`
`[19,
`V
`
`Parker et al.
`
`[11]
`
`[45]
`
`4,403,004
`
`Sep. 6, 1983
`
`SANDWICH METALIZED RESIN
`
`4,275,099
`
`6/1981 Dani .................................... .. 428/31
`
`[54]
`
`[75]
`
`[73]
`
`[21]
`
`[22]
`
`[51]
`
`[52]
`
`[53]
`
`[56]
`
`Primary Examiner—Thomas J. Herbert, Jr.
`LAMINATE
`Attorney, Agent, or Firm—David A. Jackson; Daniel H.
`Inventors: Harry A. Parker, Murray Hill;
`B01315
`Joseph Greenman Plainfield, both of
`ABSTRAC1‘
`[57]
`N-1
`’
`A decorative metallized laminate having improved bril-
`Assign‘?-3‘ Transfef Prim F0115: 1'”-o East
`liance, reflectance and weatherability comprises a base
`Br“n5W1Cks N-1
`Laytir ;S)re;Earee:1 ft'rhon1e(a;fthern::(—“f0rrrit21t]b1e‘resin fslm, wtitg
`APPL NOJ 314,314
`0
`ur ac '
`er
`coa
`W]
`V‘ por
`eposi e
`metal layers. An outer protective capping layer pre-
`Filed:
`Oct. 23', 1981
`fggggtfggg 30213;]:1;jg‘55:;glagtaflrglerigrfgrfcgfgtgg:3;
`Int. cu ...................... mm 13/00; 1329c 19/00;
`...................................._. 444
`the metallized surfaces of the base layer. A pressure and
`156/244.27; 423/332; 428/335; 428/337;
`heat -sensitive elastomeric adhesive coating is disposed
`428/339; 428/343; 423/347; 428/913; 428/914
`between the capping layer and the metallized surface of
`Field of Search ............... .. 428/31, 343, 335, 337,
`the base layer, to form the bond between the two layers.
`428/347, 339, 421, 463, 913, 914; 156/244.27,
`A compatible thermo—formable resin backing layer may
`243
`be laminated to the free metallized surface of the base
`layer, to provide a composite laminate suitable for ther-
`mo-forming and injection molding to manufacture a
`variety of products.
`A method for preparing the metallized laminate is also
`disclosed.
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`3,152,950 10/1964
`3,720,567
`3/1973
`3,811,989
`5/1974
`4,101,698
`7/1978
`4,235,949 11/1980
`
`Palmquist et al.
`................ .. 428/335
`Shanok et al.
`..
`......... .. 428/31
`Hearn ............ ..
`156/244.27 X
`
`Dunning et al.
`. . . .
`. . . . . . . . . .. 428/31
`Van Manen et al.
`............... .. 428/31
`
`18 Claims, 4 Drawing Figures
`
`
`
`Wavelock . Exhibit 1009
`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:28)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:20)
`
`
`
`U.S. Patent
`
`Sep.A6,,1983
`
`Sheet 1 of2
`
`4,403,004
`
`Wavelock
`Exhibit1009
`Page2
`(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:28)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:21)
`
`
`
`U.S. Patent
`
`Sep 6 1983
`
`‘ Sheet 2 of2
`
`4,403,004
`
`00
`
`£:3u<>
`
`0?
`
`V?
`
`mm
`
`no3NNfm
`Nam2.‘0.
`
`am
`
`2om
`
`NV
`
`mm
`
`
`
`
`
`I".--IIIIIII.IIIIIIIIIIIIl-IIII.IIIIIIIIIIIIIIIIIIIIIIII‘\.:/V:t.n.H!n«g§EU:§§E§E§Eh §§éE=F§V.
`
`
`rugs‘II.IHa»?IIIIIIII”llI'llIIIII!ll
`
`NM2
`
`a.......:'l...l-"".DH"l9
`
`L?
`
`ON
`
`Wavelock
`Exhibit1009
`Page3
`(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:28)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:22)
`
`
`
`
`
`
`1
`
`4,403,004
`
`SANDWICH METALIZED RESIN LAMINATE
`
`BACKGROUND; OF THE INVENTION
`1. Fieldof the Invention
`,
`The present invention relates to reflective ‘decorative
`laminates, and more parzticulyarlypto such laminates as
`are useful in applications requiring exposure to mechan-
`ical stress and environmental extremes.
`'2. Description of the Prior Art
`n
`A variety of decorative, reflective laminates prepared
`‘with a variety of resin materials, have been developed
`and in existence for some time. With the increasing
`' concern for safety and weight reduction, that has devel-
`oped in the automotive industry, for example, the use of
`such reflective ‘laminates in place‘ of reflective articles
`prepared entirely from metal, has been on the increase.
`Thus, structures such as bumpers, side trim, grill work
`and the like, previously prepared from relatively rigid
`and heavier chromium-plated metals, ar'e"be_ing replaced
`by the lighter weight resinous materials.
`While wide-spread employment of resinous materials
`exists, their use has been primarily in thelinstance where
`pigmented non-reflective hardware such as bumpers,
`and the like, is acceptable in the design of the vehicle. In
`those instances where reflective surfaces are desired,
`however, the manufacturers tend to continue their use
`of the conventional plated metal, because they find that
`the reflective surfaces prepared from resinous laminates
`‘tend to be of inferior brightness and reflectivity, and
`frequently exhibit surface defects when exposed to me-
`chanical impact, as well, as deterioration of the metallic
`layer after relatively short exposure to atmospheric air
`and sunlight.
`,
`_
`A variety of laminates specifically designed for auto-
`motive application have been devel_oped, all of which
`have attempted to remedy the aforementioned deficien-
`cies, by providing, in pertinentpart, a reflective metal
`layer, usually vapor deposited upon a transparent resin
`film, with the resulting metal coated film bonded adhe-
`sively to one or more further-‘resin films, so that the
`metal layer is presumably securely disposed within the
`resulting laminates. Variations on this construction are
`illustrated in the following U.S. Pat. Nos. 4,275,099;
`4,235,949; 4,101,698; 3,811,989; and 3,720,567. Natu-
`rally, the foregoing listing is illustrative only, as other
`patents, and related publications illustrate yet further
`variations in construction -and preparation of such lami-
`nates.
`,
`,
`Of the patents listed, U.S. Pat. No. 4,275,099 to Dani
`is of particular interest, as it-discloses in its general
`, -discussion, a laminate construction that
`is presently
`popular, that of the.—»tri-larninate-.:Dani describes this
`construction as essentially three-ply, constituted of an
`aluminized polyester film, adhesively bonded to outer
`polyvinylfluoride film and bonded on its opposite side
`to a base layer of what patenteeterms a “virgin vinyl
`resin.” Thepatentee states further, that the tri-laminate
`maybe either heat fused or otherwise adhesivelybofnded
`to a three dimensional extrusion, to form products: such
`as automotive trim stripstand the like.
`-
`The deficiencies of this stateof the art construction
`are also noted by Dani, in that patentee remarks that the
`laminated products tend to delaminate in use after rela-
`tively short exposure to outside environments. Dani
`notes that delamination frequently occurs at the adhe-
`sive interface between the metallized surface and -the
`
`2
`. next adjacent resin film, and proposes a specific adhe-
`sive formulation that purportedly remedies this defect.
`In addition to those deficiencies noted by Dani, the
`present inventors found that the commercial production
`of the known tri-laminates was exceeding difficult if not
`impossible, when attempts were made to adapt these
`tri-laminates to the preparation of automotive»accesso-
`ries by thermo forming techniques. Thus,‘ it was ob-
`:served that when the temperaturesof the tl1ermo;form-
`ing operation fluctuated outside illustrative tolerances,
`of about 5° F., the resulting products exhibited surface
`-crazing, the development of a haze in the~resi_n films that
`reduced brightness and reflectivity, and an effect
`known as ffrainbow,” i.e., a multi-color hue that appears
`due to the distortion of the polyester film during the
`thermo forming process. Further, the appearance of any
`of the foregoing defects would result in the rejection by
`automobile manufacturers of products having these
`defects. .
`.
`v_
`.
`g _A further problem, noted by Dani, and others in the
`art, comprises the susceptibility of the resin laminate. to
`attack and rapid deterioration upon exposure to ultra-
`violet_ light. Dani proposes to includean ultra-violet
`inhibitor in the polyester film to. reme_dy,.this.defect. The
`present inventors have found, however, that the adhe-
`sive utilized in .the laminates presentlyknown, have
`generally low resistance to deterioration fromexposure
`toultra-violet light, and therefore fail within an unac-
`ceptably short period of time after their.installation.
`Further, the prior art adhesives,ap,pear to attack the
`adjacent metal layeriand to cause it to corrode, with the
`result that desired appearance and laminate integrity
`rapidly deteriorate.
`‘
`_
`I
`.A need therefore exists for the development of an
`improved laminate and associated method of prepara-
`tion that can efficiently and economically cure the
`noted product deficiencies.
`SUMMARY OF THE INVENTION
`
`10
`
`I5
`
`20
`
`25
`
`30
`
`35
`
`In accordance with the present‘ invention, a’d’ecora-
`tive metallized laminate exhibiting improved brilliance,
`reflectance and weatherability is disclosed which com-
`prises a base layer prepared from a thermo formable
`resin film having both surfaces thereof coated with a
`thin, adherent layer of metal, and an outer, protective
`capping layer prepared from a film ‘having at least one
`surface treated for receptivityto adhesive bonding and
`resistanceto attack by ultra-viiolet radiation, the cap-
`pinglayer adhesively bonded to’ one of théimetallized
`surfaces of the base layer. A’ ‘pressure and heat sensitive
`elastomeric adhesive coating, also resistant to attack by
`ultra-violet radiation and harmless to the metal layers, is
`disposed between the capping layer and the metallized
`surface of the base layer, and forms the bond therebe-
`tween. The present laminate maybe bonded to a com-
`‘ patable thermo"-formable resin backing layer that may
`be laminated to the free metallized surface of the base’
`layer.
`The base "layer is a non-oriented resin film prepared
`from material selected from the group consisting of
`amorphous polyester resins, polycarbonate resins, sub-
`stituted and unsubstituted vinyl polymers, and their
`co-polymers. Preferably,
`the non~oriented resin com-
`prises an amorphous polyester, such as polyethylene
`terephthalate and ranges in thickness from about 3 to
`about 8 mils. The metal layers may be applied by con-
`ventional techniques, such as vapor deposition, and may
`
`50
`
`55
`
`4 60
`~
`
`65
`
`Wavelock
`Exhibit1009
`iPage4
`(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:28)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:23)
`
`
`
`4,403,004
`
`3
`include chromium, nickel, iron, aluminum, and others,
`with aluminum preferred.
`The capping layer may be a material selected from
`the group consisting of fluorinated vinyl polymers,
`fluorinated polyolefins, and polyesters treated for resis-
`tance to ultra-violet radiation. Preferably, the capping
`layer comprises a polyvinylfluoride.
`The adhesive coating maybe a silicone resin or an
`acrylic resin, and preferably includes a catalyst
`in
`amount ranging from about 2% to about 6% by weight
`of the resin solids of the adhesive. Preferrably, the adhe-
`sive is a silicone resin such as a substituted polysiloxane,
`and the catalyst is a silicone compound as well.
`The present invention includes a method for prepar-
`ing the decorative metallic laminate, comprising the
`steps of applying the metal layer to one surface of the
`base layer, adhesively bonding the capping layer to the
`metallized surface of the base layer and thereafter met-
`allizing the free surface of the base layer. The resulting
`laminate may then be bonded by standard laminating
`techniques, such as extrusion lamination, to a backing
`layer of a thermo-formable resinous material. The re-
`sulting laminate may be extrusion molded to a pre-
`formed substrate or maybe formed into a three dimen-
`sional article by injection molding with additional resin-
`ous material adhesively compatible with the composi-
`tion of the backing layer. Such resinous material may
`include various known polyolefins, vinyl compounds
`such as polyvinylchloride, and others.
`The present laminates are particularly useful in the
`instance where automotive products for exterior expo-
`sure are prepared, as the combined inertness of the
`adhesive and the ultra-violet resistance of both the ad-
`hesive and the capping layer, substantially extend the
`useful life of the laminate surface, to resist ultra-violet
`radiation, chemical attack from the environment, and
`resistance to fracture from mechanical
`impact. The
`presence of the catalyst in the adhesive of the present
`laminate, promotes the formation of a firm bond be-
`tween the capping layer and the underlying base layer,
`that resists surface defect formation and delamination
`during subsequent thermo-forming operations, and pro-
`vides improved transparency that enhances the bril-
`liance and reflectivity of the metal layer.
`Finally, the provision of the sandwich of metallized
`surfaces surrounding the base layer, totally eliminates
`the “rainbow" effect that can result from the deforma-
`tion of the base layer during thermo-forming, as the two
`layers cooperate to provide a continuous surface re-
`gardless of the extent to which the base layer may be
`deformed in susequent manufacturing procedures.
`The present product is easily and inexpensively pre-
`pared without resorting to rigorous processing. Product
`uniformity is substantially improved so that the reject
`rate for formed parts drop well within commercially
`acceptable tolerances.
`'
`Accordingly, it is a principal object of the present
`invention to provide a decorative metallized laminate
`exhibiting improved brilliance, reflectance and weath-
`erability,
`that
`is capable of successfully undergoing
`thermo-forming operations.
`It is a yet further object of the present invention to
`provide a laminate as aforesaid, which eliminates the
`frequency of surface defects,
`loss of reflectance and
`breakdown of the metal layer upon exposure to ultra-
`violet light.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`65
`
`4
`It is a yet further object of the present invention to
`provide a laminate as aforesaid that is particularly useful
`for the formation of exterior automotive parts.
`It is a yet further object of the present invention to
`provide a method for preparing a bright, metallized
`laminate,
`that is simply and inexpensively practiced
`without resorting to rigorous conditions.
`It is a yet further object of the present invention to
`provide a method as aforesaid, forms a laminate product
`capable of successfully undergoing subsequent thermo-
`forming operation.
`Other objects and advantages will become apparent
`to those skilled in the art from a consideration of the
`ensuing description, which proceeds with reference to
`the following illustrative drawings.
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`FIG. 1 is a schematic fragmentary sectional view of a
`laminate in accordance with the present invention.
`FIG. 2 is a schematic representation of the process of
`the present invention.
`FIG. 3 is a schematic representation illustrating the
`state of preparation of the laminate at the various points
`of the process illustrated schematically in FIG. 2.
`FIG. 4 is a schematic perspective illustrating a typical
`automotive product utilizing the laminate of the present
`invention.
`
`DETAILED DESCRIPTION
`
`Referring to FIG. 1, the decorative laminate 10 is
`illustrated schematically and comprises a base layer 12
`that is prepared from a thermo formable resin film. The
`base layer 12 is preferably prepared from a non-oriented
`film selected from the group consisting of amorphous
`polyester resins, polycarbonate resins, substituted and
`unsubstituted vinyl polymers, and their copolymers.
`More particularly, the amphorous polyesters may in-
`clude polyethylene terephthalate, the polycarbonates
`may include acrylonitrile-butadiene-styrene resins, the
`vinyl polymers may include polyvinylchloride homo-
`or copolymers as well as other commercially available
`vacuum formable or thermo-formable materials.
`A preferred material for base layer 12 comprises a
`polyethylene terephthalate sold by Allied Chemical
`Corporation, known as “Petra.” The invention how-
`ever is not limited to this later material, so long as the
`base layer is substantially non-oriented, that is to say,
`has not been previously mechanically treated, to en-
`hance rigidity and “memory.”
`Base layer 12 may be provided in a variety of thick-
`nesses, depending upon the specific application for the
`resulting laminate, however, in the instance where an
`automotive laminate is contemplated,
`that
`is to be
`formed by injection molding as described hereinafter,
`base layer 12 preferably possesses a thickness ranging
`from about 3 mils to about 8 mils, and more specifically
`made be utilized at a thickness of 5 mils.
`Base layer 12 is provided on both of its surfaces with
`tightly adherent, reflective metal coatings 14 and 16.
`While metal coatings 14 and 16 may be applied by a
`variety of well recognized techniques, it is preferable in
`the present invention that metal coatings 14 and 16 be
`applied by vapor deposition. The techniques of vapor
`deposition, particularly as utilized in connection with
`the preparation of aluminized polyester films, are well
`known, and are described, for example, in the Modern
`Plastics Encyclopedia (1970-1971). at pages 7l0 and
`following. For example,
`in the instance where alumi-
`
`Wavelock
`Exhibit1009
`Page5
`(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:28)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:24)
`
`
`
`4,403,004
`
`5
`num is to be vapor deposited upon base layer 12, the
`aluminum (99+% pure) is held in a heated crucible in
`the form of pellets or the like, and is thereafter vapor-
`ized in a high vacuum chamber by resistance or induc-
`tion heating. Preferably, base layer 12 comprises a con-
`tinuous film, the running length of which is passed
`through the chamber so that one surface of the film is
`exposed to contact with the vaporized metal at a run-
`ning rate sufficient to deposit a uniform layer of the
`metal onto the film, to a thickness of from 100 to 200
`Angstroms. Simultaneously,
`the opposite side of the
`film may be subjected to cooling by contact with a
`cooling cylinder, to effect the condensation of the alu-
`minum on the metallized surface. Both of the metal
`coatings 14 and 16 may be prepared by the foregoing
`method, to the thicknesses specified above,
`in accor-
`dance with one embodiment hereof.
`The provision of metal coatings 14 and 16 on both
`broad surfaces of base layer 12, forms a sandwiching
`relationship therewith that obscures visual distortion
`that frequently results when base 12 is subjected to
`subsequent deformation by thermo forming techniques.
`Metal layers 14 and 16 are applied in a particular se-
`quence, that will be discussed later on with reference to
`the method of the present invention.
`Referring again to FIG. 1, an outer protective cap-
`ping layer 18 is provided, adhesively bonded to base
`layer 12, against metal coating 14. The exact sequence
`of application of capping layer 18 will be discussed later
`on with respect to the present method.
`is
`Capping layer 18 is prepared from a film that
`treated to resist attack to ultra-violet light, and to be
`receptive to adhesive bonding. In particular, capping
`layer 18 may receive surface treatments in a variety of
`ways, within the skill of the art, to provide both proper-
`ties, such as, by corona discharge treatment, or by the
`application of known ultra-violet inhibitors and the like.
`In the instance where ultra-violet resistance is imparted
`by the application of a coating composition, a variety of
`ultra-violet inhibitors and stabilizers may be utilized,
`among them compounds containing a benzotriazole or
`benzophenone nucleus. These materials are well known
`and commercially available, and may be selected for use
`in accordance with the skill of the art.
`Capping layer 18 itself comprises a resin having par-
`ticular resistance to ultra-violet radiation, and the corre-
`sponding capability to successfully undergo a thermo-
`forming operation. Layer 18 may thus be prepared from
`a material selected from the group consisting of fluori-
`nated vinyl-polymers, fluorinated polyolefins, and poly-
`esters treated for resistance to ultra-violet radiation. In
`particular, capping layer 18 may comprise a p¢lyvinyl-
`fluoride, generally available and manufactured by Du-
`Pont under the name “Tedlar.” The capping layer 18
`may range in thickness from 1 to 2 mils, as it is provided
`to present a uniform and protective exterior surface to
`laminate 10.
`
`Capping layer 18 is adhesively bonded to metal coat-
`ing l4 by a pressure and heat sensitive elastomeric adhe-
`sive coating 20. Adhesive coating 20 is resistant to at-
`tack by ultra-violet radiation and is harmless with re-
`spect to metal coating 14, and thus possesses favorable
`qualities lacking in the adhesives utilized in the prior art.
`As noted earlier, prior art adhesives tend to attack the
`metal layer and to cause its deterioration, and, by virtue
`of their instability in Contact with ultra-violet light, tend
`to deteriorate unilaterally, and to allow delamination
`and other surface discontinuities to appear in the lami-
`
`6
`nate over a short period of time. The adhesive coating
`20 may be a composition such as a silicone resin or an
`appropriate acrylic polymer, and is preferably the for-
`mer. In particular, the adhesive coating 20 may com-
`prise homopolymers and copolymers of siloxane resins,
`such as those commercially manufactured by the Gen-
`eral Electric Company, and others.
`The compositions of adhesive coating 20, preferably
`contain a polymerization ccatalyst
`in amount
`that
`ranges from about 2% to about 6% by weight of the
`adhesive resin solids. The provision of the catalyst
`within this range is particularly advantageous, as it
`confers a partial cure to the adhesive that promotes
`improved bonding and stability of the adhesive after its
`application and disposition between capping layer 18
`and metal coating 14, that resists distortion and resulting
`surface discontinuities during subsequent thermo-form-
`ing operations. One of the problems that has attended
`the use of various adhesives, particularly in contact
`with the metal layer of reflective laminates, has been the
`tendency of the adhesive, not only to attack the metal
`layer, but to undesirably migrate during subsequent
`thermo-forming. The present adhesive compositions
`neither attack the metal layer nor migrate in such man-
`ner, and permit the formation of faithfully uniform,
`thermo-formed products, having retained,
`improved
`brilliance and reflectivity.
`A variety of polymerization catalysts may be utilized
`in the compositions of adhesive coating 20, among them
`benzoyl peroxide, substituted benzoyl peroxide, amino-
`substituted compounds and silicone compounds. A pre-
`ferred catalyst comprises an amino-substituted silane,
`such as gamma aminopropyl triethoxysilane.
`Adhesive coating 20 is preferably applied to the sur-
`face of capping layer 18 that is to be bonded to metal
`coating 14, prior to the bonding thereof. The exact
`procedure associated with the application of adhesive
`coating 20, will be discussed with reference to the
`method of the present invention, later on. Preferably,
`adhesive coating 20 is applied to a dry thickness ranging
`from about 0.3 mils to about 0.8 mils, and particularly
`may be applied to a thickness ranging from 0.35 mils to
`0.4 mils.
`As noted earlier, metal coatings 14 and 16 may be
`prepared from a variety of metals well known for im-
`parting highly reflective corrosion and abrasion resis-
`tant surfaces. In particular, such metals may comprise
`chromium, alloys of chromium, nickel, nickel and chro-
`mium alloys such as Nichrome, iron, alloys of iron and
`chromium, stainless steel, aluminum, alloys of alumi-
`num and others. Preferably, and as indicated earlier, the
`metal applied to form metal coatings 14 and 16 com-
`prises aluminum.
`Referring again to FIG. 1, laminate 10 is illustrated
`therein with a backing layer 22, that is laminated by
`conventional techniques to the free surface of coating
`16. Backing layer 22 may be prepared as a sheet or the
`like from a variety of resins, including various polyole-
`fins, vinyl polymers and copolymers, polycarbonates,
`acrylic polymers and copolymers, and other materials
`capable of undergoing a thermo-forming operation. In
`particular, backing layer 22 may be prepared from poly-
`vinylchloride homo- and co-polymers, polyethylene, its
`copolymers and interpolymers, acrylonitrile-butadiene-
`styrene copolymers, and suitable mixtures thereof. Pref-
`erably, backing layer 22 comprises an ion-linked and
`modified ethylene interpoloymer, known commercially
`as “Surlyn.”
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`Wavelock
`Exhibit1009
`Page6
`(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:28)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:25)
`
`
`
`4,403,004
`
`7
`Backing layer 22 may vary in thickness, and, for
`example, may have a thickness of 20 mils, when pro-
`vided for
`thermo-forming and subsequent
`injection
`molding for exterior automotive application. In such
`instances, additional resinous material, either identical
`to or variant but compatible with the composition of
`backing layer 22 may be laminated to the free surface
`thereof, or injection molded into association therewith
`by processes described further, later on.
`In accordance with a further embodiment of the pres-
`ent invention, a method for preparing the present lami-
`nates is disclosed, which comprises first applying a
`metal coating on one surface of base layer 12, adhe-
`sively bonding capping layer 18 to the metallized sur-
`face provided, for example, by metal coating 14, and
`thereafter applying a second metal coating 16 to the
`uncoated free surface of base layer 12. As noted above,
`the resulting laminate 10 may optionally include a back-
`ing layer 22 that is subsequently applied by lamination
`techniques known in the art, including extrusion lamina-
`tion, and the like.
`The present method will be better understood from a
`review of FIG. 2, comprising a schematic representa-
`tion of the important manufacturing steps. Initially, the
`first step of the present method, not shown in FIG. 2,
`ltowever, comprises the deposition of metal coating 14
`on one surface of base layer 12. Preferably, base layer" 12
`is disposed in an extended strip of varying widths, main-
`tained on a roll, and is continually fed through a vac-
`uum deposition chamber, in the manner described ear-
`lier, to provide a metallized surface on one side of the
`film strip. After metallization is completed,
`the one-
`sided metallized strip of base layer 12 is gathered by a
`take up reel, not shown, and is stored in this condition
`for further processing in accordance herewith. The
`foregoing treatment is performed in accordance with
`well’ known conventional
`industry standards, and a
`specific illustration thereof is not believed to be neces-
`sary.
`The next step comprises application of adhesive coat-
`ing 20 to one surface of the film defining capping layer
`18. As shown in FIG. 2, capping layer 18 may be paid
`out from a continuous roll 24 to provide a strip of mate-
`rial for continuous adhesive coating. Capping layer 18
`then passes through an adhesive coater where a regu-
`lated amount of adhesive composition is applied to the
`lower surface of layer 18, such as, for example, by the
`schematic assembly 26 illustrated herewith. In particu-
`lar, assembly 26 may comprise a trough having a quan-
`tity of adhesive compositions therein, a dip roll 30rthat
`initially picks up the adhesive composition and relays it
`to a transfer roll 32, for application to the surface of
`capping layer 18. Proper coating pressure maybe pro-
`vided by a squeeze roll 34, so that a uniform coating 20
`results. Thereafter, the coated layer 18 maybe exposed
`to heat to dry adhesive coating 20, by passage through
`a drying tunnel 36, where heat is applied by forced air
`impinging on the wet surface. Drying may take place at
`a temperature on the order of about 240° F. with the
`coated layer 18 travelling at a speed of, for example, 70
`feet per minute. Naturally, the foregoing parameters are
`illustrative only. The resulting composite layer 38 is
`now ready for further processing in accordance with
`the present method.
`The next step in the process comprises the adhesive
`bonding of composite capping layer 38 with the base
`layer 12 previously coated on one side with a metal
`coating such as metal coating 14. As noted earlier, the
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`8
`application of coating 14 is conventional and is not
`illustrated schematically-herein. Accordingly, a pay out
`reel 40 bearing the base layer 12 having the first metal
`coating 14 thereon, hereinafter referred to as first com-
`posite base layer 42 is brought into contact with the
`adhesive coated surface of composite capping layer 38,
`with its metal coated surface disposed thereagainst. At
`this point, adhesive coating 20 is dry, however,
`the
`bonding of coating 14 to coating 20 may take place
`under pressure alone, as coating 20, noted earlier,
`is
`pressure sensitive. Alternatively, bonding may take
`place under combined heat and pressure, and these
`latter conditions are preferred. As illustrated in FIG. 2,
`composite layers 38 and 42 maybe bonded by passage
`between pressure rollers 44 and 46, which may likewise
`be heated to impart both heat and pressure to the mate-
`rials. For example, bonding may take place at tempera-
`tures ranging from about 140° to 150° F., and pressures
`ranging from about 30 to about 60 psi. Naturally, the
`foregoing parameters are illustrative only.
`the
`' After exiting from pressure rollers 44 and 46,
`resulting capped, metallized base 48 consists essentially
`of four discrete layers, namely, capping layer 18, adhe-
`sive coating 20, metal coating 14 and base layer 12.
`Metallized base 48 is thereafter coated on the free sur-
`face of base layer 12, with a second reflective metal
`coating 16, by feeding base 48 through a conventional
`vacuum rnetalization chamber schematically illustrated
`at 50. As illustrated in FIG. 2 and described earlier, a
`quantity of metal in pelletized form within a container
`suchias crucible 52, is heated, such as by inductive heat-
`ing means 54 to cause a fine layer of metal to deposit on
`the adjacent side of base 48, whereby layer 16 is formed.
`Layer 16 like layer 14, maybe formed to a thickness of
`from 100 to 200 Angstroms,«and the resulting product
`emerging from chamber 50 will comprise the prelimi-
`nary laminated structure 56 that is the essence of the
`present invention. Optionally, as illustrated herein and
`discussed earlier, a backing layer 22 disposed on a simi-
`lar pay out reel 58 may be bonded to the free surface of
`metal coating 16, of laminated structure 56, by conven-
`tional
`techniques,
`including, as
`illustrated, passage
`through heated pressure rollers 60 and 62. While bond-
`ing by heat and pressure is illustrated schematically
`herein, it is to be understood, as discussed earlier, that
`the bonding of backing layer 22 to laminated structure
`56 may be performed by other laminating techniques
`known in the art, within the scope of the present inven-
`tion.
`
`The product exiting from rollers 60 and 62 comprises
`laminate 10, illustrated in FIG. 1.
`,
`Referring briefly to FIG. 3, a schematic cross-sec-
`tional illustration of the various layers coated and other-
`wise combined in accordance with the present method
`is provided, to illustrate the manner in which the re-
`spective layers are accumulated and brought together.
`Thus, the left hand portion of the figure shows capping
`layer 18 both before and after application of adhesive
`coating 20, and the resulting composite capping layer 38
`produced thereby. Likewise, first composite base layer
`42 and its components, metal coating 14 and base layer
`12 are illustrated being brought together with compos-
`ite capping layer 38, to form the multi-layered capped,
`metallized base 48. In turn, metallized base 48 is shown
`after vacuum deposition of metal coating 16 on the free
`surface of base layer 12, to form preliminary laminated
`structure 56, and the final laminate 10 is shown to result
`
`Wavelock
`Exhibit1009
`Page?
`(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:28)(