Mined States Patent
`Dani
`
`[19]
`
`4,275,099
`[11]
`[45] Jun. 23, 1981
`
`
`
`[54] METALIZED POLYESTER RESIN
`LAMINATE
`
`[75]
`
`Inventor:
`
`Mahesh J. Dani, Newtown, Pa.
`
`[73] Assignee:
`
`Dunmore Corporation, Newtown, Pa.
`
`[21] Appl. N0.: 91,367
`
`[22] Filed:
`
`Nov. 5, 1979
`
`[51]
`
`Int. 01.3 ...................... B60R 13/00; B60R 21/14;
`c091 5/04
`[52] U.S. C1. ...................................... 428/31; 156/315;
`156/331.4; 293/128; 428/416; 428/422;
`428/4246; 428/4244; 428/458; 428/463;
`428/480; 428/483
`[58] Field of Search ..................... 260/4595 F; 293/1,
`293/128; 156/315, 331; 428/31, 458, 424.4,
`424.6, 416, 422, 463, 480, 483
`
`[5 6]
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`3,440,129
`3,494,075
`3,531,348
`3,538,055
`
`4/ 1969 Anselm .................................. 428/31
`..... 49/462
`2/1970 Kunevicius
`
`9/1970 Kunevicius .......
`156/164
`11/1970 Camilleri et a1.
`................. 428/4246
`
`3,577,211
`3,681,180
`3,687,502
`3,881,042
`3,914,482
`3,922,460
`3,935,164
`3,949,134
`3,959,538
`3,970,498
`3,982,780
`4,010,297
`4,081,504
`4,208,465
`
`5/1971 Wilson ........................... 260/4595 F
`8/1972 Kent
`428/31
`
`Loew ........... 293/1
`8/1972
`
`4/1975 Ungerer ......
`428/67
`Sawa et al.
`..
`10/1975
`428/31
`Jackson ............... 428/31
`11/1975
`
`1/1976
`Spivack
`260/4595 F
`
`...... 428/458
`4/1976 Wildorf
`
`5/1976
`Loew ......
`428/31
`
`7/1976
`Loew ......
`428/31
`
`9/1976 Keith .......
`293/1
`
`3/1977 Wenrick ......
`428/31
`3/1978 Wenrick et a1.
`428/31
`
`Chang .................................. 428/416
`6/1980
`
`Primary Examiner—William R. Dixon, Jr.
`Attorney, Agent, or Firm—B. Max Klevit
`
`[57]
`
`ABSTRACT
`
`A laminate, particularly useful for application to resin
`extrusion strips applied as trim molding to sides and
`doors of automobile bodies, is formed of a surface met-
`alized polyester resin film bonded to a vinyl resin sheet-
`ing by an in-situ formed polyester-isocyanate adhesive.
`
`36 Claims, 5 Drawing Figures
`
`P013! l/INYL
`
`FL UOR/DE FILM
`
`PRIMER
`
`i2
`r3
`'
`
`20
`
`iPOLYESTER FILM
`
`14LUMW/ZED
`
`PR IMER
`
`(IRE THAME Ml/ESIVE
`
`PVC FILM
`
`Wavelock
`Exhibit 1010
`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:20)(cid:19)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:20)
`
`

`

`US. Patent
`
`Jun. 23, 1981
`
`4,275 @91‘9)
`
`m
`PRIMER COAT
`
`12
`
`LACQUERCOAT
`‘ POLYESTER FILM
`
`ALUMINUM DEPOSIT
`
`
`135W \URETHANE ADHESIVE
`
`20
`
`2:
`
`PVC FILM
`
`.
`
`fa’
`
`WEATHER PROOF /"
`I2
`
`POLYESTER FILM "32$“qu
`"
`52/ L20
`
`PVC FILM
`
`FL UOR/DE FILM
`
`POLY VINYL
`
`F G‘ 4
`/
`
`13
`
`20
`
`MUM/WEED
`
`PRIMER
`
`URET/IANE MIIESIVE
`
`F/G 5 PVC FILM
`
`53 SHIELD 0/? M? mow/ER
`
`
`
`PLASTIC/2'50
`V/NYL RES/IV
`
`
`WA TER
`
`CHILL TANK
`F I G 5
`
`COLD
`
`Wavelock
`Exhibit 1010
`Page 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:20)(cid:19)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:21)
`
`

`

`1
`
`4,275,099
`
`I
`
`METALIZED POLYESTER RESIN LAMINATE
`
`BACKGROUND OF THE INVENTION
`
`1. Field of the Invention
`The present invention relates to thin laminate struc—
`tures comprising a film layer of metalized resin, which
`laminate structure is to be exposed in use to extremes in
`weather environment. It is particularly concerned with
`such laminates employed in protective and decorative
`trim molding strips applied to doors and side panels of
`automobile bodies and to edges of automobile doors.
`2. Prior Art
`Within about the past decade, metal molding strips
`employed as decorative or protective (“rub-rails”) trim
`on the doors and side panels of automobiles have been
`largely replaced by plastic extrusions. Typical extruded
`moldings and edgings for application to the sides of
`automobiles and to the edges of the doors respectively
`are well known in the art as shown for example in the
`US.
`Pat. Nos.
`3,440,129;
`3,494,075;
`3,531,348;
`3,681,180; 3,687,502; 3,881,042; 3,914,482; 3,922,460;
`3,970,498; 3,982,780; 4,010,927. Certain of the listed
`patents, among others, disclose plastic extrusions pro-
`vided with a laminated layer comprising a metalized or
`metal-coated resin film. The typical structure widely
`employed for such application is formed of a three-ply
`laminate which generally is comprised of an aluminized
`polyester (such as aluminized “Mylar”) film of about 0.5
`mil thickness, adhesively bonded to an outer polyvinyl
`fluoride protective film of about 1 mil thickness. The
`opposite side of the metalized polyester film is adhe-
`sively bonded to a base layer of a virgin vinyl resin. This
`tri-laminate is applied to a running length of the ex-
`truded molding strip generally comprised of a virgin
`vinyl resin. The tri-laminate may be heat fused to the
`extruded strip or may be further provided with a back-
`ing of suitable adhesive to enhance or facilitate bonding
`to the resin extrusion. One form of such tri-laminate is
`disclosed in the US. Pat. No. 3,982,780, Example 2.
`While tri-laminates of the type above described are
`widely used commercially, these as well as other pro-
`posed laminate structures have been found to present
`frequent problems, particularly from the standpoint of
`peeling or delamination. Such delamination tendency is
`at times already observed on standard testing of samples
`of the laminate or of the finished extrusion strip to
`which the laminate is applied, when the sample is sub-
`jected to prescribed weather environment conditions
`for indicated time periods. Even such products that are
`deemed acceptable in having successfully passed the
`prescribed tests, are in many instances later found defec—
`tive and subject to subsequent complaints by automo-
`bile users and dealers. Such loss of bonding of the lami-
`nated molding strip often results from seepage of water
`between layers of the laminate, particularly between the
`metalized surface and the next adjacent layer. Appar-
`ently, the contained water penetrating the laminate is
`caused to evaporate when exposed to the sun’s radiant
`heat and thus tends to break the bond between the
`strata. In other instances breaks in the continuity of the
`surface film of the molding strip as a result of impact or
`scratching, expose areas at which delamination may be
`initiated.
`Among the objects of the present invention, there-
`fore, are to provide an improved laminate structure
`comprising a metalized resin film layer, designed to
`
`5
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`20
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`25
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`2
`overcome or largely mitigate the problems hitherto
`encountered in the use of such laminates.
`
`SUMMARY OF THE INVENTION
`
`In accordance with the present invention, a novel
`metalized resin film—containing laminate of improved
`weathering properties and enhanced resistance to de-
`lamination is obtained by employing as an adhesive
`bond between said film and the film layer next adjacent
`the metalized surface, a specially developed in-situ
`formed polyester-isocyanate polyurethane. The pre-
`ferred laminate of the present invention comprises a
`clear transparent polyester resin film having on one side
`thereof a thin coating of vacuum deposited aluminum
`metal and on its opposite side, a clear weather resistance
`coating of a polyester resin preferably containing ultra-
`violet inhibitor. The metal coated surface of the film is
`bonded to a vinyl resin film by the in-situ formed ther-
`mosetting adhesive bond comprising the polyurethane
`formed by the reaction of the isocyanate with hydroxy
`groups of the polyester polyol. To enhance the strength
`of the bond between the metalized surface and the poly-
`urethane adhesive layer and thus strengthen the overall
`bonding of the laminate layers, a thin priming layer is
`applied to the metalized surface before application of
`the urethane adhesive composition.
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`The operation of the invention will be understood
`and its several advantages appreciated from the detailed
`description which follows, read in connection with the
`accompanying drawings, wherein:
`FIG. 1 is an exaggerated schematic representation of
`the preferred laminate showing the several layers in
`detached form. The illustrated thicknesses of the com-
`ponent layers are not scaled in proportion to actual size.
`FIG. 2 is a similar representation of an alternative
`embodiment.
`FIG. 3 is a similar representation of a further alterna-
`tive embodiment depicting a tri-laminate instead of the
`di-laminate embodiments illustrated in FIGS. 1 and 2.
`FIG. 4 is a perspective view of one form of automo-
`bile trim strip showing the application of the laminate to
`an extrusion strip, a portion of said strip being broken
`away.
`FIG. 5 is a schematic illustration of the manner of
`applying the laminate layer to an extruded plastic strip.
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`FIG. 1 of the drawings shows the component succes-
`sive layers of the preferred bilaminate structure of the
`present invention, the thickness of the several compo-
`nent layers being highly exaggerated and not scaled to
`relative dimension. As shown in FIG. 1, the laminated
`structure comprises a preformed film of polyester resin
`10 and a preformed film of vinyl resin 20. The polyester
`film may be of about 50 to 200 gauge thickness (12 to 50
`microns), preferably 12 to 25 microns, and has thereon
`a substantially uniform vacuum-deposited coating of
`vaporized aluminum, indicated at 11, of desired thick-
`ness, which may preferably be in the range of 100 to 200
`Angstroms.
`To improve bonding of the metalized surface to the
`next adjacent adhesive layer, the metalized surface is
`coated with a primer composition 12, which is an acid-
`modified vinyl chloride copolymer in suitable solvents,
`said polymer preferably being cross-linked. To the thus
`
`Wavelock
`Exhibit 1010
`Page 3
`(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:20)(cid:19)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:22)
`
`

`

`4,275,099
`
`3
`primed surface there is next applied the adhesive coat-
`ing 13, the composition of which is an important feature
`of the present invention. The adhesive layer 13, which
`will be more specifically hereinafter described,
`is a
`polyurethane formed from selected polyester polyols
`dissolved in suitable organic solvents and selected poly-
`isocyanates in controlled proportions.
`The outer surface of the polyester film 10 in the em-
`bodiment of FIG. 1 is coated with a weather resistant
`transparent lacquer 15 capable of providing a protective
`coating for the metalized polyester film 10, said lacquer
`containing U.V. inhibitor.
`The under surface 21 of the vinyl film may be pro-
`vided with a dried coating of a suitable adhesive, if so
`desired, to facilitate or improve bonding between the
`laminate and the vinyl extrusion strip. The use of the
`adhesive at 21 may not always be necessary since the
`vinyl film of the laminate can be fuse bonded to the
`Vinyl extrusion molding and obtain good adhesion
`thereby.
`Aluminized polyester film and methods for its pro-
`duction are well known in industry. Various commer-
`cial methods for production thereof are described in
`Modern Plastics Encyclopedia (1970—1971, at pages 710
`and following). In the preferred method for production
`of the metalized polyester film 10, 11, employed in the
`laminate of the present invention, the aluminum (99+%
`pure) held in a heated crucible in the form of pellets or
`the like,
`is vaporized in a high vacuum chamber by
`resistance or induction heating. Running lengths of the
`polyester resin film are passed through the chamber so
`that one surface of the film is exposed to contact with
`the vaporized metal at a running rate to deposit a uni-
`form layer of the metal onto the film at a thickness of
`100 to 200 Angstroms, while the opposite side of the
`film is subjected to cooling by contact with a cooling
`cylinder, to effect condensation of the aluminum on the
`metalized surface. The polyester film is a linear conden-
`sation product of a glycol and an unsaturated dibasic
`carboxylic acid, preferably poly- (ethylene terephalate),
`having a thickness in the preferred range of about 10 to
`25 microns. Suitable commercial polyester film that can
`be employed include those marketed as “Mylar” (du-
`Pont) and “Melinex” (I.C.I. Ltd.).
`After repressuring of the vacuum chamber to about
`atmospheric pressure the metalized film is removed
`from the chamber and the metal side is primed with a
`reactive vinyl resin solution preferably a solution of an
`acid-modified vinyl chloride vinyl acetate copolymer
`resin. The primer may be applied by a coating cylinder
`to a thickness in the range of about 0.01 to 1.0 microns,
`preferably 0.1 to 0.3 microns. Any of the usual organic
`solvents for such modified vinyl resin may be em—
`ployed, typically methylethyl ketone (MEK), methyl
`isobutyl ketone (MIBK) or mixtures of these together.
`: The function of the primer is to enhance the adhesion
`of the aluminum coated surface to its support as well as
`to strengthen the adhesive bond between the metalized
`surface and the next applied polyurethane adhesive
`compostion. The presence of the carboxyl functionality
`in the acid-modified polyvinyl chloride serves this pur-
`pose. While not absolutely essential in practice of the
`present invention, optimum results are obtained by the
`incorporation of cross-linking agents in the primer com-
`position. Among the typical cross-linking agents that
`can be so employed are included: solutions of organic
`polyisocyanates, epoxidized vinyl compounds, epoxy
`resin compounds or mixtures among these or with other
`
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`cross-linking agents. Among the commercially avail-
`able Vinyl resin solutions that can be employed in the
`primer composition reference is made to “Bakelite
`Vinyl Solution Resin VMCH” (Union Carbide) and
`mixtures of the VMCH with other vinyl resins in solu-
`tion such as VMCC and/or VMCA (Union Carbide).
`VMCA is a vinyl chloride acetate copolymer modified
`with 2.2 to 2.5% by weight maleic acid and containing
`79 to 82% by weight polyvinyl chloride. VMCH is a
`similar copolymer of somewhat higher molecular
`weight than VMCA, comprising 85 to 88% by weight
`polyvinyl chloride and 0.8 to 1.2% maleic acid. VMCC
`is a copolymer simlar to VMCH comprising 81.5 to
`84.5% by weight of PVC and 0.8 to 1.1% maleic acid.
`Among the commercially available cross-linking
`agents of these several type noted above are:
`Polyisocyanates:
`Desmodur IL (Mobay)—a polyisocyanate of 16 to
`17% NCO content having an average equivalent
`weight of 525; dissolved in butyl acetate.
`Mondur CB-75 (Mobay)—an aromatic polyisocya-
`nate adduct of 12.5 to 13.5% NCO content hav-
`ing an average equivalent weight of about 325;
`dissolved in ethyl acetate.
`Epoxidized vinyl resins:
`VERR (Union Carbide)~—an epoxidized vinyl
`chloride polymer solution comprising 78% PVC
`and 1% oxirane oxygen. The cross-linking reac-
`tion is catalyzed with uranyl nitrate.
`Epoxy resins:
`Epon 828 (Shell)—a liquid epoxy resin having an
`epoxy equivalent of 185 to 192 and a viscosity of
`110 to 150 poise at 25° C.
`A typical primer composition employing VMCH
`may comprise about a 12.6% by weight solution of the
`resin in toluol and methyl ethyl ketone (80—20), having
`a viscosity in the order of about 16 secs. (#2 Zahn cup).
`As cross-linking agent an epoxy resin compound is
`preferred such as Epon 828,
`together with tertiary
`amine and organo-tin catalysts to promote the cure.
`The primer solution is applied and dried at tempera-
`ture as in the range of about 200° to 260° F. (140°—l45“
`C.), depending in part on the composition of the partic-
`ular primer selected, the presence or absence of cross-
`linking agents and the particular cross-linking agents
`employed.
`To secure good bonding adhesion between the
`primed metalized surface of the polyester resin film and
`the vinyl film 20, an adhesive coating is applied to the
`primed surface. The novel composition of the adhesive
`here employed is an important factor contributing to
`the advantageous properties exhibited by the laminates
`of the present invention. The adhesive coating applied
`comprises an organic solution of components forming in
`situ a thermosetting polyester-urethane. The solution
`comprises as one of the reacting components a hydroxy
`polyester formed by condensation of a polyhydric alco-
`hol particularly a glycol such as butanediol and/or
`neopentyl glycol with isophthalic and/or terephthalic
`acid or mixtures of these glycols and/or acids in con-
`trolled ratios, providing a copolymer of maximum pos-
`sible heat resistance while still maintaining solubility in
`normal lacquer type solvents. The polyester desirably
`should have reactive hydroxyl and a softening point in
`excess of about 100° C. after evaporation of solvents. To
`react with the hydroxyl polyester in the adhesive coat—
`ing there is added thereto a mixture of certain organic
`polyisocyanates and suitable tertiary amine catalyst.
`
`Wavelock
`Exhibit 1010
`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:20)(cid:19)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:23)
`
`

`

`4,275,099
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`Preferred catalysts include dimethylethanolamine and
`diethylethanolarnine.
`Among the preferred polyisocyanate mixtures is one
`comprising both an aromatic triisocyanate adduct and
`an aliphatic triisocyanate. The ratio of aliphatic triisocy-
`anate to aromatic triisocyanate may be in the range of
`between about 5:95 to 30:70, with the preferred ratio
`being about 15 to 85. The polyisocyanates and hydroxy
`polyester are dissolved in organic solvent employing a
`weight ratio of hydroxy polyester to isocyanates up to
`about 4:1. Generally the higher the percent of polyiso-
`cyanate the better the performance of the formed adhe-
`sive (such as heat resistance), but with a high content of
`the isocyanates processing of the adhesive becomes
`more difficult, particularly from the standpoint of
`shorter pot life. The applied adhesive, in the presence of
`tertiary amine catalyst of moderate activity, does not I
`develop its ultimate properties until final cure by stand-
`ing for a week or more after lamination, depending on
`humidity and other environmental conditions.
`A commercially available aromatic triisocyanate that
`may be employed in the described adhesive coating
`(designated 13) is “Mondur CB-75” (Mobay Chemical
`Co.) formed by reacting three moles of tolylene diisocy-
`anate with one mole of trimethylol propane, and dis-
`solving the product in ethyl acetate (about 75% solids in
`solution). The product has an average equivalent
`weight of 325 and an NCO content of 12.5 to 13.5%. A
`commercially available aliphatic triisocyanate that may
`be employed is “Desmodur N—75”, which is supplied as
`a 75% solids solution in equal parts of ethyl glycol
`acetate and xylene. This product has an average equiva-
`lent weight of 255 and an NCO content of 16 to 17%. It
`may be formed by reacting three moles of hexamethyl-
`ene diisocyanate with one mole of water.
`The preferred hydroxy polyester resin employed in
`the adhesive composition (13) is one having an acid/OH
`ratio of less than 0.5, wherein the hydroxy] number is
`preferably above 3 and up to 10, and a maximum acid
`number of up to 2.0, preferably below 1; best below 0.2.
`The polyester resin solution in Toluol/MEK (50/50),
`before addition of the polyisocyanate solution, prefera-
`bly should have a Brookfield viscosity in the range of
`120 to 180 cps, at 25° C.
`The polyester-isocyanate adhesive coating 13 may be 45
`applied to the primed surface 12 by roller coating at a
`dry thickness of about 5 to 10 microns and dried at
`temperatures in the order of 150° to 250° F. (65° to 125°
`C.). The laminate structure, now comprising the layers
`12 and 13 coating the aluminized surface 11 of the poly-
`ester film 10, is press laminated to the vinyl film 20 at
`175° to 350° F. (80° to 175° C.). The vinyl film em—
`ployed is that commonly used for automobile body trim
`laminates and may have a thickness in the order of
`about 2 to 8 mils (50 to 200 microns). The commercially 55
`available vinyl film commonly recommended for lami-
`nates used in automobile body trim is a monomer plasti-
`cized polyvinyl chloride having a Shore durometer “A”
`hardness of 75 to 100+. The plasticizer generally em-
`ployed for such film essentially is an alkyl phthalate,
`such as isooctyl phthalate, applied at a ratio of about 24
`parts per hundred parts resin.
`The vinyl film 20 may be directly bonded to the vinyl
`extrusion strip by heat fusion. If desired, however, a dry
`heat seal adhesive layer may be applied to the underside
`21 of the vinyl film 20 to facilitate or enhance such
`bonding. For this purpose any of the known heat—soft-
`ening adhesive compositions for vinyl-vinyl bonding
`
`6
`may be used. The adhesive layer, if used, may be ap-
`plied to the underside of the vinyl film 20 at a thickness
`in the range of 2 to 3 microns.
`v
`The preferred lacquer coating 15 applied to the outer
`side of the polyester film 10, comprises an organic solu-
`tion of a polyester resin, since such lacquer has excellent
`adhesion properties when applied to polyester film and
`provides a highly weatherable protective coating. An
`ultraviolet inhibitor is incorporated in the lacquer solu-
`tion, which may be any one of the known organic U.V.
`stabilizers, preferably from among U.V. adsorber com—
`pounds containing a benzotriazole or benzophenone
`nucleus. Typical examples include: 2,4 dihydroxy ben-
`zophenone; 2,2' dihydroxy; 4,4’ dimethoxy benzophe-
`none; 2,2,4,4’ Tetrahydroxy benzophenone; 2 hydroxy-
`4-methoxy benzophenone; 2,2’ dihydroxy-4—methoxy
`benzophenone. The more preferred benzophenone
`compounds are those containing a hydroxyl group
`ortho to the oxo linking group on at least one of the
`benzene rings and in which one or both of the 0—
`hydroxy substituted rings’may further contain a hy-
`droxy or methoxy group in the paraposition. The pre-
`ferred U.V. adsorber compounds correspond generally
`to the formula:
`
`wherein x is OH or CH3, y is H or OH, and z is H, OH
`or CH3. Among the preferred commercially available
`U.V. inhibitors is “Uvinul D-50” (GAF), which is 2,2’,
`4,4’,-tetrahydroxy benzophenone,
`Any known solvent or mixture of organic solvents
`for polyester resin may be employed to dissolve the
`resin used in the lacquer coating 15. Excellent perfor-
`mance has been obtained when employing a solution of
`the resin in methyl ethyl ketone and toluene having a
`viscosity of 22 seconds (#2 Zahn cup). The U.V. ad-
`sorber constitutes 2 to 3 parts per hundred parts of the
`resin (W/W). The protective lacquer 15 may be applied
`to film 10 at a thickness of from above 1 to 2 or more
`microns and dried thereon by a flowing hot air stream at
`a temperature generally in the range of 105° to 125° C.
`The obtained laminate is thus provided in the form of
`rolled webs having a thickness of from about 2.5 to 10
`mils (0.06 to 0.25 mm.), which if desired, may be cut up
`into sheets or strips of desired dimension.
`The components of the laminate structure depicted in
`the alternative embodiment of FIG. 2 are largely the
`same as those in FIG. 1 with the noted exception that in
`the FIG. 2 embodiment the lacquer coating 15 is omit-
`ted. If one employs as the outermost film 10' a weather-
`resistant polyethylene terephthalate such as one already
`containing ultra-violet inhibitor, in forming the laminate
`of the present invention, it is not necessary to apply a
`weather proof lacquer coating thereover. Such weath-
`er—resistant polyethylene terephthalate films are com-
`mercially available. Of course, if one desires neverthe-
`less to apply such weather proofing lacquer coating to
`the surface of an already weather resistant polyethylene
`terephthalate film (10’), to satisfy customer demand or
`otherwise, the same may be practiced without depar— '
`ture from the present invention.
`
`Wavelock
`Exhibit 1010
`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:20)(cid:19)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:24)
`
`

`

`7
`As hereinabove indicated, the present existing stan—
`dard in the industry calls for a trilaminate wherein the
`outer exposed surface of the laminate is covered with a
`preformed protective film of polyvinyl fluoride (“Te-
`dlar”). If so desired, the laminate of the present inven-
`tion may be made in trilaminate form as depicted in the
`alternate embodiment of FIG. 3. Thus, as shown in
`FIG. 3, the metalized polyester film 10 or 10' may be the
`same as that employed in the embodiments of FIGS. 1
`and 2; however, since an overlying protective film layer
`is to be employed the polyester film 10 or 10’ may be at
`the thinner end of the range, as at about 50 gauge thick-
`ness (12 microns). The successive coatings 11, 12, 13
`and‘the vinyl film 20 may be the same as in the previ-
`ously described embodiments. To secure good bonding
`between the non-metalized surface of the polyester film
`10 and the superimposed Tedlar (polyvinyl fluoride)
`film 25 an adhesive and primer are sandwiched between
`the underside of the Tedlar film 25 and the upper face of
`the polyester film 10. Thus, as shown in FIG. 3, a
`primer composition 26 is applied to the exposed non—
`metalized surface of the polyester film 10 which was
`already laminated to the vinyl film 20 as previously
`described in embodiments of FIGS. 1 and 2. An adhe—
`sive coating 27 is next applied over the primer 26, and a
`second primer 28 is applied between the adhesive 27
`and the under surface of the Tedlar film 25. The primer
`28 optionally may be applied to the under surface of the
`Tedlar film or directly to the surface of the adhesive
`layer 27.
`The composition of the primers 26 and 28 will depend
`upon the particular type of adhesive employed at 27.
`The preferred adhesive for bonding the Tedlar film to
`the polyester film 10 is the sameas that employed in
`bonding the aluminized surface of the polyester film to
`the polyvinyl film 20. If such in—situ formed polyure—
`thane adhesive is employed at 27, primer 26 may be a
`thinned version of lacquer coating 15, preferably
`thinned with 50/50 mixtures of DMF/Ethylene glycol
`monoethyl ether acetate and catalyzed with isocyanates
`such as CB-75 to a degree of between 5 to 25% of the
`polyester solids. The dry thickness of this primer should
`be in the range of 0.05 to 2 microns. Applied with a
`roller coater, it should be dried at elevated temperatures
`of 200° to 250° F.
`
`The primer employed at 28 may be commercially
`available polymers characterized by good adhesion to
`25, polyvinyl fluoride (Tedlar) film. Particularly useful
`are the acrylic based coatings and adhesives available
`from the fabrics and finishes division of DuPont. The
`primer 28 is applied to treated surface of “Tedlar” film
`via roller coating and dried at temperatures of 175° to
`250° F. The dry thickness of this primer should be in the
`range of 0.05 to 4 microns.
`FIG. 4 of the drawings shows the application of the
`laminate to a length of vinyl extrusion to employed as a
`side molding on the body of an automobile. In the illus-
`trated embodiment the strips of laminate 30 are applied
`at the sides 31, 32 and only to part of the adjacent upper
`(outer) surfaces of the vinyl extrusion, leaving an inter-
`mediate exposed portion 35 free of laminate. The partic-
`ular configuration of the molding strip may vary with
`different automobile trim users or producers and is not
`claimed as part of the present invention.
`In a typical process for producing auto side trim
`molding the metalized laminate strip is applied to the
`vinyl extrusion in an in-line continuous process as the
`molten vinyl extrusion leaves the extrusion die. Thus, as
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`4,275,099
`
`8
`illustrated in FIG. 5, the plasticized vinyl strip 50 is
`extruded in molten form through a die 51 of desired
`cross sectional shape. The laminated sheet 30 is un-
`wound from a carrier roll 53 and fed onto the surface of
`strip 50 while the latter isstill in tacky condition. Con-
`ventional means are provided, as schematically indi-
`cated at 54, for shaping and tucking the laminate to fit
`the portions of the vinyl extrusion to which it is being
`applied. As heretofore indicated, the laminate sheet 30
`comprises at its underside, to be bonded to the vinyl
`extrusion, the vinyl film 20 (FIG. 1) or may be under-
`coated with an adhesive layer. After the desired attach-
`ment of the laminate 30 to the vinyl extrusion strip 50 is
`had, the bond therebetween is fixed by passing the com-
`posite through a chill tank 55 containing cold water or
`other suitable chilling medium.
`Typical molding strips for use as automobile side trim
`having substantially the shape illustrated in FIG. 4 are
`well known in the art, as shown in US. Pat. Nos.
`3,959,538; 3,982,780 and 4,010,297. As therein indicated,
`these may have different shapes as styled by the auto—
`mobile body manufacturers and may have the metalized
`laminate applied to all or part of the exposed outer
`surface of the molding strip.
`While the use of the laminate of the invention has
`been more particularly described in connection with
`side molding trim for automobiles, it will be understood
`that the invention is not limited thereto. The laminates
`of the invention may also be used on vinyl resin strips
`employed as protective edge guards on the doors of
`vehicles as well as a component of moldings used in
`window framing and windshield trim.
`The following example illustrates production of a
`preferred two ply laminate intended for application to a
`vinyl extrusion strip employed as a side trim for auto-
`mobile bodies and doors.
`
`EXAMPLE
`
`A running length of clear transparent biaxially ori—
`ented polyethylene terephthalate film (Melinex 442;
`1.01. Americas) of 23 micron thickness is passed
`through a vacuum metalizing chamber at a rate to de-
`posit aluminum metal on one surface of the film at a
`thickness of about 150 angstroms. The vacuum is main-
`tained at below 5 microns Hg and the aluminum in the
`chamber is heated by induction to a point at which a
`steady rate of evaporation of the aluminum is main-
`tained. Condensation of the aluminum on the exposed
`surface of the film is effected by contacting the opposite
`face thereof with a cooling cylinder at 45° F. (approxi-
`mately 7“ C.).
`The metalized surface of the film is coated with a
`mixture comprising a solution of VMCH in toluene and
`methyl ethyl ketone (70—30) to which there was added
`per 100 parts by weight of the dry VMCH: 30 parts of
`Epon 828, 0.025 parts of tertiary amine catalyst and
`0.014 parts of stannous octoate. The mixture has a vis-
`cosity of 16 seconds (#2 Zahn cup) at 12.6% solids and
`it is applied with a 200 Quad gravure cylinder at a dry
`thickness of about 0.2 microns and cured on a condition-
`ing drum at 280° F. (approximately 138° C.).
`The polyurethane-forming adhesive composition is
`applied over the primed surface of the metalized Meli-
`nex as a layer of about 7 micron dry thickness. The
`adhesive is usually applied at 30% solids with a 60 line
`trihelical gravure cylinder at a viscosity of 17 seconds
`(#3 Zahn cup). The solvent system consists of equal
`parts of methyl ethyl ketone and toluene; up to 10%
`
`Wavelock
`Exhibit 1010
`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:20)(cid:19)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:25)
`
`

`

`9
`cyclohexanone may be used if higher boiling solvents
`are desired. The primary resin is a hydroxy polyester in
`a range of 10,000 to 40,000 molecular weight having a
`hydroxyl number of 3 to 10 and an acid/hydroxy] ratio
`of O to 1.0. Per 100 dry parts of this polyester polyol are
`added: 6.25 parts of Desmodur N-75 and 35.5 parts of
`Mondur CB-75; and 0.85 parts of dimethylaminoethanol
`as a tertiary amine polyurethane catalyst.
`The adhesive coated film was laminated to an opaque
`film of plasticized PVC of 8 mil (approximately 2 mm)
`thickness (Stauffer, Regal 683).
`As a weatherproofing protective coating there was
`applied to the exposed non-metalized face of the Meli-
`nex film a lacquer coating of a weather resistant polyes—
`ter resin, with an acid number of approximately 50 and
`the coated laminate oven dried at 160° to 225° F. (71° to
`107° C.). The r