EP3645769B1 - Method of making an article - Google Patents

Method of making an article Download PDF

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Publication number
EP3645769B1
EP3645769B1 EP18755304.5A EP18755304A EP3645769B1 EP 3645769 B1 EP3645769 B1 EP 3645769B1 EP 18755304 A EP18755304 A EP 18755304A EP 3645769 B1 EP3645769 B1 EP 3645769B1
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EP
European Patent Office
Prior art keywords
film
thermally
cex
graphite
softenable
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EP18755304.5A
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German (de)
English (en)
French (fr)
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EP3645769A1 (en
Inventor
Megan A. CREIGHTON
Morgan A. PRIOLO
Joel A. Getschel
Taylor J. Kobe
Onur Sinan YORDEM
Benjamin R. COONCE
Eric A. VANDRE
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

Definitions

  • the present disclosure broadly relates to methods for improving the durability of particle coatings on thermally-softenable films, and articles preparable thereby.
  • Coatings of certain particles (e.g., graphite) on substrates can be formed by rubbing a powder containing the particles against a substrate such as, for example, a thermoplastic film.
  • a powder coating will be referred to herein as "powder-rubbed coatings".
  • powder-rubbed coatings examples include those disclosed in U. S. Pat. No. 6,511,701 B1 (Divigalpitiya et al. ).
  • powder-rubbed coatings and methods of forming them include those disclosed in U. S. Pat. No. 6,511,701 B1 (Divigalpitiya et al. ).
  • such films are typically prone to damage by methods such as abrasion and/or rinsing with solvent.
  • US Patent 6511701B1 discloses a method of coating a polymer substrate with a dry composition comprising particles.
  • the particles have a Mohs hardness between 1 and 2.5 and preferably a largest dimension of less than 100 microns.
  • the particles are buffed on the substrate with an applicator which moves in a manner parallel to the surface of the substrate.
  • US patent US4741918 discloses a abstract coated with a coating material by rubbing substantially dry discrete particles of the coating material across the surface of the substrate with a sufficient rate of energy input to cause them to adhere. The particles are carried on the surface of a soft, resilient buffing wheel rotating sufficient rapidly to give peripheral speeds of from 2 to 200 m/s.
  • Exemplified coating materials include metals, metal oxides and plastics.
  • US patent application US2014329082 discloses an article including a substrate having a first major surface and optionally a second major surface. A layering arrangement is disposed on either or both of the first major surface and the second major surface. The layering arrangement includes a carbon layer and a conducting polymer layer.
  • US patent US5925402 discloses coating powder is applied to a substrate as a means of providing a patterned coating on a substrate, either decorative or functional. Then the coating powder is fused or fused and cured in selected portions by computer-guided laser.
  • US patent application US2015344712 discloses methods and compositions for creating durable surface marks and/or decorations on substrates including metal, glass, ceramic, porcelain, natural and engineered stone, as well as plastics, polymer composites and other organic materials with color, high resolution and high contrast using inkjet technology and laser, NIR diode or UV LED energy. Smoothness and durability are obtained by using nanoparticles of silica, pigments and other materials in such marking processes.
  • the present disclosure provides a method of making an article comprising exposing a particle coating disposed on a thermally-softenable film to a modulated source of electromagnetic radiation wherein the thermally-softenable film comprises a thermoplastic polymer, wherein the modulated source of electromagnetic radiation comprises a flashlamp, wherein the particle coating consists essentially of graphite, wherein the particle coating comprises loosely bound distinct particles that are not covalently bonded to each other, and are not retained in a binder material other than the thermally-softenable film.
  • An article prepared according to the above method comprises a thermally-softenable film having a particle coating disposed thereon, wherein the particle coating comprises distinct particles that are not covalently bonded to each other, and are not retained in a binder material other than the thermally-softenable film, and wherein at least one portion of the particle coating corresponding to a predetermined pattern has a greater transmittance to visible light than at least one portion of the particle coating that is not disposed within the predetermined pattern.
  • An article prepared according to the above method comprises a thermally-softenable film having a particle coating disposed thereon, wherein the particle coating comprises distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable film, and wherein the change in transmittance is at most 60 percent after abrading the particle coating according to ASTM D6279-15 "Standard Test Method for Rub Abrasion Mar Resistance of High Gloss Coatings" with the 25 mm friction element being outfitted with a two inch square Crockmeter cloth soaked in isopropanol for three seconds.
  • powder refers to a free-flowing collection of minute particles.
  • pulsed electromagnetic radiation refers to electromagnetic radiation that is modulated to become a series of discrete spikes with increased intensity.
  • the spikes may be relative to a background level of electromagnetic radiation that is negligible or zero, or the background level may be at a higher level that is substantially ineffective to increase adhesion of particles in the particle coating to the film.
  • thermo-softenable means softenable upon heating.
  • particle coating refers to a coating of minute particles which may or may not be free-flowing.
  • the present disclosure provides an easy method to enhance the durability of particle coatings (e.g., to solvent abrading) on thermally-softenable films using instantaneous heating by exposure to a modulated source of electromagnetic radiation comprising a flashlamp.
  • exemplary article 100 comprises a thermally-softenable (e.g., thermoplastic) film 110 having a particle coating 120 disposed thereon.
  • the particle coating comprises distinct particles that are not covalently bonded to each other and are not retained in a binder material other than the thermally-softenable film.
  • Particle coatings on thermally-softenable films can be prepared by various known methods including, for example, exposure to an aerosolized powder cloud, contact with a powder bed, coating with a solvent-based powder dispersion coating followed by evaporation of solvent, and/or triboadhesion (rubbing dry particles against a substrate to form a powder-rubbed coating) of the powder using a rubbing process.
  • triboadhesion methods can be found in U. S. Pat. Nos. 6,511,701 B1 (Divigalpitiya et al. ), 6,025,014 (Stango ), and 4,741,918 (Nagybaczon et al. ). The remaining methods will be familiar to those of ordinary skill in the art.
  • Useful powders comprise minute loosely bound particles capable of absorbing at least one wavelength of the pulsed electromagnetic radiation, preferably corresponding to a majority of the energy of the pulsed electromagnetic radiation.
  • Suitable powders are preferably at least substantially unaffected by electromagnetic radiation, but are moderate to strong absorbers of it. This is desirable to maximize the light (electromagnetic radiation) to heat conversion yield without altering the chemical nature of the powder particles.
  • Powders include powders comprising graphite, clays, hexagonal boron nitride, pigments, inorganic oxides (e.g., alumina, calcia, silica, ceria, zinc oxide, or titania), metal(s), organic polymeric particles (e.g., polytetrafluoroethylene, polyvinylidene difluoride), carbides (e.g., silicon carbide), flame retardants (e.g., aluminum trihydrate, aluminum hydroxide, magnesium hydroxide, sodium hexametaphosphate, organic phosphonates and phosphates and ester thereof), carbonates (e.g., calcium carbonate, magnesium carbonate, sodium carbonate), dry biological powders (e.g., spores, bacteria), and combinations thereof.
  • inorganic oxides e.g., alumina, calcia, silica, ceria, zinc oxide, or titania
  • metal(s) e.g., aluminum boronitride,
  • the powder particles have an average particle size of 0.1 to 100 micrometers, more preferably 1 to 50 micrometers, and more preferably 1 to 25 micrometers, although this is not a requirement.
  • the particle coating according to the invention consists essentially of graphite.
  • the particle coating after application, consists essentially of (i.e., be at least 98 percent by weight, preferably at least 99 percent by weight, or even consist of) graphite particles.
  • the particle coating Prior to exposure to the electromagnetic radiation the particle coating comprises loosely bound distinct particles that are not covalently bonded to each other, and are not retained in a binder material other than the thermally-softenable film itself.
  • the thermally-softenable film comprises one or more thermally-softenable (e.g., lightly crosslinked and/or thermoplastic) polymers.
  • thermally-softenable polymers that may be suitable for inclusion in a thermally-softenable film include polycarbonates, polyesters, polyamides, polyimides, polyurethanes, polyetherketone (PEK), polyetheretherketone (PEEK), polyphenylene sulfide, polyacrylics (e.g., polymethyl methacrylate), polyolefins (e.g., polyethylene, polypropylene, biaxially-oriented polypropylene), and combinations of such resins.
  • a pulsed electromagnetic radiation may come from any source(s) capable of generating sufficient fluence and pulse duration to effect sufficient heating of the thermally-softenable film to cause the particle coating to bind more tightly to it.
  • sources may be effective for this purpose: flashlamps, lasers, and shuttered lamps.
  • flashlamps lasers
  • shuttered lamps The selection of appropriate sources will typically be influenced by desired process conditions such as, for example, line speed, line width, spectral output, and cost.
  • the pulsed electromagnetic radiation is generated using a flashlamp.
  • xenon and krypton flashlamps are the most common. Both provide a broad continuous output over the wavelength range 200 to 1000 nanometers, however the krypton flashlamps have higher relative output intensity in the 750-900 nm wavelength range as compared to xenon flashlamps which have more relative output in the 300 to 750 nm wavelength range.
  • xenon flashlamps are preferred for most applications, and especially those involving graphite powder.
  • Many suitable xenon and krypton flashlamps are commercially available from vendors such as Excelitas Technologies Corp. of Waltham, Massachusetts and Heraeus of Hanau, Germany.
  • a pulsed electromagnetic radiation can be generated using a pulsed laser.
  • Suitable lasers may include, for example, excimer lasers (e.g., XeF (351 nm), XeCl (308 nm), and KrF (248 nm)), solid state lasers (e.g., ruby 694 nm)), and nitrogen lasers (337.1 nm).
  • a pulsed electromagnetic radiation is generated using a continuous light source and a shutter (preferably a rotating aperture/shutter to reduce overheating of the shutter).
  • Suitable light sources may include high-pressure mercury lamps, xenon lamps, and metal-halide lamps.
  • the electromagnetic radiation spectrum is preferably most intense at wavelength(s) that are strongly absorbed by the powder particles, although this is not a requirement.
  • the electromagnetic radiation spectrum is preferably most intense in spectral regions in which the powder is least reflective, although this is not a requirement.
  • the source of pulsed electromagnetic radiation is capable of generating a high fluence (energy density) with high intensity (high power per unit area), although this is not a requirement.
  • high fluence energy density
  • intensity high power per unit area
  • the pulse duration is preferably short; e.g., less than 10 milliseconds, less than 1 millisecond, less than 100 microseconds, less than 10 microseconds, or even less than 1 microsecond, although this is not a requirement.
  • the pulsed electromagnetic radiation preferably be powerful, but the exposure area is preferably large and the pulse repetition rate is preferably fast (e.g., 100 to 500 Hz).
  • the modulated electromagnetic radiation may be directed through a mask having transmissive and non-transmissive regions according to a predetermined pattern (e.g., see Fig 2 .). Accordingly, exposed regions of the particle coating may become more transparent to visible light than unexposed region of the particle coating (see Fig. 3 ).
  • an optional development step e.g., mild abrasion with a solvent-soaked wiper
  • a particle coating remains in the exposed region according to the predetermined pattern while it is substantially or completely removed in the unexposed (i.e., blocked) region (see FIG. 4 ).
  • the present disclosure provides a method comprising exposing a particle coating disposed on a thermally-softenable film to a modulated source of electromagnetic radiation, wherein the thermally-softenable film comprises a thermoplastic polymer, wherein the modulated source of electromagnetic radiation comprises a flashlamp, wherein the particle coating consists essentially of graphite, wherein the particle coating comprises loosely bound distinct particles that are not covalently bonded to each other, and are not retained in a binder material other than the thermally-softenable film.
  • the present disclosure provides a method according to the first wherein the particle coating comprises a powder-rubbed coating.
  • the present disclosure provides a method according to any one of the first to second embodiments, wherein the particle coating is exposed to the pulsed electromagnetic radiation according to a predetermined pattern.
  • PET polyethylene terephthalate (PET) film 125 micrometers thick, glass transition temperature (T g ) of 76°C, obtained from DuPont Tejin Films, Chester Virginia, as MELINEX ST505 polyester film
  • T g glass transition temperature
  • MELINEX ST505 polyester film Bare PET PET film, 2-mil, (51 micrometers) thickness
  • MICRO 850 Graphite powder 3-5 micrometers particle size, 13 m 2 /g surface area, 0.088 ohm ⁇ cm resistivity, obtained from Ashbury Graphite Mills, Inc., Kittanning, Pennsylvania as MICRO850 graphite Isopropanol (IPA) solvent, obtained from Aldrich Chemical Company, Milwaukee, Wisconsin
  • graphite coatings were applied onto PET films by placing a small amount of MICRO850 on the PET films. The graphite was then rubbed against the film using a WEN 10PMC 10-inch (25.8-cm) random orbital waxer/polisher (WEN Products, Elgin, Illinois) equipped with a wool polishing bonnet. The relative amount of graphite coating deposited on the PET film was determined by measuring the surface resistivity using a four-point probe and/or light transmittance.
  • CEX-C and EX10 to EX12 were evaluated for durability according to ASTM D6279-15 "Standard Test Method for Rub Abrasion Mar Resistance of High Gloss Coatings", ASTM International, West Conshocken, Pennsylvania, with the 25 mm friction element being outfitted with a two inch (5.1 cm) square Crockmeter cloth soaked in isopropanol for three seconds.
  • Crockmeter cloth is available from Testfabrics, Inc. West Pittson, Pennsylvania.
  • Crockmeter cloth conforms to the specifications of ASTM D3690-02(2009) "Standard Performance Specification for Vinyl-Coated and Urethane-Coated Upholstery Fabrics-Indoor".
  • Transmittance of graphite-coated film specimens was measured before and after durability testing. All transmittance measurements represent an average of at least 3 measurements.
  • T film is the transmittance of the underlying polymer film
  • T C is the transmittance of that same film after the coating and treatments had been applied
  • T abraded is the transmittance of the coating after being subjected to the desired number of abrading cycles.
  • Transmittance values of the films are typically around 92 ⁇ 5%, depending on the quality of the substrate used. Smaller changes in transmittance ( ⁇ T, %) are indicative of higher retention of the total fraction of carbon on the original film.
  • CEX-A to CEX-C and EX-1 to EX-12 were prepared by subjecting graphite coated PET substrate films prepared as described above to an Intense Pulsed Light (IPL) irradiation.
  • IPL Intense Pulsed Light
  • the source used was a SINTERON S-2100 Xe flashlamp equipped with Type C bulb from Xenon Corporation, Wilmington, Massachusetts.
  • the substrate was Bare PET.
  • EX-1 was placed under the flashlamp with the graphite-coated surface facing up and treated ten times at a pulse rate of 1 Hz and an energy density of 0.4 J/cm 2 .
  • CEX-B was prepared in the same manner as CEX-A, except that the substrate was Melinex PET.
  • EX-2 was prepared in the same manner as EX-1, except that the substrate was Melinex PET and treated 5 times at a pulse rate of 1 Hz and an energy density of 0.3 J/cm 2 .
  • EX-3 and EX-4 were prepared in the same manner as EX-2, except that the film was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.5 J/cm 2 (EX-3) and 1.0 J/cm 2 (EX-4).
  • EX-5 was prepared similarly to EX-4, except the film was flipped over such that the graphite coated surface was facing away from the flashlamp bulb.
  • EX-6 to EX-8 were prepared by coating three separate sheets of Bare PET with differing amounts of graphite to achieve differing surface resistivity values for each Example. EX-6 to EX-8 were placed under the flashlamp with the graphite-coated surface facing up and treated ten times at a pulse rate of 1 Hz and an energy density of 0.4 J/cm 2 . Table 2, below, reports the change in transmittance ⁇ T in %. TABLE 2 EXAMPLE INITIAL SURFACE RESISTIVITY, ⁇ /square ⁇ T, % EX-6 250 14.5 EX-7 564 22.3 EX-8 975 23.4
  • the substrate coated with graphite was Bare PET.
  • a chromium/glass patterned photomask shown in Fig. 2
  • the area directly adjacent to the mask is denoted as the unmasked area, whereas the area beneath the mask was shielded from IPL and is denoted as the masked area.
  • the photomask included linear shape openings in the chrome layer having width of approximately about 250 micrometers or having width of approximately about 500 micrometers. This demonstrates the ability of these coatings to be patterned, with the openings portion of the mask representing a desired pattern for improved particle retention.
  • Table 3 report the effects of IPL on particle retention of masked and unmasked (patterned) graphite coated PET.
  • Fig. 3 shows the resulting pattern, with the portion beneath the openings and masked portion.
  • Fig. 4 shows the resulting pattern after being subjected to abrasion as described above, with the portion beneath the openings remaining coated with carbon and the masked portion being devoid of carbon due to abrasion.
  • the substrate was Bare PET.
  • EX-10 was placed under the flashlamp with the graphite-coated surface facing up and treated ten times at a pulse rate of 1 Hz and an energy density of 0.4 J/cm 2 .
  • EX-11 was prepared in the same manner as EX-10, except that the film was coated with a different amount of graphite to achieve a higher surface resistivity value than EX-10.
  • EX-12 was prepared in the same manner EX-10, except that the substrate was Melinex PET and treated 5 times at a pulse rate of 1 Hz and an energy density of 0.3 J/cm 2 .
  • Tables 5-7 summarize the effect of heat gun (Table 5), e-beam (Table 6), and biaxial stretch (Table 7) exposures had on particle retention ( ⁇ T, %, average normalized change in transmission).
  • ⁇ T particle retention
  • % average normalized change in transmission

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP18755304.5A 2017-06-29 2018-06-27 Method of making an article Active EP3645769B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762526720P 2017-06-29 2017-06-29
PCT/IB2018/054772 WO2019003153A1 (en) 2017-06-29 2018-06-27 ARTICLE AND METHOD OF MANUFACTURE

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EP3645769A1 EP3645769A1 (en) 2020-05-06
EP3645769B1 true EP3645769B1 (en) 2025-04-30

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US (1) US20200115804A1 (enrdf_load_stackoverflow)
EP (1) EP3645769B1 (enrdf_load_stackoverflow)
JP (1) JP7170677B2 (enrdf_load_stackoverflow)
CN (1) CN110832116B (enrdf_load_stackoverflow)
WO (1) WO2019003153A1 (enrdf_load_stackoverflow)

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US11241711B2 (en) 2017-03-22 2022-02-08 3M Innovative Properties Company Buff-coated article and method of making the same
JP7326167B2 (ja) 2017-06-29 2023-08-15 スリーエム イノベイティブ プロパティズ カンパニー 物品及びその製造方法
KR102461992B1 (ko) * 2020-12-30 2022-11-03 마이크로컴퍼지트 주식회사 육방정 질화붕소 입자를 포함하는 코팅액의 코팅 방법 및 이에 의하여 제조되는 방열부재

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GB8401838D0 (en) 1984-01-24 1984-02-29 Tribohesion Ltd Coating process
US5827368A (en) 1997-06-02 1998-10-27 Marquette University Device for depositing a layer of material on a surface
US5925402A (en) * 1998-07-15 1999-07-20 Morton International, Inc. Method of forming a hidden identification using powder coating
US6511701B1 (en) * 2000-05-09 2003-01-28 3M Innovative Properties Company Coatings and methods
JP3631982B2 (ja) * 2000-06-16 2005-03-23 三菱重工業株式会社 遮熱コーティング材の製造方法
FR2832736B1 (fr) * 2001-11-28 2004-12-10 Eppra Procede perfectionne de revetement d'un support par un materiau
JP3979464B2 (ja) * 2001-12-27 2007-09-19 株式会社荏原製作所 無電解めっき前処理装置及び方法
US7569174B2 (en) * 2004-12-07 2009-08-04 3D Systems, Inc. Controlled densification of fusible powders in laser sintering
JP2009124029A (ja) * 2007-11-16 2009-06-04 Shinshu Univ インクジェットによる電子回路基板の製造方法
JP2015507560A (ja) * 2011-12-22 2015-03-12 スリーエム イノベイティブ プロパティズ カンパニー 炭素コーティングされた物品及びその製造方法
US9744559B2 (en) * 2014-05-27 2017-08-29 Paul W Harrison High contrast surface marking using nanoparticle materials
WO2015197811A1 (en) * 2014-06-26 2015-12-30 Shell Internationale Research Maatschappij B.V. Coating method and coated substrate

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US20200115804A1 (en) 2020-04-16
JP2020525271A (ja) 2020-08-27
CN110832116B (zh) 2023-01-13
EP3645769A1 (en) 2020-05-06
WO2019003153A1 (en) 2019-01-03
JP7170677B2 (ja) 2022-11-14
CN110832116A (zh) 2020-02-21

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