(12) United States Patent
`(16) Patent N0.:
`US 6,455,138 B1
`
`Murano
`(45) Date of Patent:
`Sep. 24, 2002
`
`U5006455138B1
`
`(54) METALLIZED SHEETING, COMPOSITES,
`AND METHODS FOR THEIR FORMATION
`
`(75)
`
`Inventor: Adam Murano, West Chesterfield, NII
`(US)
`
`.
`.
`.
`(73) ASSlgnee‘ Te???“ SyStem corporatmm
`W1 mmgtom MA(US)
`,
`,
`,
`,
`,
`(*) Notlcei
`811met to any dlSClalmer, the term 0fth15
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`
`.
`(21) Appl’ NO” 09/223545
`(22) Filed:
`Dec. 30, 1998
`
`4,115,619 A
`4,188,358 A
`4,211,822 A
`
`42152170 A
`4,403,004 A
`4,407,871 A
`4,431,711 A
`4,503,189 A *
`4,713,143 A
`5,174,434 A
`5,198,272 A
`5,284,679 A
`5,290,625 A
`5,320,869 A
`5,384,161 A
`5,464,661 A
`5,468,518 A
`
`
`
`9/1978 Kurfman et al.
`2/1980 Withoos et al.
`7/1980 Kurfman et al.
`
`............ 428/336
`..
`..... 264/255
`
`.
`..... 428/412
`
`N 428328
`7/1980 Vilaprinyo ~~~~~~
`428/31
`9/1983 Parker et al.
`10/1983 Eisfeller ...................... 428/31
`2/1984 Eisfeller ...................... 428/31
`3/1985 Igarashi et al.
`..... 525/104
`
`12/1987 Eisfeller .............. 156/655
`12/1992 Bourgoine
`198/80301
`
`3/1993 Eisfeller ..................... 427/251
`............ 427/240
`2/1994 Eisfeller et al.
`
`3/1994 Eisfeller et al.
`..... 428/216
`..... 427/250
`6/1994 Eisfeller et al.
`
`.
`..... 427/250
`1/1995 Eisfeller et al.
`
`..... 427/409
`11/1995 Lein etal.
`.................. 427/421
`11/1995 Lein et a1.
`
`(60)
`
`(51)
`
`Related US. Application Data
`Provisional application No. 60/070,166, filed on Dec. 31,
`1997~
`Int. C1.7 ........................... B32B 3/10; B32B 15/08;
`B32B 27/32; B32B 27/36; B32B 27/40
`....................... 428/201; 428/195; 428/198;
`(52) US. Cl.
`428/206; 428/208; 428/209; 428/421; 428/422;
`428/4246; 428/425.8; 428/425.9; 428/447;
`428/448’ 4‘8/450’ 428/457’ 428/458’ 428/461’
`428/462; 428/463; 428/474.4; 428/480;
`428/483; 428/515; 428/516; 428/518; 428/520;
`428/522; 428/523
`
`(58) Field of Search ................................. 428/422, 421,
`428/355 R, 355 EN, 355 N, 423.1, 424.2,
`4246, 4248, 457’ 4258, 4259, 461, 195’
`201, 203, 204, 206, 208, 209
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`3,118,781 A
`1/1964 Downing ................... 117/333
`3,916,048 A * 10/1975 Walles ..............
`428/35
`
`.............. 428/31
`4,101,698 A
`7/1978 Dunning et al.
`
`IO
`
`FOREIGN PATENT DOCUMENTS
`0358445 A2
`3/1990
`EP
`0392082 A2
`10/1990
`EP
`06/16906 A2
`9/1994
`EP
`WO 96133026
`“V1996
`W0
`4 cited by examiner
`'
`Primary Examine,_\,ivian Chen
`(74) Attorney, Agent, or Firm—Hamilton, Brook, Smith &
`Reynolds PC
`’
`'
`
`'
`
`(57)
`
`ABSTRACT
`
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`6“.“91’ as.”
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`1 me a £156 Cfmpos‘? fompf‘tngla
`ayer,.a
`ISCOH 111110115. 1H erme 10.6 ayer comprlsmg
`IS-
`crete 1slands of metal 1n an adheswe, and a second thermo-
`.
`.
`.
`.
`.
`plast1c layer. The metalhzed c0mpos1tes of the 1nvent10n can
`be. employed as. reflective surfaces, such as are used as
`m1rrors 0r subst1tutes for chrome trim on automoblles. A
`particularly preferred metal as a component of the discon-
`“Imus layer Of the comp051te IS mmum‘
`
`36 Claims, 3 Drawing Sheets
`
`
`
`
`
`V
`
`
`
`I6
`
`22
`
`Wavelock
`Exhibit 1001
`Page 1
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:19)(cid:20)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:20)
`
`

`

`US. Patent
`
`Sep. 24, 2002
`
`Sheet 1 0f3
`
`US 6,455,138 B1
`
`
`
`FIG. 2
`
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:19)(cid:20)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:21)
`
`

`

`
`
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:19)(cid:20)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:22)
`
`

`

`US. Patent
`
`Sep.24,2002
`
`Sheet3 0f3
`
`US 6,455,138 B1
`
`
`
`mm
`
`
`IIIIIlIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIMIIIIIIIIIIIIIIIIIIIIIIIII‘IIIIII
`)’"““"‘l“’|l“I"‘II"“"“I“
`
`mum
`
`Nm
`
`Wavelock
`Exhibit 1001
`Page 4
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:19)(cid:20)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:23)
`
`
`
`
`

`

`US 6,455,138 B1
`
`1
`METALLIZED SHEETING, COMPOSITES,
`AND METHODS FOR THEIR FORMATION
`
`RELATED APPLICATION
`
`This application claims priority to US, Provisional Appli-
`cation No. 60/070,166, filed Dec. 31, 1997, the contents of
`which are incorporated herein by reference in their entirety.
`BACKGROUND OF THE INVENTION
`
`Metallized polymer sheeting is now commonly employed
`as a substitute for decorative chrome parts, especially in the
`automotive industry. Typically, such metallized polymer
`sheeting includes a layer of metal disposed between two
`polymer sheets.
`There are several problems, however, with many types of
`known metallized polymer sheets. For example, laminates
`typically include an electrically continuous metal
`layer
`sandwiched between two polymer sheets. Such materials are
`often subject to delamination consequent to poor binding
`between the metal layer and the polymer layers on either
`side. Further, corrosion of the metal layer, which is usually
`aluminum can spread between the polymer layers, thereby
`causing significant diminution in appearance.
`One attempt to reduce the likelihood of delamination and
`loss of appearance resulting from corrosion of the metal
`layer has been to form a discontinuous metal layer on a
`aolymer basecoat, such as a resinous urethane. A monomer
`op-coat, such as a solvent-based aliphatic urethane, is then
`deposited on the discontinuous metal
`layer, and subse-
`quently polymerized to encapsulate metal islands of the
`discontinuous metal layer and to bond them to the polymer
`3asecoat.
`
`
`
`However, formations of metal islands on various types of
`wolymers can be difficult. Also, bonding of a urethane top
`layer during polymerization to a polyurethane basecoat can
`3e poor. One attempt to improve adhesion has been to etch
`he basecoat and discontinuous metal layer with a sodium
`iydroxide solution to remove residual metal between islands
`of the discontinuous metal layer. A limitation to this method
`is that etching can result in the formation of blackened areas
`in the metal layer, thereby detracting from the appearance of
`he resulting laminated part.
`There are several other problems that can be associated
`with polymerizing a top layer in situ to form metallized
`Jolymeric sheeting. For example, polyurethanes,
`in
`aarticular, generally are not sufliciently hydrophobic to
`3revent weathering over extended periods of time and are
`easily attacked by sodium hydroxide and acids, such as nitric
`acid. Thicker layers of polyurethane top-coat are difficult to
`form because in situ polymerization can cause the resulting
`composite to appear irregular. In addition, evaporation of a
`solvent component during polymerization of urethanes can
`cause “popping” or bubbles to form, also diminishing the
`appearance of the finished product. Further, methods which
`employ deposition of a basecoat, such as a resinous urethane
`basecoat, require that the basecoat be applied to a substrate,
`from which the resulting metallized composite generally
`cannot be removed. Therefore, the utility of this method for
`forming various products, having different applications, is
`limited.
`
`Therefore, a need exists for a metallized composite and a
`method for forming such a metallized composite that over-
`comes or minimizes the above-referenced problems.
`SUMMARY OF THE INVENTION
`
`The present invention is directed to a metallized sheeting,
`such as a formable metallized plastic sheet, and a composite.
`
`5
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`30
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`2
`The invention is also directed to a method for forming the
`sheeting and composite.
`In one embodiment, the invention is a formable metal-
`lized plastic sheet which, upon molding, does not cause
`degradation of reflectivity of the metal sheet.
`In another embodiment, metallized composite includes a
`first thermoplastic layer and a discontinuous layer on the
`first layer. The discontinuous layer is formed of discrete
`islands of metal in an adhesive. Asecond thermoplastic layer
`is disposed over the discontinuous layer, whereby the dis-
`continuous layer is between said first and second thermo-
`plastic layers.
`the metallized sheeting
`In still another embodiment,
`includes a continuous thermoplastic sheet and at least one
`discontinuous layer of metal within said thermoplastic sheet.
`The method includes depositing a metal on a first ther—
`moplastic layer to form a discontinuous layer of the metal.
`A second thermoplastic layer is laminated onto the discon-
`tinuous layer.
`invention has several advantages. For
`The present
`example, neither thermoplastic layer of the composite is
`polymerized in situ. Rather,
`the thermoplastic layers are
`laminated together to sandwich the discontinuous layer of
`metal islands in an adhesive bedding. Consequently, a wider
`variety of polymers can be employed to form the composite,
`thereby enabling greater opportunity for improving specific
`qualities of the composite and for tailoring construction of
`the composite for specific uses. For example, the choice of
`polymerized web materials can be selected for improved
`formation of discrete metal islands, such as by combining a
`particular metal with a polymer web that minimizes residual
`metal between metal islands. Alternatively, a polymer web
`can be selected that is preferably suitable for specific meth-
`ods of metal deposition. By minimizing the amount of metal
`that remains between metal
`islands of the discontinuous
`
`layer, the need for etching can be significantly reduced or
`eliminated.
`
`Further, because a top polymeric layer is not formed in
`situ, greater thicknesses can be employed without diminish-
`ing the appearance of the finished product, thereby improv-
`ing resistance to environmental use conditions, such as
`weathering. In some instances, a plasma of unsaturated
`monomers, such as acrylates or methacrylates, may need to
`be polymerized on indium in vacuo; in such instances, the
`top layer would be added in another operation. Also, evapo-
`ration of solvents during polymerization is eliminated,
`thereby preventing “popping” and other potential processing
`problems. Moreover, a wider variety of methods of forming
`the composite can be employed, such as by depositing metal
`islands first on a thermoplastic drum surface, and subse-
`quently transferring the metal islands to a first continuous
`thermoplastic web. A second thermoplastic web can then be
`applied over the discontinuous layer to form the composite.
`In other embodiments, the first and second thermoplastic
`webs can be bonded to each other by melting, use of an
`adhesive, or by compression. All of these processing options
`provide potential sources for reducing the cost of production
`and increasing overall product quality and productivity.
`Different polymers can be employed for the two thermo-
`plastic sheets, thereby further broadening the utility of the
`composites of the invention. In addition, neither the first nor
`the second thermoplastic web is bound to a substrate.
`Consequently, composites of the invention can be made to
`be flexible. Specific applications of flexible reflectors or
`mirrors can include adjustable rear-view mirrors for use in
`automobiles and as substitutes for conventional chrome-
`
`Wavelock
`Exhibit 1001
`Page 5
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:19)(cid:20)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:24)
`
`

`

`US 6,455,138 B1
`
`3
`plated metal parts. In another embodiment, the composites
`can be molded after formation without degradation of the
`reflectivity of the discontinuous metal layer. Molding, such
`as embossing, for example, can provide an inexpensive
`means for incorporating a logo into flexible patches, such as
`can be applied to apparel, footwear, etc.,
`that have the
`appearance of being perfectly reflective.
`Other uses include in—mold decoration, blow molding and
`thermoforming. In-mold decoration, for example, includes
`injection molding a thermoplastic behind the sheet of com-
`posite to enable formation complex plastic art, such as parts
`having a reflective, mirror-like surface. The injection mold-
`ing resin should be compatible with the first layer (the layer
`that will contact
`the molten injection molding resin).
`Preferably, the composition of the injection molding resin
`and the composition of the first layer of the composite will
`be the same; for example, injection molding a thermoplastic
`polyolefin (TPO) onto a composite which has as its first
`layer (facing the polymer melt) a TPO. Alternatively, the
`first thermoplastic layer and the injection molding resin
`should be compatible in the melt stage. An example of such
`a combination is a thermoplastic sheet of polycarbonate and
`an injection molding resin of polycarbonate-ABS blend.
`Blow molding is similar to injection molding except that
`the molding resin is melted, extruded through a die and then
`blown with air or gas pressure against the walls of a mold
`cavity. In this case, a sheet of composite would be inserted
`into the mold and then the resin would be injected behind it.
`In a thermoforming operation, the sheet is heated to soften
`it and then pushed into a cavity of a particular shape by a hot
`die surface. Vacuum forming is a similar process that also
`incorporates a vacuum to draw the softened sheet into the
`mold cavity as die pressure is applied to the opposite face.
`BRIEF DESCRIPTION OF TIIE DRAWINGS
`
`FIG. 1 is a cross-section of one embodiment of the
`
`composite of the invention, wherein first and second ther-
`moplastic layers are bound together by an adhesive.
`FIG. 2 is a cross-section of another embodiment of the
`
`composite of the invention, wherein a continuous thermo-
`plastic layer encapsulates a discontinuous layer of metal.
`FIG. 3 is a schematic representation of one embodiment
`of apparatus suitable for forming a composite of the inven-
`tion.
`
`FIG. 4 is a schematic representation of an alternate
`apparatus for forming a composite of the invention.
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`The features and other details of the apparatus and method
`of the invention will now be more particularly described
`with reference to the accompanying drawings and pointed
`out in the claims. It will be understood that the particular
`embodiments of the invention are shown by way of illus-
`tration and not as limitations of the invention. The principal
`features of this invention can be employed in various
`embodiments without departing from the scope of the inven-
`tion. All parts and percentages are by weight unless other-
`wise specified.
`The invention is directed to a formable metallized plastic
`sheet and a method for forming the metallized plastic sheet.
`The term “formable,” as defined herein, includes, inter alia,
`suitability for
`in-mold decoration, blow molding,
`thermoforming, vacuum forming, etc. The formable metal-
`lized plastic sheet, upon molding, does not cause degrada-
`tion of reflectivity of the metal sheet.
`
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`60
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`65
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`4
`In one embodiment, shown in FIG. 1, metallized com-
`posite 10 includes first thermoplastic layer 12. Discontinu-
`ous layer 14 is on first thermoplastic layer 12 and includes
`first side 16 and second side 18. Discontinuous layer
`includes discrete islands of metal 20 and adhesive 22.
`Second thermoplastic layer 24 is on discontinuous layer 14,
`whereby discontinuous layer 14 is between the first and
`second thermoplastic layers. Discontinuous layer 14 prefer-
`ably includes discrete specular islands of metal. Suitable
`metals, as defined herein, are those that can be deposited, or
`formed, on a suitable thermoplastic polymer. Examples of
`suitable metals include indium, zinc, tin, gallium, aluminum,
`cadmium, copper, nickel, cobalt, chromium,
`iron, gold,
`platinum, palladium, rhodium, etc. Preferably, the metal is
`indium. Also, preferably, discontinuous layer 14 is reflec—
`tive; most preferably, discontinuous layer 14 has a mirror or
`mirror-like appearance. Optionally, discontinuous layer 14
`can include specular islands of metal alloy. Examples of
`suitable alloys include stainless steel, nichrome, etc.
`Examples of suitable adhesives of discontinuous layer 14
`include at
`least one compound selected from the group
`consisting of styrene-butadiene copolymers, ethylene Vinyl
`acetates, polyesters, polyamides, epoxies, acrylic pressure—
`sensitive adhesives, silicone pressure-sensitive adhesives,
`polyurethanes and isocyanate-cured polymers. The adhesive
`can be a thermally-activated adhesive.
`In one specific embodiment, the adhesive includes two
`components. Preferred embodiments of adhesives that
`include at least two components include combinations of
`polyester, polychloroprene or polyurethane with isocyanate—
`functional crosslinkers, and a combination of water-based
`polyurethane dispersion with aziridine or with a water-
`dispersable isocyanate crosslinker.
`In another specific
`embodiment,
`the adhesive can be suitable for curing by
`exposure to ultraviolet light. An example of such an adhe-
`sive is ultraviolet light-curable pressure-sensitive adhesive.
`First and second thermoplastic layers include at least one
`suitable thermoplastic polymer. These layers can also be
`formed of the same material, or they can be formed of
`different materials. A suitable thermoplastic polymer, as
`defined herein, is a thermoplastic polymer that effectively
`shields discontinuous layer 14 from environmental factors,
`such as weathering, humidity, and acidic or basic solutions
`encountered during ordinary intended final use of the com-
`posite. Examples of acidic and basic solutions include mild
`solutions of nitric acid or caustic. Specific examples of
`suitable thermoplastic polymers include,
`inter alia,
`polyethylene, polystyrene, polycarbonate, polyethylene
`terephthalate (PET), glycol-modified polyethylene tereph-
`thalate (PETG), polyvinylchloride (PVC),
`thermoplastic
`polyurethane (TPU), acrylonitrile butadiene styrene (ABS),
`polymethylmethacrylate, polypropylene, polyvinyl fluoride
`(PVF), TPO, polyethylene napthalate (PEN),
`polymethylpentene, polyimide, polyetherimide, polether
`ether ketone (PEEK), polysulfone, polyether sulfone, ethyl-
`ene chlorotrifluoroethylene, cellulose acetate, cellulose
`acetate butyrate, plasticized polyvinyl chloride, polyester
`polycarbonate blends, ionomers (Surtyn), and co-extruded
`films or sheets of these thermoplastics, etc. The thermoplas—
`tic polymers can be elastomeric thermoplastics, and are
`commonly referred to as thermoplastic elastomers or TPE’s.
`Examples include polyurethane (TPU), styrene-butadiene-
`styrene (SBS), styrene-ethylene-butadiene-styrene
`(SEEBS). Examples of opaque or translucent thermoplatics
`include polypropylene, polyamide, polyphenylene sulfide
`(PPS), styrene-maleic anhydride, polytetrafluoroethylene
`(PTFE), polycarbonate-ABS blends, polycarbonate polyes-
`ter blends, modified polyphenylene oxide (PPO).
`
`Wavelock
`Exhibit 1001
`Page 6
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:19)(cid:20)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:25)
`
`

`

`US 6,455,138 B1
`
`5
`In one embodiment, first thermoplastic layer 12 predomi-
`nantly includes a first thermoplastic polymer and a second
`thermoplastic layer 24 predominantly includes a second
`thermoplastic polymer. Examples of suitable combinations
`of first and second thermoplastic polymers are combinations
`of polyvinylidene difiuoride (PVDF) and acrylonitrile buta-
`diene styrene (ABS), PVDF/TPO, TPU/PVC, etc.
`First thermoplastic layer 12 or second thermoplastic layer
`24, or both, can be clear or tinted. Examples of suitable
`components for tinting continuous thermoplastic layers 12
`and or 24 include suitable organic or inorganic dyes or
`pigments, etc. As an alternative to tinting the thermoplastic
`layer, the adhesive can be tinted. This has the advantage of
`being cheaper than adding colorant
`to plastic sheeting;
`moreover, the plastic sheeting can screen the colorant for
`exposure to ultraviolet light (UV), thus making it possible to
`use nonlight—fast colorants.
`In another embodiment, first
`thermoplastic layer 12 or second thermoplastic layer 24 can
`be opaque. Examples of suitable components that can cause
`opacity include carbon black, iron oxide, titanium dioxide,
`etc.
`
`Metallized composite 10 can be embossed, such as by a
`conventional method, including, for example, heat pressing.
`As another option, metallized composite 10 can be formed,
`for example, to form a part that is to exhibit a translucence
`that
`is a multiple of the translucence of a single-ply of
`metallized composite. As another alternative, metallized
`composite 10 can be supported by a substrate, whereby
`metallized composite 10 is in contact with the substrate.
`Examples of suitable substrates include thermoplastic
`polyurethane, polyvinylchloride, glycol modified
`polyethylene,
`thermoplastic polyolefin,
`fiber reinforced
`nylon, fiberglass, aluminum, and metal alloys, such as steel,
`etc.
`
`In another embodiment, metallized composite 26, shown
`in FIG. 2, includes continuous thermoplastic sheet 28 that
`encapsulates discontinuous layer 30 of metal. The metal, or
`metals of discontinuous layer 30, and suitable thermoplastic
`polymers of continuous thermoplastic sheet 28 are the same
`as those described above with reference to FIG. 1.
`As with the embodiments set forth above and shown in
`FIG. 1, metallized composite 26 of FIG. 2 can include one
`or more thermoplastic layers that are clear, tinted or opaque.
`Also, elastomeric thermoplastic composite can be supported
`by a substrate, formed or embossed. In one embodiment,
`discontinuous layer 30 substantially partitions thermoplastic
`sheet 28, whereby thermoplastic sheet 28 predominantly
`includes a first thermoplastic polymer at first side 32 of
`discontinuous layer 30, and predominantly includes a sec-
`ond thermoplastic polymer at second side 34 of discontinu-
`ous layer 30.
`The method for forming a metallized composite of the
`invention generally includes depositing a metal on a first
`thermoplastic layer to form a discontinuous layer of the
`metal. A second thermoplastic layer is laminated onto the
`discontinuous layer. Suitable methods for deposition of
`metal on the first
`thermoplastic layer includes electron
`evaporation, sputtering, ion plating, induction heating, ther-
`mal evaporation, transfer of a preformed metal layer from a
`separate substrate, etc.
`Optionally, the method includes bonding the first thermo-
`plastic layer to the second elastomeric thermoplastic layer.
`Examples of suitable methods for bonding the thermoplastic
`layers include heating, to thereby cause the layers to melt
`combined and form a single, continuous thermoplastic layer.
`Alternatively, the layers can be bonded by heating without
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`melting, pressing the layers together, or applying a suitable
`adhesive to the first and/or second thermoplastic layer before
`laminating the layers together.
`In embodiments where an adhesive is employed that is
`curable by ultraviolet light, the method includes exposing
`the thermoplastic composite to ultraviolet light to thereby
`cure the adhesive. Alternatively, a UV—curable adhesive
`applied to one thermoplastic layer can be exposed to UV
`light and then laminated to a second thermoplastic layer.
`Conventional methods can be employed to conduct other
`optional steps, such as molding, folding, and/or embossing
`the metallized composite. In one embodiment, apparatus 40,
`shown in FIG. 3, is employed to conduct a method of the
`invention. Therein, first
`thermoplastic layer 42 is drawn
`from roll 44 across deposition guns 46 by reel 48. Deposi-
`tion guns 44 deposit a suitable metal, such as indium on first
`thermoplastic layer 42. Deposited metal forms discrete
`islands on first thermoplastic layer 42, which then passes
`across roller 50. Preferably, roller 50 cools first thermoplas-
`tic web 42. Optionally, first elastomeric thermoplastic web
`42 is coated with an adhesive deposited prior to or after
`deposition of specular islands of metal.
`Second elastomeric thermoplastic layer 52 is drawn from
`roll 54 by reel 48. Optionally, second thermoplastic layer 52
`is coated with an adhesive. First and second thermoplastic
`layers 42, 52 meet at rollers 56. In one embodiment, rollers
`56 are heated. Preferably, in embodiments where rollers 56
`are heated, they are heated to a temperature of about 300° F.
`First and second elastomeric thermoplastic layers 42, 52
`become bonded to each other while passing through rollers
`56, to thereby form a thermoplastic composite 58 of the
`invention. Thermoplastic composite 58 is drawn across
`roller 60 and then collected on reel 48.
`
`In another embodiment, apparatus 70, shown in FIG. 4, is
`employed to conduct a method of the invention. In this
`embodiment, drum 72 includes a suitable thermoplastic
`coating 74. Asuitable thermoplastic coating is one that will
`enable formation of discrete metal
`islands thereon by
`deposition, such as by electron beam evaporation, and which
`is suitable for transfer of metal islands to a first thermoplas-
`tic layer. An example of a suitable thermoplastic coating of
`drum is JPS 1880 Glossy 2® sheet stock material (urethane).
`Drum 72 rotates, whereby metal plumes formed by depo-
`sition guns 76 cause deposition of the metal onto thermo-
`plastic coating 74 of drum 72. As drum 72 rotates, discon-
`tinuous layer 78 of metal islands forms on thermoplastic
`coating 74 of drum 72.
`First thermoplastic layer 80 is drawn from drum 82 by
`take-up reel 84. During conveyance from drum 82 to take-up
`reel 84, first thermoplastic layer 80 passes between rollers 86
`and drum 72. Rollers 86 press first thermoplastic layer 80
`against discontinuous layer 78 on drum 72, thereby trans-
`ferring discontinuous layer 78 to thermoplastic layer 80. In
`one embodiment, rollers 86 are heated.
`Second thermoplastic layer 88 is drawn from drum 90 by
`take-up reel 84. Optionally, an adhesive is deposited on
`second thermoplastic layer 88. First and second thermoplas-
`tic layers 80, 88 meet at rollers 92. Rollers 92 cause contact
`between first and second thermoplastic layers 80, 88.
`Preferably, rollers 92 are heated. Contact between first and
`second thermoplastic layers 80, 88 at rollers 92 causes
`formation of a thermoplastic composite of the invention. The
`thermoplastic composite is subsequently collected on take-
`up reel 84.
`In another embodiment, indium is vacuum deposited on a
`first thermoplastic layer. The metallized sheet is removed
`
`Wavelock
`Exhibit 1001
`Page 7
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:19)(cid:20)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:26)
`
`

`

`US 6,455,138 B1
`
`7
`from the vacuum chamber and laminated to a second ther-
`moplastic layer or to the second thermoplastic layer with
`adhesive pre-applied, using conventional laminating meth-
`ods employed in the coating/laminating industry.
`Alternatively, the deposited indium layer is coated in vacuo
`with a thin plasma-polymerized coating to protect the met-
`allization.
`
`In still another embodiment, an interleaf of plastic film,
`usually polyethylene or polyethylene terephthalate is wound
`with the indium metallization to protect the metal layer as it
`is rewound. It is subsequently stripped out as the metallized
`sheeting is coated or laminated.
`In a further embodiment, the metallized sheeting is lami-
`nated to a film adhesive. A film adhesive consists of a layer
`of adhesive between two release liners. One liner at a time
`can be removed and the adhesive laminated to one thermo-
`plastic sheeting. The second liner can then be removed and
`the laminate is adhered to the second thermoplastic layer.
`The performance of the metallized composite can be
`further improved by overcoating or overlaminating addi—
`tional
`layers of polymerized plastics or films over the
`composite to further improve abrasion resistance, chemical
`resistance, weathering resistance, etc. For example, a
`UV—curable hardcoat can be applied to the metallized c0111-
`posite and then cure the coating by exposure to high-
`intensity UV light.
`The invention will now be further described by the
`following examples, which are not intended to be limiting in
`any way. All parts and percentages are by weight unless
`otherwise specified.
`EXEMPLIFICATION
`
`Example 1
`
`Asample 0f A-4100® clear urethane sheet stock, made by
`Deerfield Urethane, A Bayer Company, South Deerfield,
`Mass., was metallized in a 72" metallizer
`(Part
`#EJWIN403MM30, made by Kurt J. Lesker Co.,
`Inc.,
`Clairton, Pa.). About 300 A A of indium was deposited,
`through electron beam deposition, onto the surface of the
`urethane. A second sheet of A—4100® clear urethane sheet
`
`stock was removed from its polyester released liner backing
`and was gently pressed onto the surface of the indium.
`Special attention was given to removing air bubbles that
`might expand in the convection process. A heat gun was then
`utilized to heat the two samples. The conventional heat gun
`was set to a temperature of 400° F. and was held at a distance
`of approximately 4 inches from target. When exposed to the
`heat,
`the two identical sheets of material
`immediately
`showed signs of melting as the two materials appeared to be
`fused together. The indium layer slightly discolored during
`the convection heating. Samples of the same type were
`repeatedly run to attempt to maximize appearance. Finally,
`a convection oven set at a temperature of 300° F. was used
`to melt the materials together over a 4—5 minute duration.
`Slight iridescence persisted with the fusing process. Since
`the initial trials with the A-4100® clear urethane sheet stock,
`it was been determined that the metallized unprotected sheet
`appeared to have a finite shelf life, whereafter the sample
`will discolor, and eventually turn white with thermal appli-
`cation of the top film. In practice, it should be the intent of
`the designer to have the materials mated as soon as possible
`to prevent this occurrence.
`
`Example 2
`A sample of JPS 1880 Glossy 2® sheetstock material
`(urethane) was metallized in a 72" metallizer (Part
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`Inc.,
`#EJWIN403MM30, made by Kurt J. Lesker Co.,
`Clairton, Pa.). About 300 A of indium was deposited,
`through electron beam deposition, onto the surface of the
`urethane. A sample of the A-4100® clear urethane sheet
`stock, with the polyester release liner backing removed, was
`then gently applied to the surface of the indium. The
`sandwiched samples were then inserted into a 300° F.
`convection oven for a duration of 2 minutes. The samples
`were then removed from the oven and allowed to cool to the
`
`touch. The samples were then manually pulled apart by
`starting a separation at the edge. At this point it was noted
`that
`the indium had been effectively transferred to the
`A-4100® clear urethane sheet stock substrate. The indium
`surface maintained its superior reflective properties with no
`distortion evident. The sample of the JPS material was
`discarded, while a second sheet of A—4100® clear urethane
`sheet stock was thermally adhered to the first using the same
`process outlined above.
`
`Example 3
`
`Additional work was performed using an adhesive tech-
`nique for application of the protective film. Two samples of
`sheet, JPS 1880 Glossy 2® sheet stock and 30 mil E-grade
`double polished PVC film were used. Both of the sheets
`generally had a transparent appearance, but the E-grade
`double polished PVC film material had a slight blue tint due
`to the resin’s inherent nature. They were a metallized in a 72'
`metallizer (Part #EJWIN403MM30, made by Kurt J. Lesker
`Co., Inc., Clairton, Pa.). About 300 A of indium was
`deposited, through electron beam deposition, onto the sur-
`face of the urethane. After metallization, an adhesive-backed
`film of PVC, KPMF® black, supplied through Kay Auto-
`motive Graphics, Inc. from KPMF, Inc., Wells, Okla., was
`carefully applied to the indium layers of each sample. The
`sample, when viewed through the JPS 1880 Glossy 2® sheet
`stock material or E-grade double polis