I
`Umted States Patent
`
`Eisfeller
`
`[19]
`
`4,407,871
`[1 1]
`
`
`[45]
`Oct. 4, 1983
`
`[54] VACUUM METALLIZED DIELECTRIC
`SUBSTRATES AND METHOD OF MAKING
`SAME
`
`[75]
`
`Inventor: Richard C. Eisfeller, Greenland,
`N.H.
`
`[73} Assignee:
`
`Ex-Cell-O Corporation, Troy, Mich.
`
`[21] App1~ No: 309,783
`.
`[22] “at
`
`Oct 8’ 1931
`
`[63]
`
`Related US. Application Data
`Continuation-impart of Ser. No. 133,857, Mar. 25,
`1980’ab3"d°“‘5d~
`,
`,
`Int. CLS .......................... 1333323353/19’ B32B 3/18,
`[51]
`/16’C23C 13/02
`[52] U.S. Cl. ...................................... 428/31; 427/250;
`427/294;427/296; 423/142;428/143;423/201;
`428/203; 423/208; 428/213
`[58] Field of Search ............... 427/250, 294, 296, 404;
`428/31, 201, 203, 204, 206, 208, 213, 215, 216,
`328, 142, 148
`
`[56}
`
`References Cited
`
`US" PATENT DOCUMENTS
`
`.. 428/148
`2,039,372
`5/1936 Wichmann
`.. 428/686
`2,096,170 10/1937 Geisler et a1.
`
`..
`2,413,604 12/1946 Colbert et a1,
`427/50
`
`..
`.. 427/166
`2,413,606 12/1946 Colbert et a1,
`
`2,450,850 10/1948 c0156“ :4 a1_ ..
`_, 427/166
`
`2,450,851 10/1948 Colbert et a1.
`..
`.. 427/166
`
`6/1954 Judd .........
`.. 427/164
`2,680,695
`
`
`2,724,663 “/1955 Bond
`427/50
`2,765,520 10/1956 Donley ................................ 428/642
`1/1957 Dreyer ................................ 350/397
`2,776,598
`
`2,923,651
`2/1960 peg-13110
`264/127
`2,940,950 6/1960 Gasman
`525/203
`
`7/1961 Fustier .....
`.. 427/250
`2,992,125
`7/1961 Fisher et a1,
`2,993,806
`427/404
`
`3/1962 Nuessle et a1.
`..
`3,025,181
`428/248
`
`8/1962 Buechler at 211.
`3,048,496
`428/473
`
`3,061,564 10/1962 Zdanowski ..
`524/599
`
`2/1963 Ault ................... 428/447
`3,076,726
`
`,,,,,,,,,, 428/432
`3,076,727
`2/1953 Harwig
`
`3,084,073 4/1963 Kine et a1.
`428/196
`3,085,913 4/1963 Caswell ............................... 427/250
`
`
`3,086,284 4/1963 Schetky ........................... 428/608
`3,118,781
`1/1964 Downing
`428/215
`
`6/1964 Charbonneau .
`3,138,517
`428/248
`3,152,950 10/1964 Palmquist et a1.
`...........
`428/335
`3,157,473 11/ 1964 Acton ............................... 428/626
`3,201,271
`8/1965 Simmons, Jr. et al.
`428/416
`3,223,554 12/1965 Newman ...........
`427/152
`
`3,232,818
`2/1966 Loew et a1.
`428/122
`3,276,905 10/1966 Porter, Jr. ..
`428/416
`
`229/45
`3,286,904 11/1966 Vieth et a1.
`,. 29/620
`3,380,156 4/1968 Lood et :11.
`9/1968 Blumberg et al.
`427/404
`3,400,014
`
`3,415,672 12/1968 Levinstein et a1.
`................. 427/250
`3,425,071
`2/1969 Frieder et a1.
`........................ 441/40
`3:11:23? 22323 $111535“?
`4222/82/5357?
`
`3,473,996 10/1969 Whalen, Jr.
`428/339
`
`3,476,593 11/ 1969 Lehrer .
`428/642
`3,480,464 11/1969 Lacy ......
`428/336
`
`ovac et a1.
`.....
`,
`,
`428/551
`3488166
`1/1970 K
`
`2/1970 Fitzgerald 81; a].
`...... 293/71
`3,493,257
`...........i .......... 204/38 A
`3,505,098
`4/1970 Miller et a1.
`............................ 428/31
`3,506,532 4/1970 Bock et a1.
`
`
`428/680
`3,508,887 4/1970 Chezel ex 211.
`.
`3,515,579 6/1970 Shephard et al.
`.
`. 428/436
`
`3,516,720 6/1970 Mauer ............
`350/1
`6/1970 Windecker .......................... 428/251
`3,518,156
`
`3,520,716 7/1970 Okamoto et a1.
`....... 427/250
`3,533,919 10/1970 Prior ..............
`.. 204/38
`
`3,537,855 11/1970 Lubin et a1.
`, 430/564
`
`2/1971 Ryan ----------
`35621235
`428/220
`
`- 116/28 R
`3,590,768
`7/1971 ' Shanok
`3,617,348 11/1971 Kelley et a1.
`.
`...... 427/89
`
`2/1972 Schwartz et a1,
`.1 204/38 S
`3,640,815
`. 427/248.1
`7/1972 Best ...........
`3,677,792
`
`3,681,180
`8/1972 Kent .......
`428/ 189
`8/1972 Genma CI 81-
`-
`3,631,225
`3 428/630
`
`8/1972 Ruff ...............
`3,687,792
`428/189
`
`. 427/383.1
`3,698,929 10/1972 Diebold etal.
`3,700,485 10/1972 Rubin .................................. 427/251
`3,720,567
`3/1973 Shanok et a]. .................... 428/31
`
`3,737,380
`6/1973 Bahmeier
`204/15
`
`3,740,254 6/1973 Lansbury et a1.
`. 428/4237
`
`
`3,741,800
`6/1973 Baier et al.
` ....... . 428/625
`3,741,881
`6/1973 Abu-Isa et a1.
`204/30
`
`3,744,835 7/ 1973 Carbone ................ 293/ 1
`
`8/1973 Theuerer et al,
`3,751,293
`427/52
`
`- 428/151
`3,770,479 11/1973 Dunning -------
`3,770,545 11/1973 Jackson ............................... 156/221
`3,775,157 11/1973 Fromson ............................. 427/250
`3,783,012
`l/ 1974 Morita et al.
`----------------------- 428/462
`
`Wavelock
`Exhibit 1012
`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:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:20)
`
`

`

`
`Page 2
`
`4,407,871
`
`5/1974 Askew ................................. 428/209
`3,809,568
`
`---- igfigg
`31:52:32: 323;:
`1111:5112; 21:11
`.. 313/94
`3:838:304 9/1974 McDonie .
`3,839,129 10/1974 Neumann .
`'... 428/61
`. 428/35
`3,843,475 10/1974 Kent ................
`
`. 427/250
`3,847,650 “/1974 Gregory et a1.
`
`..
`. 427/250
`3,873,347
`4/1975 Walker et a1.
`4/1975 Rairden, III ........
`. 427/250
`3,874,901
`
`428/31
`3,911,178 10/1975 McDowell et a1.
`
`. 427/250
`..
`3,914,472 10/ 1975 Nakanishi et al.
`
`3,915,809 10/ 1975 Wheatley ................... 204/15
`.
`. 427/265
`3,922,400 11/1975 Kawanoke et a1.
`
`1/1976 Rhodes, Jr. et a1.
`3,933,938
`428/31
`
`1/ 1976 Polinsky ..............
`3,934,059
`427/90
`
`2/1976 Brill et a1. ............ 427/343
`3,936,545
`3,949,139 4/1976 Dunning et a1. ......... 428/328
`
`8/1976 Lombardo et al.
`.
`..... 427/299
`3,978,252
`. 525/287
`3,987,127 10/1976 Dickie et a1.
`
`427/90
`.
`3,987,217 10/1976 Greeson et a1.
`
`..... 428/651
`3,998,603 12/1976 Rairden, III
`
`.. 427/255.6
`4,008,084 2/1977 Ikeda et a1.
`....... 427/90
`4,035,526 7/1977 Konantz et a1.
`
`9/1977 White et a1. ......... 427/250
`4,048,349
`
`9/1978 Sato et al. ....................... 427/250
`4,112,190
`
`FOREIGN PATENT DOCUMENTS
`39268/78 2/ 1980 Australia .
`37497/78 7/ 1981 Australia .
`
`OTHER PUBLICATIONS
`
`J. F. Pocza, A. Barna and P. B. Barna, “Formation
`Processes of Vacuum—Deposited Indium Films and
`Thermodynamical Properties of Submicroscopic Parti-
`cles Observed by In Situ Electron Microscopy”, Jour-
`nal of Vacuum Science and Technology, vol. 6, No. 4,
`Jul/Aug. 1969, pp. 472—475.
`Maisel, Leon 1. and Reinhard Gland, Eds., Handbook of
`Thin Film Technology, McGraw Hill, New York, 1970,
`pp. 8—26 to 8—37.
`Murakami, Yoshio, “Sticking Coefficients of Gold
`Atoms in the Nucleation and Growth Process of Gold
`Deposits on P01yfluoroethylene—propylene”, Japanese
`Journal ofApplied Physics, vol. 10, No. 1, Jan. 1971, pp.
`63—71.
`Murr, Lawrence B, “Effect of Electric and Magnetic
`Fields, Substrate Temperature, Pressure, and Evapora-
`tion Rate on the Nucleation, Structure, and Residual
`Properties of Vapor Deposited Metal Films”, USCEE
`
`Report 339, USC—113P22—2, Annual Progress Report
`No. 2, Department of Materials Science, University of
`Southern California, Period Apr. 1, 1969 to Mar. 31,
`1971.
`
`Port, C. Otis, “Restoring the Luster to Metallized Mar-
`kets”, Modern Plastics, Dec. 1974, pp. 42—46.
`Hale, G. J., G. W. White and D. E. Meyer, “Ion Plating
`Using a Pure Ion Source: An Answer Looking for
`Problems”, Electronic Packaging and Production, May
`1975, pp. 39—45.
`_
`Thornton, John A., “Influence of Substrate Tempera-
`ture and Deposition Rate on Structure of Thick Sput-
`tered Cu Coatings”, J. Vac Sci. Technol, vol. 12, No. 4,
`JUL/Aug. 1975, pp. 830—835.
`Pal, Arun K. and S. Chaudhuri, “Effect of Grain—-
`Boundary Scattering on the Electrical Resistivity of
`Indium Films”, Journal of Materials Science, vol. 11,
`1976, pp. 872—876.
`Eickelberg, Frederick, “Continuous Vacuum Metalliz-
`ing”, Modern Plastics, Dec. 1977, pp. 42—45.
`Halliday, David and Robert Resnick, “Interference
`from Thin Films,” Physics, John Wiley & Sons, N.Y.,
`1978, pp. 1006—1011.
`Sorg, Richard T., “Automotive Exterior Vacuum
`Metallizing—Past, Present, Future”, Society of Vac-
`uum Coaters (SVC) Tech. Conf., 1978, pp. 66—68.
`Norman, Michael K., “Vacuum Metallized Auto Ex-
`teriors—Past, Present, and Future,” SAE, Jun. 7, 1978,
`10 pp.
`Chopra, Kasturi, L., Thin Film Phenomena, Robert
`Krieger Publishing Co., Huntington, N.Y., 1979, pp.
`159—171.
`
`Schrantz, Joe, “Sputtering in Production at Chevrolet”,
`Industrial Finishing, Oct. 1979, pp. 33—35.
`Lindsay, D. M., “Alternatives to Conventional Chrome
`Plated Plastics,” SVC Annual Conference, 1979, pp.
`24—31.
`Smith, Hugh R., Jr., “A Critique on Current Deposition
`Techniques”, SVC Annual Conference,
`1979, pp.
`58—61.
`Kovacs, G. J. and P. S. Vincett, “Summary Abstract:
`Formation of Novel Vacuum Evaporated Submicron
`Particulate Monolayers Just Beneath a Heated Polymer
`Surface", J. Vac. Sci. Technol, vol. 20, No.3, Mar. 1982,
`pp. 419—420.
`
`Wavelock
`Exhibit 1012
`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:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:21)
`
`

`

`4,407,871
`
`Page 3
`
`Springborn Laboratories, Inc., “Future of Metallic Fin-
`ishesfor Plastics”, Apr. 1982, pp. 10, 20 and 92.
`Craighhead, H. G., R. E. Howard, J. E. Sweeney and
`D. M. Tennant, “Textured Surfaces: Optical Storage
`and Other Applications”, J. Vac. Sci. Technol, vol. 20,
`No. 3, Mar. 1982, DP. 316—319.
`“First Surface Mirrors and Beam Splitters”, from Evap-'
`orated Metal Films, Evaporated Metal Films Corp.,
`Ithaca, NY, (1959), 7 pp.
`Weast, Robert C., Handbook of Chemistry and Physics,
`Slst Ed., The Chemical Rubber Co., 1970, p. E204.
`Bozorth, Richard M., Ferromagnetism, D. Van Nos—
`trand Company, Inc., New York, 1951, pp. 146—148.
`“Metals Handbook”, 8th Edition, vol. 2, ASM Hand-
`book Committee, American Society for Metals, Metals
`Park, Ohio, 1964, pp. 517 and 518.
`
`Primary Examiner——William J. Van Balen
`Attorney, Agent, or Firm—John C. Evans
`
`[57]
`
`ABSTRACT
`
`on a dielectric substrate consists of minute specular
`electrically—discrete “islands” of the metal topcoated
`with a clear resinous layer which encapsulates and insu-
`lates the islands, one from another. The metal islands
`are less than one thousand angstroms thick and have an
`average diameter of less than three thousand angstroms.
`This island structure is secured by stopping the growth
`of the metal as it is deposited between the nucleation
`stage and the stage of channelization or formation of an
`electrically conductive film. The island structure per-
`mits the dielectric resinous topcoat
`to penetrate in,
`about and under the metal islands encapsulating and
`securely bonding them to the substrate.
`A preferred application of this invention is the manufac-
`ture of exterior automobile trim components the base
`structure of which is a flexible elastomer such as a ther-
`moplastic urethane and which have the appearance of
`electrodeposited chrome parts.
`
`A surprisingly corrosion and abuse resistant plastic
`object vacuum-metallized with a corrosion prone metal,
`
`16 Claims, 5 Drawing Figures
`
`Wavelock
`Exhibit 1012
`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:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:22)
`
`

`

`U.S. Patent
`
`Oct. 4, 1983
`
`Sheet 1 of3
`
`4,407,871
`
`REFLECMNCE
`
`D/FFUSE
`
`420
`
`460
`
`500
`
`540
`
`620
`
`660
`
`700
`
`740
`
`WAVE LENGTH {NM}.
`
`F/G.“ /
`
`Wavelock
`Exhibit 1012
`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:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:23)
`
`

`

`US. Patent
`
`Oct. 4, 1983
`
`Sheet 2 of 3
`
`4,407,871
`
`
`
`Wavelock
`Exhibit 1012
`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:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:24)
`
`

`

`U.S. Patent
`
`Oct. 4, 1983
`
`Sheet 3 of 3
`
`4,407,871
`
`
`
`FIG.4
`
`W.
`
`
`
`Wavelock
`Exhibit 1012
`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:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:25)
`
`

`

`1
`
`4,407,871
`
`VACUUM METALLIZED DIELECTRIC
`SUBSTRATES AND METHOD OF MAKING SAME
`
`RELATED APPLICATION
`
`This application is a continuation-in-part of applica-
`tion Ser. No. 133,857, “Vacuum Metallized Articles”
`filed Mar. 25, 1980 by the present inventor, now aban-
`doned,
`the description of which is incorporated by
`reference.
`
`PRIOR ART
`
`Vacuum metallizing of plastic and similar dielectric
`substrates has been practiced for some time, see US.
`Pat. Nos.
`2,992,125-—Fustier,
`2,993,806—Fisher,
`3,118,781—Downing
`3,914,472——-Nakanishi
`4,101,698—Dunning,
`4,131,530—Blum,
`4,211,822~Kaufman, and 4,215,170—Oliva.
`The automobile industry has had a desideratum for
`metallized trim components that could be substituted
`for conventional chrome-plated metal parts. See “Re-
`storing the Luster to Metallized Markets”, Modern Plas-
`tics, December,
`1974, page 42, et seq. However,
`weather, abuse and corrosion resistance of such metal-
`lized plastic parts has been marginal and their color
`match with electroplated chrome has been poor.
`Work has been done in other fields with the vacuum
`depositing of indium, e.g.
`see Japanese Pat. No.
`15812/78
`by Nobuyoshi
`Fujihashi
`and Hiroo
`Miyamoto. Work has also been reported on the effect of
`vacuum metallizing conditions on the deposited metal
`grain structure. See “Influence of Substrate Tempera—
`ture and Deposition Rate on Structure of Thick Sput-
`tered Cu Coatings” by John A. Thornton, J. Vac. Sci.
`Tee/21101., Vol. 12, No. 4, July/August 1975, page 830, et
`seq.
`Recently some commercial products have been
`made. See “Sputtering in Production at Chevrolet”,
`Industrial Finishing, October, 1979, describing the
`Camaro Berlinetta grilles coated with a chrome alloy;
`“Alternatives to conventional Chrome Plated Plastics”
`by D. M. Lindsey of the General Motors Chevrolet
`Engineering Center; and a “Critique on Current Prepa-
`ration Techniques” by Hugh R. Smith, Jr. of Industrial
`Vacuum Engineering, the latter two papers having been
`presented at the 1979 Society of Vacuum Coaters An-
`nual Conference; “Ion Plating Using 3 Pure Ion Source:
`An Answer Looking for Problems”, by Hale et a1, Elec-
`tronics Packaging and Production, May 1975, pg. 39 et
`seq; and “Continuous Vacuum Metallizing”, Modern
`Plastics, December, 1977, page 42 et seq. While these
`articles describe the supposed successful manufacture of
`exterior automobile trim components that can reason—
`ably be expected to give the performance required in
`service, they all fail to give the slightest hint that the
`vacuum metallized products do not look or appear as
`they should—that they are in fact substantially darker
`appearing than electro—deposited chrome and thus do
`not have the bright sheeny chrome look and showroom
`sparkle that a purchaser of a new automobile expects
`and demands.
`,
`No reference has been found that relates metal film
`
`island structure and spacing to the appearance and per-
`formance of a commercial product, to the conductivity
`of the metal layer, to the corrosion resistance of the
`metal layer and/or to the adhesion of the top coat. Nor
`does the prior art relate nucleation and film growth to a
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`2
`desired island structure and spacing that achieve these
`ends.
`With regard to the last statement, two excellent refer-
`ence books are:
`
`Thin Film Phenomena, Kasturi L. Chopra, Robert E.
`Kreiger Publishing Company, Huntington, NY. 1979.
`See especially pp. 163 et seq.
`Handbook of Thin Film Technology, Leon 1. Maissel
`and Reinhard Glang, McGraw-Hill Book Company,
`New York, NY. 1970. See especially pp 8—32 et seq.
`These texts discuss and illustrate the stages of metal
`film growth by vacuum deposition from metal nucle-
`ation and nuclei growth, to liquid coalescence, to elec-
`trically discrete islands, channelization with incipient
`film conductivity and finally full continuous film forma-
`tion. Film formation of vacuum deposited metals on
`plastic substrates for commercial products, especially
`on elastomeric plastic substrates, is not discussed. Nor is
`the interdependence of the natures of the metal film and
`the top coating correlated with product performance.
`None of the references show an awareness of the
`significant difference in performance to be obtained
`with a vacuum metallized flexible plastic product, top
`coated, where the metal particles are coalesced only to
`the island state instead of being allowed to coalesce to
`beyond the channellization stage where film conductiv-
`ity is established. A careful reading of the patent litera-
`ture will show that while a patentee may speak of the
`metal film being in particle form, these particles have
`resulted from the breaking up of a conductive coalesced
`continuous film by application of a solvent-containing
`top coating with the solvent attacking and causing
`swelling of the plastic base and consequent cracking
`and crazing. This cracking and crazing effect in most
`instances is quite striking, occurring within a few sec-
`onds of the application of the liquid top coat. The “is-
`lands” or particles formed by top coating of an electri—
`cally conductive metal film, while they may be electri-
`cally discrete after the top coat has been heat treated,
`are usually planar and have generally linear and angular
`corners as compared to the rounded, coalesced islands
`of the present inventions. In the present invention, the
`separate islands have coalesced from separate nucle—
`ation points, are globular or rounded and fused appear-
`ing and are part of the nucleation and growth process.
`The islands formed by cracking are substantially larger
`0n the average. They might better be termed “platelets"
`and can be likened to the cracked surface of a dried mud
`puddle, which cracks are usually visible to the naked
`eye and detract from the appearance.
`In general, the coalesced islands forming the indium
`films of the present invention are smaller and there is a
`much greater spacing between them that can be filled
`with the resin of the top coating, in effect encapsulating
`the islands and binding them to the substrate surface.
`The rounded islands are better protected by the resin
`and the film over all
`is far more corrosion resistant,
`surprisingly so. The metal film is much more securely
`adhered to the substrate—a very significant advantage.
`The appearance of the globular island product is bet-
`ter—it is more specular, more reflective.
`The construction of the metal island structure on an
`organic substrated and top coated with a resinous film
`gives a new product not heretofore known. From the
`literature it appears that others in depositing metals by
`vacuum evaporation allowed the films to become con-
`ductive,
`i.e. grow beyond the island stage, at a point
`
`Wavelock
`Exhibit 1012
`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:20)(cid:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:26)
`
`

`

`4,407,871
`
`3
`where their light transmission is too high to be useful, at
`least for the purposes of this invention.
`In U.S. Pat. No. 3,118,781, while the patentee refers
`to the “particles of the vapor-deposited metal layer”
`(Col. 4) in the same breath he says the applied top coat
`“will penetrate into minute or microscopic cracks or
`spaces” between them (emphasis added). This patentee
`vacuum deposits gold, an inherently corrosion-resistant
`metal, which by the time it
`is of a thickness to give
`sufficient reflectivity of visible light (4,000—7,000° A) to
`be of interest, forms an electrically continuous and con-
`ductive layer. Following application of his top coating,
`(Col. 5, line 32 et seq) the patentee secured an increase
`in light transmission, which is consistent with crazing or
`cracking of a continuous metal film having occurred
`during application of the top coat. The patentee uses an
`“ultra thin” top coat because of the cohesion of the thin
`coating is not great as its adhesion to the metal. His tape
`tests show that the resin does not flow about and encap-
`sulate his metal particles and bond well to the substrate
`under the platelets particles. Such an ultra-thin coating
`offers no physical protection to the metal film. In the
`present invention a top coat at least é mil thick is ap-
`plied to impart good abrasion resistance besides effect-
`ing the requisite encapsulation.
`U.S. Pat. No. 4,215,170 speaks of “an extremely thin
`coat of metallic particles deposited on a finely finished
`transfer agent." (Col. 2 lines 11-12) Those skilled in the
`art will appreciate that “particles" are not, cannot, be
`deposited from the vapor phase, Subsequently (Col. 4,
`line 23) the patentee refers to the “interstices or spaces
`between the metallic particles" following application of
`the top coat. Considering the metals (aluminum) and
`substrates (polypropylene) employed and the metal film
`thickness (105° A),
`it
`is obvious that his particles re-
`sulted from crazing of a continuous metal film. An alu-
`minum film deposited to that thickness is electrically
`conductive until
`top coated. To secure the discrete
`coalesced islands of this invention from spaced nucle-
`ation points, it is necessary that the melting point of the
`metal be low enough, and the temperature of the receiv—
`ing surface be high enough to effect the desired liquid
`coalescence of the metal. This could not happen in U.S.
`Pat. No. 4,215,170.
`U.S. Pat. No. 4,101,698 says that a metal layer “is
`applied to the elastomeric film as a separate, discontinu-
`ous or captured, (sic) generally planar, reflective seg—
`ments, preferably being applied in individual micro-
`scopic dots by vacuum-deposition.” (Col. 2, line 29 et
`seq). As discussed in the textbook references, the “pla-
`nar” stage of particle shape is reached only after there
`has been sufficient coalescence for
`film formation.
`While this patentee may have thought that his “seg-
`ments” were a result of the vacuum deposition, this was
`not the case—it was the result of the fracturing of a
`continuous film by application of the top coat.
`The fundamental fault with U.S. Pat. No. 4,101,698 is
`that this patentee does not describe a means or appara-
`tus for securing the “microscopic dots" he desired to
`have by vacuum deposition. At Col. 6 line 67 et seq., the
`patentee says the metal is vacuum deposited “in discon-
`tinuous quantities, or separate planar reflective seg-
`ments such as dots”. Did he use a screen or a grid of
`some type interposed between the source and the sub-
`strate? The size of the “dots” is not specified and in all
`probability they are ten to one hundred-fold times
`larger than the coalesced islands here of concern. In the
`present invention, the metal is not “applied” as “micro-
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`6O
`
`65
`
`4
`scopic dots” by “vacuum-deposition” (which is impos-
`sible) but are formed into “dots” or coalesced islands
`during the metallization.
`Neither U.S. Pat. No. 4,101,698 nor any other refer-
`ence makes mention of the highly improved corrosion
`resistance that can be secured via the placing of the
`metal in the coalesced island form. In fact, U.S. Pat. No.
`4,101,698 states in Co]. 2 that he prefers to use corrosion
`resistant metals with the preferred metal being chro-
`mium. Chromium cannot be formed into the coalesced
`islands of the present invention on the substrate and
`under
`the conditions disclosed in U.S. Pat. No.
`4,101,698.
`U.S. Pat. No. 4,211,822 deposits indium on a plastic
`substrate. Careful reading of this patent establishes that
`the patentee carried the deposition of the indium
`through the coalescence stage to the point where chan-
`nelization has occurred such that there is an intercon-
`necting network of conductive paths and the metal film
`overall appears to be conductive. The corrosion resis-
`tance of this metal film because it is conductive overall
`would be terrible even if a relatively good insulating
`topcoat were placed over the metal film. This patentee
`obviously had no appreciation of the advantage of limit-
`ing the growth of the metal nuclei to the coalesced
`island stage such that there could be no innerconnecting
`electrically conductive pathways between the co-
`alesced islands and the particles would be “free-float-
`ing” as desired in U.S.-Pat. No. 4,101,698 and in the
`present invention. It is believed that the theory of the
`patentee-in U.S. Pat. No. 4,211,882, Col. 2, line 17 et seq.
`is an erroneous theory as it is not the supposed melting-
`/ductility of the metal that is permitting its formability
`as described by the patentee. Instead the coalescence of
`the metal has been carried to a reticulate structure
`which accepts flexing and stretching of the plastic un-
`dercoat without loss of the conductive electrical path-
`ways.
`The prior art has (1) not appreciated the possibility of
`vacuum depositing a metal on an organic surface
`(which surface is “impure” and causes a high nucleation
`rate) and arresting the film growth before the channeli-
`zation/conductive stage of file formation is reached,
`using a metal and conditions to achieve a sufficient
`reflectivity to be of commercial interest, or (2) relating
`the resulting island structure to a desired product per-
`formance.
`
`PRESENT INVENTION
`
`The present invention is an article of manufacture
`comprising an organic dielectric base or substrate hav-
`ing a smooth surface such as a molded plastic, a macro-
`scopically continuous-appearing very thin layer thereon
`of a vacuum deposited corrosion—prone metal. The
`metal is in the form of minute specular electrically dis-
`crete rounded metal islands. There is a topcoating over
`the metal film of an intimately adhered clear dielectric
`resinous film encapsulating and protecting the metal
`particles, and binding them firmly to the substrate.
`This product is particularly useful in the automotive
`applications as an automobile exterior trim component
`to replace heavier and more expensive conventional
`chrome-plated metal parts.
`The present invention is based on the finding that
`with a thin vacuum metallized layer if the metal layer as
`it is being deposited or coalesced into electrically dis-
`crete islands and maintained electrically non-conduc-
`tive, the metal layer is corrosion resistant if adequately
`
`Wavelock
`Exhibit 1012
`Page 8
`(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:21)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:27)
`
`

`

`4,407,871
`
`5
`topcoated even though the metal is one that is corrosion
`prone such as indium. The metal film is‘ non-conductive
`as deposited because the metal nuclei initially deposited
`from the vapor phase are allowed to grow in molten
`phase only to a discrete island stage with the particles
`being electrically isolated from one another. The coat-
`ing is kept quite thin and there is insufficient metal de-
`posited to bring about a bridging or coalescence of the
`metal particles and formation of an electrically conduc-
`tive film. For most metals, the metal layer should have
`a nominal thickness less than lOOO’A, preferably less
`than 600° A. By “nominal thickness” is meant the thick-
`ness determined by the weight of metal'deposited per
`unit area as if a continuous film. An interferometer gives
`about the same reading.
`The metal film on the other hand must be thick
`enough to reflect sufficient light, i.e. it must be opaque
`enough, to make the coated article appear as a metal
`article. Desirably the film will pass less than 25% of the
`light incident thereon at an angle greater than 60° . With
`some metals, such as aluminum and silver it is impossi-
`ble at a practical temperature, to vacuum deposit suffi-
`cient metal to give the desired opacity and reflectivity
`and not to deposit so much as secure film electrical
`conductivity, i.e. bridging between the metal islands.
`The nature and temperature of the substrate surface and
`the operating condition can be important in this regard.
`For most metals,
`the minimum useful nominal
`film
`thickness will be at least 150° A.
`If the individual metal islands have a diameter that is
`a fraction of the wave length of light, say a diameter of
`less than 3500° A, preferably less than 3000” A on the
`average, the metal layer is quite bright and specular and
`not milky or whitish as occurs when the island size
`exceeds about 4000° A. The appearance of an indium
`layer deposited according to this invention and top
`coated approximates that of electroplated chrome.
`While vacuum metallized commercial products have
`heretofore been made from metals that are inherently
`corrosion resistant such as chromium or stainless steel,
`such vacuum metallized films are electrically conduc-
`tive, and dark and unsatisfactory appearing. They do
`not look like electrodeposited chrome.
`The metal film can be deposited by thermal evapori-
`zation, sputtering, ion plating, induction heating, elec-
`tron beam evaporization and like methods. See Thin
`Film Technology, by Berry et al. D. Van Nostrand Com-
`pany,
`Inc. Princeton, N.J.,
`1968, Lib. of Cong.
`68-25817. Better or more uniform'coverage appears to
`be secured especially with three dimensidnal objects
`having corners, edges, or recesses if some atoms of an
`inert gas such as argon are present in the vacuum cham-
`ber in excess of those required for‘ the evaporation. The
`vacuum deposition is preferably carried 'out at a vacuum
`of 5 ><10—3 Torr Or leSs.
`When the spacing between the metal islands of the
`film is such as to have the metal film electrically non—
`conductive, improved adhesion of the protective plastic
`topcoat results. This adhesion can be measured for ex-
`ample by the Ford adhesion test, specification No. ESB-
`M2P-105 B, or the Chevrolet tape adhesion test, Speci-
`fication No. CTZ VM003 AA. This improved adhesion
`appears to be related to the separation betweenvthe
`individual metal islands or width of the. channels, i.e. to
`the distinctiveness of the islands, rather'than to their
`diameter or size. The top coating in cross sec‘tiori'ap-
`pears to encapsulate the islands, extending around and
`
`6
`under them to secure good wetting of and adhesion to
`the substrate surface.
`A novel and important point of this invention is this
`feature of encapsulating the metal islands to “fix" the
`electrical non-conductivity of the metal film and thus to
`increase manifold the corroSion resistance of the film. If
`the integrity of the topcoat is broken and moisture en-
`ters it only causes oxidation of the metal islands contigu-
`ous to the break and the blight of the corrosion cannot
`travel along the plane of the film under the topcoat as it
`can with the usual vacuum metallized and coated ob-
`jects made with corrosion prone metals such as alumi-
`num or conductive indium;
`The resinous topcoat also improves resistance to me-
`chanical abuse. Clear moisture resistant acrylic, ure-
`thane, and like coatings applied as a latex and more
`preferably as a solvent solution are suitable. For critical
`applications the topcoat will be baked to assure that a
`good tough continuous film is produced. The plastic
`film appears to fill the interstices and voids between and
`around the individual metal islands and helps further
`isolate one from another.
`This invention is most usefully applied to metals and
`alloys which are not inherently strongly corrosion resis-
`tant: zinc,
`tin, gallium, aluminum, cadmium, copper,
`nickel, cobalt or iron as opposed to stainless steel, gold,
`platinum, chromium, nichrome, palladium and rho-
`dium. Some of the latter such as rhodium are prohibi-
`tively expensive. With some of these metals such as
`nickel, cobalt, chromium and copper it has not been
`demonstrated as yet that the metal can be made to yield
`to the desired rounded island structure on a plastic
`substrate at an operable substrate temperature. The
`metal should have a melting point in the range of 100° to
`350° C., preferably 125° to 250°. The word “metal” as
`used in the claims includes metal alloys having these
`characteristics, as well as pure metals.
`Any suitable dielectric,
`i.e. electrically insulating,
`material can be used to receive the vacuum deposited
`metal such as dry wood, glass, or a plastic. For the
`intended automobile trim component application 2 cas-
`table or moldable plastic is used, preferably an elasto-
`mer that is tough and abuse resistant with so