive engaging the sublimation dye on the carrier sheet and first ends of the plurality of fibers, and a permanent adhesive engaging seconds ends of the fibers, wherein the first and second ends are in an opposing relationship.

23. The method of claim 22, wherein the release adhesive vaporizes during the sublimation printing step.

24. The method of claim 1, wherein the fiber-containing surface comprises a carrier sheet, a plurality of fibers, and a release adhesive engaging the carrier sheet and fibers and further comprising: contacting a permanent adhesive film with second ends of the fibers, first ends of the fibers engaging the release adhesive and the first and second ends being in an opposing relationship; and laminating together the adhesive film and fiber-containing surface, wherein the contacting step is after the sublimation printing step.

25. The method of claim 24, wherein the permanent adhesive film is at least one of a calendered, extruded, and co-extruded film, wherein the permanent adhesive film is a thermosetting adhesive, and wherein the permanent adhesive film is thermoset in the laminating step.

26. The method of claim 1, wherein the sublimation printing step comprises: contacting a transfer, comprising sublimation dye, with the fiber-containing surface; and heating and applying pressure to the contacted transfer, whereby sublimation dye is transferred from the transfer to the fibers.

27. A method for providing a molded article comprising: providing a flock fiber-containing surface, the fiber-containing surface comprising at least about 25 wt. % of a terephthalate polymer or copolymer having a repeating unit of the formula: embedded image

where “R” represents hydrogen or independently a substituted or unsubstituted alkyl or aryl group and “S” is an aromatic or nonaromatic cyclic residue which can include one or more heteroatoms; forming the fiber-containing surface into a three dimensional shape; positioning the formed fiber-containing surface in a mold; and introducing a resin into the mold to form a molded article.

37. The method of claim 19, wherein the fibers have a melting point of at least about 200 degrees Celsius.

38. The method of claim 36, wherein the polymer has a glass transition temperature of at least about 75 degrees Celsius, wherein the fibers are oriented transversely to an adhesive film contacting ends of the fibers, and wherein the fibers are free-standing.

39. The method of claim 36, wherein the fibers have a percent elongation of at least about 25%, a compression recovery (from 34.5 mPa) of at least about 30%, and a deflection temperature at 18.8 kg/square cm of at least about 215 degrees Celsius.

40. The method of claim 36, wherein the polymer is poly(cyclohexylene-dimethylene terephthalate).

41. The method of claim 36, wherein the fiber-containing surface comprises a release sheet, a plurality of fibers and a release adhesive between the flock fibers and the release sheet.

42. The method of claim 36, wherein the fiber-containing surface comprises a plurality of fibers adhered to a hot melt adhesive.

43. The method of claim 36, wherein the fiber-containing surface comprises a plurality of fibers adhered to a thermoplastic backing film.

44. The method of claim 36, wherein the sublimation printing step comprises: contacting a transfer, comprising sublimation dye, with the fiber-containing surface; and heating and applying pressure to the contacted transfer, whereby sublimation dye is transferred from the transfer to the fibers.

45. A method for providing a printed article comprising: providing a fiber-containing surface having a plurality of flock fibers, the fibers comprising at least about 25 wt. % of a terephthalate polymer or copolymer having a repeating unit of the formula: embedded image

where “R” represents hydrogen or independently a substituted or unsubstituted alkyl or aryl group and “S” is an aromatic or nonaromatic cyclic residue which can include one or more heteroatoms; and sublimation printing the fiber-containing surface to form a printed article, wherein during sublimation printing the fiber-containing surface is heated to a sublimation printing temperature and wherein the polymer has a melting point greater than the maximum sublimation printing temperature, and wherein at least one of the drawing temperature and the heat set temperature of the polymer is at or above the maximum sublimation printing temperature.

46. The method of claim 45, wherein the polymer is a polyester and is at least about 20% crystallized and wherein the polymer has a glass transition temperature of at least about 75° C.

47. The method of claim 45, wherein the fibers have a softening point at least about 5% greater than a maximum sublimation printing temperature and wherein the maximum sublimation printing temperature is at least about 340° F.

48. The method of claim 45, wherein the fibers have a melting point at least about 5% greater than a maximum sublimation printing temperature and wherein the maximum temperature is at least about 340° F.

49. The method of claim 48, wherein the fibers have a melting point of at least about 200° C.

50. The method of claim 45, wherein the fibers have a shrinkage of less than about 1% in air at 190° C.

51. The method of claim 45, wherein the fibers are at least about 30% crystallized.

52. The method of claim 45, wherein at least one of an extrusion temperature, drawing temperature, and heat set temperature of the fibers is at least about 180° C.

53. The method of claim 45, wherein the fiber-containing surface comprises a thermosetting adhesive, wherein, before the sublimation printing step, the thermosetting adhesive is not thermoset, and wherein the thermosetting adhesive is thermoset during the sublimation printing step.

54. The method of claim 45, wherein the fiber-containing surface comprises a calTier sheet, a release adhesive engaging the carrier sheet and first ends of a plurality of fibers, and wherein second ends of the plurality of fibers are sublimation printed and further comprising: thereafter applying a first permanent adhesive layer to the second ends of the plurality of fibers, the first ends being opposed to the second ends.

55. The method of claim 54, further comprising: applying a barrier film to a second surface of the first permanent adhesive layer, wherein a first surface of the permanent adhesive layer contacts the fibers and wherein the first and second adhesive layer surfaces are in an opposed relationship.

56. The method of claim 55, further comprising: applying a second permanent adhesive layer to a second surface of the barrier film, wherein a second surface of the barrier film contacts the first permanent adhesive layer and wherein the first and second barrier film surfaces are in an opposed relationship.

57. The method of claim 45, wherein the fiber-containing surface comprises a carrier sheet, a sublimation dye on a first surface of the carrier sheet, a plurality of fibers, a release adhesive engaging the sublimation dye on the carrier sheet and first ends of the plurality of fibers, and a permanent adhesive engaging seconds ends of the fibers, wherein the first and second ends are in an opposing relationship.

58. The method of claim 45, wherein the fiber-containing surface comprises a carrier sheet, a plurality of fibers, and a release adhesive engaging the carrier sheet and fibers and further comprising: contacting a permanent adhesive film with second ends of the fibers, first ends of the fibers engaging the release adhesive and the first and second ends being in an opposing relationship; and laminating together the adhesive film and fiber-containing surface, wherein the contacting step is after the sublimation printing step.

59. The method of claim 58, wherein the permanent adhesive film is at least one of a calendered, extruded, and co-extruded film, wherein the permanent adhesive film is a thermosetting adhesive, and wherein the permanent adhesive film is thermoset in the laminating step.

60. The method of claim 45, wherein the sublimation printing temperature is at least about 340° F.

61. The method of claim 45, wherein the polymer is a polyester and wherein the sublimation printing step comprises: contacting a transfer, comprising sublimation dye, with the fiber-containing surface; heating and applying pressure to the contacted transfer, whereby sublimation dye is transferred from the transfer to the fibers.

Description:

FIELD OF THE INVENTION

The present invention is related generally to printing of flocked articles and specifically to sublimation printing of flocked articles.

BACKGROUND OF THE INVENTION

Flock is used in the manufacture of numerous types of articles, such as textiles. Such articles are typically manufactured by electrostatically depositing the flock onto the desired surface. In one process, the desired surface is a release-adhesive coated sacrificial carrier sheet. The free ends of the flock are then contacted with an adhesive. This structure, also known as a transfer, is thermally applied to the substrate. In another process, the desired surface is a permanent adhesive or the substrate itself. This process is known as direct flocking. The direct flocked structure generally does not include a carrier sheet and release adhesive.

Flock fibers are either pre-dyed (before application to the desired surface) or post-dyed (after application to the surface). Post-dyeing is typically effected by sublimation dyeing techniques in which the flock and dye are heated so that the vaporized dye is transferred to the flock fiber. A sublimation print in the desired design typically carries the dye for transfer to the flock either by inkjet or heat transfer techniques. As used herein, “sublimation” refers to a process where an image is printed by turning dye, ink or toner by heat and/or pressure into a gas which then impregnates itself into a substrate or a coating on a substrate.

The use of sublimation printing of flock has generally not been widely practiced for various reasons. Some polyesters, such as poly(ethylene terephthalate), can hold the dye but have little loft retention and flatten out during sublimation printing. Other polyesters typically melt or soften and deform under the high temperatures experienced during sublimation printing, losing desirable tactile characteristics (soft touch). Nylon and rayon fibers, though having loft retention, generally are unable to accept the vaporized dye consistently and/or permanently and therefore produce an irregular and/or unstable colored product.

SUMMARY OF THE INVENTION

These and other needs are addressed by the various embodiments and configurations of the present invention. The processes and articles of the present invention use a variety of thermally stable and loft retentive polymers in sublimation printed flock fibers, which are highly attractive for molded resin articles. In a particularly preferred embodiment, the flock fibers comprise poly(cyclohexylene-dimethylene terephthalate) (“PCT”), which includes modified forms of PCT such as Thermx PCTA™ manufactured by Eastman Chemical Company. As will be appreciated, Thermx PCTA™ is PCT modified using isophthalic acid.

The flock of the present invention comprises a printable flocking material. Typically, the flocking material is a white polyester or other synthetic fiber. A suitable dye or pigment is applied to the flock to cause dyeing or coloration of the flock after application to the underlying (or overlying) layer (depending on the order in which the various layers are deposited). The dyes or pigments include sublimation dyes (as noted above), acid dye inks, and pigment dyes. Sublimination is a preferred technique to provide desired color patterns to the design due to the superior feel of the design. The colored fibers in the design have a softer feel than fibers colored using other techniques or of other compositions. A softer feel is more attractive to consumers in many applications. The dye is more colorfast on the fiber as the dye is absorbed at high temperature and fixed by the fiber as opposed to simply being a surface coat on the fiber. Unlike sublimation dyes, non-sublimation dyes, such as acid dye inks, generally must be cured after application, such as by steam curing (which can be impractical and cumbersome).

The flock of the present invention, when combined with the various flocking/molding techniques set forth herein, makes it possible to obtain a wide format design inexpensively and in high volumes. Such designs are particularly attractive when combined with highly resilient flock such as PCT flock.

These and other advantages will be apparent from the disclosure of the invention(s) contained herein.

The above-described embodiments and configurations are neither complete nor exhaustive. As will be appreciated, other embodiments of the invention are possible utilizing, alone or in combination, one or more of the features set forth above or described in detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a first process embodiment according to the present invention;

FIG. 2 is a first flocked article embodiment made by the process of FIG. 1;

FIG. 3 is a second process embodiment according to the present invention;

FIG. 4 is a second flocked article embodiment made by the process of FIG. 3;

FIG. 5 is a third process embodiment according to the present invention;

FIG. 6 is a third flocked article embodiment made by the process of FIG. 5;

FIG. 7 is a fourth process embodiment according to the present invention;

FIG. 8 is a fourth flocked article embodiment made by the process of FIG. 7

FIG. 9 is a fifth process embodiment according to the present invention;

FIG. 10 is a fifth flocked article embodiment made by the process of FIG. 9;

FIG. 11 is a sixth process embodiment according to the present invention;

FIG. 12 is a sixth flocked article embodiment made by the process of FIG. 11;

FIG. 13 is a seventh process embodiment according to the present invention;

FIG. 14 is a seventh flocked article embodiment made by the process of FIG. 13;

FIG. 15 depicts the chemical formula of a family of polymers including PCT;

FIG. 16 is a side cross-sectional view of a first configuration of a die accommodating a mold insert;

FIG. 17 is a side view of a continuous lamination process for forming a mold insert;

FIG. 18 is a side view of a molded article according to an embodiment of the present invention;

FIG. 19 is a side view of a second configuration of a die accommodating a mold insert;

FIG. 20 is a plan view of a mold insert according to another embodiment of the present invention; and

FIG. 21 is a side view of a mold containing the mold insert of FIG. 20.

DETAILED DESCRIPTION

Sublimation Printed Articles

The various embodiments of the present invention utilize a thermally stable polymer, copolymer, or polymer blend with loft retention as the flocking fiber. Sublimation printing typically heats and applies pressure to the flocked article to permit dye to be transferred and heat set via the vapor phase from a substrate to the fiber. Many polyester fibers, such as polyethylene terephthalate, polyamide fibers such as nylon, and cellulose fibers such as rayon soften at such temperatures/pressures and/or have poor loft retention, because of the temperature and pressure required for sublimation dye to transfer and heat set, thereby causing an unattractive article and unpleasant surface to the touch.

The polymers, copolymers, and polymer blends of the present invention can overcome these limitations. For sublimation printing, the polymers, copolymers, and polymer blends preferably have a melting point and softening point that are greater than and more preferably at least about 5% greater than the temperature to which the flock will be heated during sublimation printing (and, if applicable, molding). This temperature is typically at least about 340° F., more typically at least about 350° F., and even more typically ranges from about 350° F. to about 400° F. The polymers, copolymers and polymer blends preferably will accept dye, and are highly flexible and elastic with a high degree of shape memory (e.g., high percentage of shape recovery after compression). These features preferably are maintained despite the temperatures and pressures experienced during sublimation printing. The pressures experienced during sublimation printing typically are at least about 2 psi, and even more typically range from about 2 psi to about 30 psi.

In one embodiment, the flock comprises a polyester having the repeating unit formula set forth in FIG. 15. With reference to that figure, “R” represents hydrogen or independently a substituted or unsubstituted alkyl or aryl group and “S” is an aromatic or nonaromatic cyclic residue which can include one or more heteroatoms. In a particularly preferred embodiment, the flock comprises the polyester poly(cyclohexylene-dimethylene terephthalate) (“PCT”), with poly(1,4-cyclohexylene-dimethylene terephthalate) being preferred and PCT polyester, such as Thermx™ or Thermx EG™, from Eastman Chemical Company being even more preferred.

PCT has a number of desirable characteristics for high temperature applications, such as sublimation printing and molding. PCT properties (and the properties of other preferred polymers, copolymers, and polymer blends) include one or more of a melting point typically of at least about 200° C., more typically at least about 265° C., and even more typically about 290° C., a safe ironing temperature typically of at least about 150° C. and more typically of about 205° C., a glass transition temperature typically of at least about 75° C. and more typically of about 90° C., a tenacity typically of at least about 2.5 and typically ranging from about 2.5 to about 3.0, a percent elongation typically of at least about 25% and more typically of at least about 35%, a compression recovery (from 34.5 mPa) typically of at least about 30% and more typically about 44%, and a deflection temperature at 18.8 kg/square centimeter typically of at least about 215° C. and even more typically of at least about 220° C. The work recovery of PCT from a 2% extension is typically at least about 50 and more typically about 90, from 5% extension at least about 40 and more typically about 55, and from a 10% extension at least about 25 and more typically about 35. The shrinkage of PCT is typically less than about 1% in air at 190° C. and less than about 0.5% in water at 100° C. PCT also has excellent resistance to chemicals such as mineral acids, hydroxides, and commonly used solvents. PCT may be provided with a conductive coating to hold a charge, which is important for electrostatic flocking applications.

PCT has a number of surprising and unexpected advantages relative to polyethylene terephthalate (“PET”), nylon, and rayon in molding applications. PCT has a higher melting point (290° C.) than nylon 66 (264° C.) and nylon 6 (223° C.), and PET (250° C.) and a higher deflection temperature for a selected applied pressure or force. PCT is more resilient than PET (e.g., PCT has a compression recovery of about 44% from 34.5 mPa while PET has a compression recovery of about 31% from 34.5 mPa).

Processes for manufacturing PCT are disclosed in U.S. Pat. Nos. 5,654,395; 5,194,523; 5,106,944; and 5,021,289, each of which is incorporated herein by this reference. Typically, PCT is formed by polymerizing a suitable ester, such as dimethyl terephthalate, with a suitable alcohol, such as 1,4 cyclohexane dimethanol; to a desired degree of polymerization under conditions and using catalysts known to those of ordinary skill in the art. After polymerization, the polymerized material is extruded in the form of a ribbon, and the ribbon hardened and cut into chips. The chips are dried and then put into hopper reservoirs for melting. The chips are melt spun into fibers by extruding through spinnerets at an extrusion temperature, cooled upon contact with the air, and wound around cylinders. The fibers are hot stretched at a drawing temperature until they are about five times their original length to decrease their width. The drawing results in optimal orientation of the molecules inside the fiber and results in a desired strength. The fibers can be annealed at an annealing or heat set temperature. The polymer may be mixed with suitable additives, such as blend compatible polymers, plasticizers, delusterants, dye stuffs, and the like.

To provide thermal stability, the polymer should be highly crystallized. Typically, the polymer in the fiber is at least about 20%, more typically at least about 30%, and even more typically from about 30% to about 70% crystallized. To make this possible, preferably at least one of the extrusion temperature, drawing temperature, and heat set temperature is/are at least as high or higher than the, maximum temperature experienced by the fiber in later processing, such as sublimation printing and molding. More preferably, the temperature is at least about 180° C., more preferably of at least about 190° C., even more preferably of at least about 200° C., and even more preferably of at least about 205° C. This temperature can be important to providing PCT with suitable properties for sublimation printing to “lock in” the resiliency. As will be appreciated, additives can be added to the PCT, as in the case of ThermxA or PCTA™ (which is isophthalic acid-modified PCT), to provide the desired degree of crystallinity.

As will be appreciated, strength, elasticity, and dye-ability can be impacted by the degree to which the fibers are drawn. Additionally, the fibers can be singed, calendared, or embossed.

The preferred polymer composition comprises at least about 25 wt. % PCT, more preferably at least about 50 wt. % PCT, and even more preferably at least about 75 wt. % PCT. The composition may include other desirable additives, typically at least about 0.1 wt % and more typically from about 0.5 to about 25 wt % plasticizer(s). Suitable plasticizers are known to those skilled in the art.

The superior properties of PCT are also amenable to flock coloration using sublimation dyes. As will be appreciated, flock can be colored by sublimation dyes by many techniques. In such coloration techniques, the flocking material is a white flock and a sublimation dye is added to the white flock by suitable techniques after flock application to the underlying (or overlying) adjacent adhesive layer. In these various techniques, the sublimation dye is heated until the dye enters the vapor phase (by direct conversion of the solid phase to the vapor phase). The fibers are also heated to about the same temperature as the vaporized dye. The fiber accepts the vaporized dye, which colors the fibers. During dye application and subsequent curing under, heat (temperatures typically of at least about 340° F. and more typically ranging from about 350° F. to about 400° F.) and pressure (typically of at least about 2 psi and more typically ranging from about 12 to about 50 psi) is/are applied to the flock and tends to flatten or deform flock fibers. In comparison to PET, PCT, due to PCT's higher melt point and greater loft and loft retention, will not flatten as much as PET, if at all. Nylon and rayon fibers will not accept sublimation dyes as well as PET or PCT.

The PCT-containing flock can be applied by electrostatic, gravity, and vibrating techniques directly to a substrate or to a carrier for indirect application to the substrate. For example and as discussed below, the PCT-containing material discussed above can be used as the flock material in the processes/articles in any of U.S. Pat. Nos. 4,810,549; 5,047,103; 5,207,851; 5,346,746; 5,597,637; 5,858,156; 6,010,764; 6,083,332; 6,110,560; U.S. patent applications Ser. No. 09/735,721 filed Dec. 13, 2000; U.S. patent application Ser. No. 09/621,830 filed Jul. 24, 2000; U.S. patent application Ser. No. 29/058,551 filed Aug. 19, 1996; U.S. patent application Ser. No. 09/548,839 filed Apr. 13, 2000; U.S. patent application Ser. No. 09/973,113 filed Oct. 9, 2001; and U.S. Provisional Applications Ser. No. 60/327,642, filed Oct. 5, 2001, U.S. Provisional Applications Ser. No. 60/344,862, filed Nov. 8, 2001, and U.S. Provisional Applications Ser. No. 60/332,647, filed Nov. 21, 2001.

The Process and Article of the First Configuration

Referring to FIGS. 1 and 2, the process and article of the first embodiment of the present invention will now be described. This process is further discussed in U.S. Provisional Application Serial Nos. 60/366,580 filed Mar. 21, 2002; 60/393,362, filed Jul. 3, 2002; and 60/416,098 filed Oct. 4, 2002.

In the first step 100 , the an adhesive-coated substrate 104 is direct flocked by known techniques using the flock of the present invention. The PCT-containing flock is typically white in color and can be flocked by any suitable technique, with electrostatic flocking being preferred. The adhesive may be applied discontinuously to the substrate in a desired (direct) image.

The adhesive used in adhesive layer 108 may be any suitable permanent adhesive (as opposed to a release adhesive) that is thermally compatible with the sublimation printing temperature used in step 112 . “Thermal compatibility” depends on the process configuration. When the adhesive is cured (e.g., fully activated, set, cross-linked, fused, otherwise fully bonded) 116 before sublimation printing in step 112 , thermal compatibility is deemed to exist when the adhesive bond will not be detrimentally impacted by the sublimation printing temperature, such as by softening, tackifying, melting, or melting down the fibers. When the adhesive is cured during or simultaneously with sublimation printing, thermal compatibility is deemed to exist when the temperature required to fully activate, set, cross-link, fuse, or otherwise fully bond the adhesive is at or below the sublimation printing temperature. When the adhesive is cured after sublimation printing, thermal compatibility is deemed to exist when the temperature required to fully activate, set, cross-link, fuse, or otherwise fully bond the adhesive is above the sublimation printing temperature.

Preferred adhesives can be any suitable adhesive, with water- and solvent-based adhesives being preferred. Particularly preferred adhesives include hot melt thermoplastic and thermoset adhesives. As will be appreciated, thermoset adhesives solidity or set irreversibly when heated above a certain temperature. This property is usually associated with a cross-linking reaction of the molecular constituents induced by heat or radiation. Thermoset adhesives can include curing agents such as organic peroxides, isocyanates, or sulfur. Examples of thermosetting adhesives include polyethylene, phenolics, alkyds, amino resins, polyesters, epoxides, polyurethanes, polyamides, and silicones.

Following curing of the adhesive layer 108 in step 116 (or 112 ), which is typically performed using radiation (e.g., heat or light) the flocked surface can be vacuumed to remove loose flock fibers. This removal of loose flock fibers can improve the quality of the image in the later sublimation printing step.

In sublimation printing step 112 , the flocked surface 120 is sublimation printed by any suitable technique to provide multi-colored flock in a desired design. As will be appreciated, common ways of performing sublimation printing include inkjet sublimation printing and heat transfer sublimation printing using devices such as an inkjet dye sub printer, a ribbon-based dye sub printer, a hybrid sublimation printer, and a small dye sub ribbon-based printer.

In inkjet (direct) sublimation printing, a special heat sensitive dye is used in a computer-controlled printer, such as an HP 550™, or Mimaki JV4™ to sublimation print the dye onto the flock fibers through vapor phase transportation of the dye from the printer to the flock fibers. The transferred dye is then heat and pressure cured.

In heat transfer sublimation printing, special heat sensitive dye is deposited on a carrier paper or film The paper or transfer is used by a suitable technique, such as offset printing, screen printing, rotograviere printing, heliographic or flexographic printing or serigraphic printing by flat plate or rotary plate to deposit dye onto a carrier. Transferring is done by placing the transfer in contact, under regulated pressure and at a predetermined temperature, generally with the aid of hot rolls, with the flocked surface, generally for a duration of about 5 to about 40 seconds. The hot rolls can comprise, in the case of printing in formats, a hot press with horizontal plates, or in the case of continuous printing from rolls of printed paper and of synthetic material to be printed, a rotating heated cylinder associated with a belt rolling under tension.

Surprisingly and unexpectedly, flock fibers 120 of the present invention, after experiencing the pressures and temperatures of sublimation printing, maintain their printing orientations. This loft retention can be facilitated by vacuuming the dyed flock fibers after rather than before sublimation printing. The retained orientation of at least most of the flock fibers is, as shown in FIG. 2, at least substantially perpendicular to the planar surface 124 of the adhesive layer 108 and surface 128 of the substrate 132 .

The substrate 132 can be any substrate that is dimensionally stable under the conditions of temperature and pressure encountered during sublimation printing and adhesive curing. An example of a preferred substrates is a formable thermoplastic material, such as a polycarbonate. In in-mold applications, the dimensionally stable substrate or backing film preferably has a melting point that is at or above the maximum temperature experienced in the closed mold (or the maximum temperature of the resin) and tensile and compressive strengths and thermal stability sufficient to withstand the maximum pressures experienced in the closed mold without warping or shrinking. As will be appreciated, it is important that the resin 6 be chemically and physically (e.g., thermally) compatible with the substrate 104 to produce a strong melt bond between materials and thus an integral article after removal from the closed mold. Preferably, the substrate or backing film is a thermoplastic polymeric material and the polymers in the substrate 104 cross-link with the polymers in the resin 6 . Exemplary backing films include monomers or polymers of styrene, acrylics, vinyls, olefins, amides, cellulosics, carbonates, esters, and mixtures thereof A particularly preferred substrate for many resins is a polycarbonate. Thus, the film is able to withstand high pressure and high temperature without degrading, cracking, or melting. The film can be later formed into a desired shape for insertion into the mold.

The product of the process is printed article 102 .

The Process and Article of the Second Configuration

Referring to FIGS. 3 and 4, the process and article of the second embodiment of the present invention will now be described. This process is further discussed in U.S. Pat. Nos. 4,810,549; 5,207,851; 5,597,637; 5,858,156; 6,010,764; 6,083,332; and 6,110,560.

In step 200 , the carrier sheet 204 containing a temporary release adhesive 208 (such as wax) in the reverse of the desired pattern or image is flocked by suitable techniques, preferably electrostatically, with the flock of the present invention.

The carrier sheet 204 can be any suitable transfer carrier, such as dimensionally stable paper, processed paper, plastic film, resin sheets, and metal foils. Depending on the desired effect and the sheet materials employed, the carrier can be transparent, translucent, or opaque, but is typically transparent. Typically (but not always), the primary carrier is a discontinuous sheet as opposed to a continuous sheet on a running web line.

The release adhesive 208 can be any adhesive that has a relatively low bonding strength with the resin film (as is commonly known for stickers or pressure-sensitive decal media). The release adhesive may be applied in the form of a solution or emulsion, such as a resin or a copolymer, e.g., a polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, acrylic resin, polyurethane, polyester, polyamides, cellulose derivatives, rubber derivatives, starch, casein, dextrin, gum arabic, carboxymethyl cellulose, rosin, or compositions containing two or more of these ingredients. Preferably, the release adhesive has a sufficiently low surface energy to enable even coating of the resin dispersion (applied in the next step) on the release adhesive.

The release adhesive 208 may be applied on the carrier in the perimeter shape of the desired design or without regard to the overall design desired. The release adhesive may be applied by any suitable technique such as, for example, by applying the release adhesive with rollers or spraying the release adhesive.

The exposed ends 216 of the flocked surface 212 are then sublimation printed in step 220 by the techniques discussed previously. As a part of the sublimation printing step 112 , the flock is subjected to heat and pressure to fix the transferred sub-dye dyes. As noted, vacuuming of the flock can be conducted before or after sublimation printing.

The exposed, printed ends 216 of the flocked surface are next contacted in step 226 with a binder adhesive 224 , such as a water based acrylic which binds the flock together as a unit. The binder 224 adhesive may contain a hot melt adhesive for binding the printed article 228 to a desired substrate.

In optional step 230 , the hot melt adhesive 232 is applied to the previously applied binder adhesive 216 . After bonding of the hot melt adhesive 232 to a desired substrate, the carrier sheet 204 can be removed to permit the dye on the now exposed surface 234 to be visible.

The Process and Article of the Third Configuration

Referring to FIGS. 5 and 6, the process and article of the third embodiment of the present invention will now be described. This process is further discussed in U.S. patent Ser. Nos. 09/548,839; 09/35,721; and 09/621,830. PCT is an ideal fiber to withstand the temperature and pressure used in the lamination process in this configuration.

In step 500 , the carrier sheet 504 containing a temporary release adhesive 508 (such as wax) in the reverse of the desired pattern or image is flocked by suitable techniques, preferably electrostatically, with the flock of the present invention.

The exposed ends 512 of the flocked surface 516 are then sublimation printed in step 520 by the techniques discussed previously. As noted, vacuuming of the flock can be conducted before or after sublimation printing.

The exposed, printed ends 512 of the flocked surface are next contacted with a first permanent adhesive 524 in step 528 . The permanent adhesive is preferably an activatable adhesive such as a thermoset or thermoplastic adhesive.

In step 532 , the first permanent adhesive 524 is contacted with an optional barrier film 536 .

The barrier film 536 can perform a number of differing purposes. For example, the barrier film can be selected to provide a desired coloration to the transfer, e.g., opacity, when viewed by a customer. The barrier film 536 could also be used to provide a desired color in areas where flock is intentionally omitted. This can produce a 3-D appearance to the viewer. Examples of film compositions for this objective include decorative media such as a textile, glitter, reflective glass, beads and etc. The film 536 can be selected to provide desired physical properties to the transfer. For example, the film 536 can have high tensile and compressive strengths and a low modulus of elasticity to provide elasticity or a high modulus of elasticity to provide rigidity. This type of barrier film is discussed in U.S. Provisional Application Ser. Nos. 60/403,992, filed and 60/405,473. Examples of film compositions for this objective include rubber and polyurethane. The film 536 can act as a barrier film to migration of the second permanent adhesive 540 into the flock 516 .

In step 544 , the second permanent adhesive 540 is optionally applied to the barrier layer 536 to permanently bond the printed article 548 to a desired substrate. The second permanent adhesive can be any of the adhesives noted above, with activatable adhesives being preferred. In one configuration, the second permanent adhesive is a preformed film, such as a polycarbonate film.

As will be appreciated, step 520 can be performed after steps 528 , 532 , and/or 544 (any one or a multiple of which can be performed separately or simultaneously by laminating techniques) and subsequent removal of the carrier sheet to provide a surface for printing.

As will be further appreciated, during thermal activation of the hot melt adhesive setting of the dye applied by sublimation printing step 520 (using inkjet techniques) can be performed when sublimation printing is done after steps 528 , 532 , and 544 . This eliminates a separate process step to set the adhesive.

The Process and Article of the Fourth Configuration

Referring to FIGS. 7 and 8, the process and article of the third embodiment of the present invention will now be described. This process is further discussed in U.S. Provisional Application Ser. No. 60/327,642, filed Oct. 5, 2001, entitled “Screen Printed Resin Film Applique Made from Liquid Plastic Dispersion”, to Abrams, Ser. No. 60/344,862, filed Nov.8, 2001, of the same title, to Abrams, and Ser. No. 60/332,647, filed Nov. 21, 2001, of the same title, to Abrams.

In step 700 , the resin dispersion 704 is applied to the carrier sheet 708 and release adhesive 712 in the direct image of the desired pattern.

The (liquid, semi-liquid, or semi-solid) resin dispersion 704 is applied, e.g., screen printed (through an image screen) using a screen printer, onto the upper surface 716 of the release coating 712 on the carrier 708 using known techniques. The resin dispersion 704 is typically applied in the perimeter shape of the desired shape or design to avoid cutting or trimming of the resin dispersion in later stages of the manufacturing process. Alternatively, the resin dispersion can be deposited on the carrier 708 by other techniques, such as spraying, extruding, and/or application through an image screen or template, that place the resin dispersion into distinct (discontinuous) image areas (as opposed to an overall (continuous) coating) onto the primary carrier.

The resin dispersion 704 can be any resin dispersion that will produce a resin film after fusing having desired characteristics. Considerations in formulating resin dispersions include screen printability, desired softness, desired thickness, color or other special effects (inclusion of glitter particles for example), acceptability and permanent adhesion of flock fibers, wash fastness, tensile strength, ability to be formed, welded and cut with a metal die in the high frequency field, and satisfactory adhesion when welded onto a desired substrate. To provide a high tensile strength, the resin dispersion typically includes at least about 0.1 wt. %, more typically at least about 0.5 wt. %, and even more typically from about 0.5 to about 2.5 wt. % of a curing agent.

Because the resin film (after the fused stage) is preferably self-supporting after removal from the primary carrier and able to withstand handling by customers, production personnel, washing/wearing, and/or machinery, the resin film (after fused stage) typically requires a minimum tensile strength. The resin dispersion should be able to form a resin film that is reactive to high frequency welding. As will be appreciated, the gelled and fused resin dispersion or resin film could be applied to a substrate by sewing, stitching or other mechanical application. Typically, the resin film will have a tensile strength similar to that of commonly available calendared, cast, and/or extruded films and greater than tensile strength of PLASTISOL™ transfer dye films. Preferably, the tensile strength of the resin film is at least about 500 psi and more preferably ranges from about 600 to about 1,000 psi. To realize this tensile strength, the thickness T _Rof the resin dispersion 16 (when applied) preferably is at least about 6 mil, more preferably ranges from about 8 to about 25 mil, and even more preferably from about 8 to about 12 mil, and the thickness of the (gelled and fused) resin film preferably is at least about 2.5 mil, more preferably at least about 4 mil, and even more preferably ranges from about 5 to about 20 mil.

The resin dispersion should also have a sufficient density (or average molecular weight) to be (highly) reactive to high frequency welding. Preferably, the viscosity of the resin dispersion ranges from about 20,000 to about 5,000,000 cp at 25° C.

Preferred resins in suitable resin dispersions include vinyls, such as plastisol (which comprises a polyvinyl chloride resin), urethanes, nylons, acrylics, acetates, and/or olefins. “Vinyls” refer to a compound including the vinyl grouping (CH ₂═CH ₂—) or a derivative thereof, “urethanes” to a compound including the grouping CO(NH ₂)OC ₂H ₅or a derivative thereof; nylons to a compound having the grouping —CONH or a derivative thereof, acrylics to a compound including the acrylonitrile grouping or a derivative thereof, acetates to an ester of acetic acid where the substitution is by a radical; olefins to a class of unsaturated aliphatic hydrocarbons having one or more double bonds; amides to a class of compounds comprising an acyl group (—CONH ₂) typically attached to an organic group “R”, where R can include hydrogen, an alkyl group, and an aryl group. More preferably, at least most of the resin is a vinyl polymer or oligomer, a urethane polymer or oligomer, an acetate polymer or oligomer, an amide polymer or oligomer, and mixtures thereof. Even more preferably, the resin is a poly (vinyl chloride), a polyurethane, a poly (ethylene vinyl acetate), a polyamide, and mixtures thereof As noted, the resins in the resin dispersion typically include polymers and/or oligomers of the foregoing compounds. Preferably, the resin dispersion comprises at least about 25 wt. %, more preferably at least about 26 wt. %, and even more preferably from about 25 to about 35 wt. % of the resin. The remainder of the resin dispersion is primarily composed of the plasticizer (which typically is from about 30 to about 40 wt. % of the resin dispersion). Typically, the resin dispersion includes no more than about 45 wt. % of the other additives noted above. A preferred resin dispersion is Rutland Screen Printing Plastisol™ manufactured by Rutland Plastic Technologies, Inc.

When the resin dispersion includes polyvinyl chloride as the resin component, the resin dispersion can be prepared by hot mixing the resin with plasticizers and, typically small proportions of, stabilizers to provide a resin film that is flexible and pliable. Pigment(s) can be included to provide resin films in a wide range of colors, as well as crystal clear. As will be appreciated, a flexible and pliable resin film is preferred over a rigid resin film as a flexible and pliable film conforms readily to undulations in the surface of the substrate to which the resin film is later applied, such as using dielectric (capacitance) welding or high frequency (HF) welding (e.g., plain welding or tear-seal welding). As will be appreciated radio frequency welding is the process of bonding materials together by applying radio frequency energy to the area to be joined. The method utilizes heat generated in poor electrical conductors, such as the resin film and substrate, when the materials are placed in varying high-frequency electromagnetic fields. The heat results from electrical losses that occur in the resin film, which is located or sandwiched between two metal plates or bars (electrodes). The sandwich forms a type of capacitor connected to a radio-frequency oscillator. The metal plates or bars (electrodes) also serve to hold the resin film and substrat