EP3645769A1 - Article and method of making the same - Google Patents

Article and method of making the same

Info

Publication number
EP3645769A1
EP3645769A1 EP18755304.5A EP18755304A EP3645769A1 EP 3645769 A1 EP3645769 A1 EP 3645769A1 EP 18755304 A EP18755304 A EP 18755304A EP 3645769 A1 EP3645769 A1 EP 3645769A1
Authority
EP
European Patent Office
Prior art keywords
particle coating
article
thermally
graphite
predetermined pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP18755304.5A
Other languages
German (de)
French (fr)
Other versions
EP3645769B1 (en
Inventor
Megan A. CREIGHTON
Morgan A. PRIOLO
Joel A. Getschel
Taylor J. Kobe
Onur Sinan YORDEM
Benjamin R. COONCE
Eric A. VANDRE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of EP3645769A1 publication Critical patent/EP3645769A1/en
Application granted granted Critical
Publication of EP3645769B1 publication Critical patent/EP3645769B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only
    • C23C24/04Impact or kinetic deposition of particles
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only

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 Bl (Divigalpitiya et al.).
  • powder-rubbed coatings and methods of forming them include those disclosed in U. S. Pat. No. 6,511,701 Bl (Divigalpitiya et al.).
  • such films are typically prone to damage by methods such as abrasion and/or rinsing with solvent.
  • the present disclosure provides a method comprising exposing a particle coating disposed on a thermally-softenable film to a modulated source of electromagnetic radiation (e.g., a flashlamp), 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.
  • a modulated source of electromagnetic radiation e.g., a flashlamp
  • the present disclosure provides an article made according to the method of the first aspect of the present disclosure.
  • the present disclosure provides an article comprising 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.
  • the present disclosure provides an article comprising 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
  • visible light refers to electromagnetic radiation having a wavelength of 400 to 700 nanometers (nm).
  • 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.
  • Fig. 1 is an enlarged schematic side view of an exemplary article 100 according to the present disclosure.
  • Fig. 2 is a digital photograph of a mask used in Example 9 (EX-9).
  • Fig. 3 is a digital photograph of the flashlamp treated graphite-coated film in EX-9.
  • Fig. 4 is a digital photograph of the flashlamp treated graphite-coated film in EX-9
  • 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.
  • 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
  • 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.
  • Suitable 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
  • 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.
  • Graphite and hexagonal boron nitride are particularly preferred in many applications.
  • the particle coating after application, may consist essentially of (i.e., be at least 98 percent by weight, preferably at least 99 percent by weight), or even consist of the powder particles (e.g., 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 may comprise 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.
  • the 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.
  • At least three types of 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.
  • 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.
  • the 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).
  • the 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.).
  • 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 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 embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
  • the present disclosure provides a method according to the first or second embodiment, wherein the particle coating consists essentially of graphite.
  • the present disclosure provides a method according to any one of the first to third embodiments, wherein the modulated source of electromagnetic radiation comprises a flashlamp.
  • the present disclosure provides a method according to any one of the first to third embodiments, wherein the modulated source of electromagnetic radiation comprises a pulsed laser.
  • the present disclosure provides a method according to any one of the first to third embodiments, wherein the particle coating comprises a powder-rubbed coating.
  • the present disclosure provides a method according to any one of the first to sixth embodiments, wherein the particle coating is exposed to the pulsed electromagnetic radiation according to a predetermined pattern.
  • the present disclosure provides an article made according to the method of any one of the first to seventh embodiments.
  • the present disclosure provides an article comprising 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.
  • the present disclosure provides an article according to the ninth embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
  • the present disclosure provides an article according to the ninth or tenth embodiment, wherein the particle coating consists essentially of graphite.
  • the present disclosure provides an article according to any one of the ninth to eleventh embodiments, wherein the thermally-softenable film comprises polyethylene terephthalate.
  • the present disclosure provides an article according to any one of the ninth to eleventh embodiments, wherein the thermally-softenable film comprises polyethylene terephthalate.
  • the present disclosure provides an article according to any one of the ninth to twelfth embodiments, wherein the predetermined pattern comprises a circuit trace.
  • the present disclosure provides an article according to any one of the ninth to thirteenth embodiments, wherein the at least one portion of the particle coating that is not disposed within the predetermined pattern comprises a powder-rubbed coating.
  • the present disclosure provides an article comprising 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.
  • the present disclosure provides an article according to the fifteenth embodiment, wherein the particle coating comprises a powder-rubbed coating.
  • the present disclosure provides an article according to the fifteenth or sixteenth embodiment, 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.
  • 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 lOPMC 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 fflm is the transmittance of the underlying polymer film
  • Tc 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
  • EXAMPLES EX-1 to EX- 12 and COMPARATIVE EXAMPLES CEX-A to CEX-C 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
  • 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 ⁇ in %.
  • the substrate coated with graphite was Bare PET.
  • a chromium/glass patterned photomask shown in Fig. 2 was situated between the flashlamp and the graphite.
  • 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.
  • CEX-C CEX-C to EX- 10
  • 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 .
  • the coated PET specimens were taped on to a moving PET web and conveyed through the e-beam processor at a voltage of 110 keV.
  • the web speed and e-beam current applied to the cathode were varied to ensure delivery of the targeted dose.
  • 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 ( ⁇ , %, average normalized change in transmission).
  • heat gun an output greater than 232°C and/or for longer than 10 minutes was also applied, but was found to result in both excessive thermal degradation of the polymer or unrealistic processing conditions for manufacturing.
  • biaxial stretching stretching larger than 5% was also applied, but was found to result in excessive tension of the polymer leading to film fracture.

Landscapes

  • 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)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé comprenant l'exposition d'un revêtement particulaire, recouvrant un film apte à être ramolli thermiquement, à une source modulée de rayonnement électromagnétique. Le revêtement particulaire comprend des particules distinctes qui ne sont pas liées de manière covalente les unes aux autres, et ne sont pas retenues dans un matériau liant autre que le film apte à être ramolli thermiquement. L'invention concerne également des articles réalisés selon ledit procédé.The invention relates to a method comprising exposing a particulate coating, covering a thermally softenable film, to a modulated source of electromagnetic radiation. The particulate coating comprises discrete particles that are not covalently bonded to one another, and are not retained in a binder material other than the thermally softenable film. The invention also relates to articles made according to said method.

Description

ARTICLE AND METHOD OF MAKING THE SAME
TECHNICAL FIELD
The present disclosure broadly relates to methods for improving the durability of particle coatings on thermally-softenable films, and articles preparable thereby.
BACKGROUND
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. Such powder coatings will be referred to herein as "powder-rubbed coatings". Examples of powder-rubbed coatings and methods of forming them include those disclosed in U. S. Pat. No. 6,511,701 Bl (Divigalpitiya et al.). However, such films are typically prone to damage by methods such as abrasion and/or rinsing with solvent.
SUMMARY
In a first aspect, the present disclosure provides a method comprising exposing a particle coating disposed on a thermally-softenable film to a modulated source of electromagnetic radiation (e.g., a flashlamp), 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.
By this technique, durability of the powder coating is improved, while alternative heating methods were prone to damaging (e.g., warping) the thermally-softenable film.
Accordingly, in a second aspect, the present disclosure provides an article made according to the method of the first aspect of the present disclosure.
In a third aspect, the present disclosure provides an article comprising 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.
In a fourth aspect, the present disclosure provides an article comprising 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. As used herein:
The term "visible light" refers to electromagnetic radiation having a wavelength of 400 to 700 nanometers (nm).
The term "powder" refers to a free-flowing collection of minute particles.
The term "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.
The term "thermally-softenable" means softenable upon heating.
The term "particle coating" refers to a coating of minute particles which may or may not be free- flowing.
Features and advantages of the present disclosure will be further understood upon consideration of the detailed description as well as the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an enlarged schematic side view of an exemplary article 100 according to the present disclosure.
Fig. 2 is a digital photograph of a mask used in Example 9 (EX-9).
Fig. 3 is a digital photograph of the flashlamp treated graphite-coated film in EX-9.
Fig. 4 is a digital photograph of the flashlamp treated graphite-coated film in EX-9
after abrading with a solvent soaked wiper.
It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the disclosure. DETAILED DESCRIPTION
Advantageously, 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.
Referring now to Fig. 1, 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. Examples of triboadhesion methods can be found in U. S. Pat. Nos. 6,511,701 B l (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.
Suitable 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. Preferably, 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. Graphite and hexagonal boron nitride are particularly preferred in many applications.
In some embodiments, the particle coating, after application, may consist essentially of (i.e., be at least 98 percent by weight, preferably at least 99 percent by weight), or even consist of the powder particles (e.g., graphite particles).
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 may comprise one or more thermally-softenable (e.g., lightly crosslinked and/or thermoplastic) polymers. Exemplary 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.
The 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. At least three types of sources may be effective for this purpose: flashlamps, lasers, and 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.
Preferably, the pulsed electromagnetic radiation is generated using a flashlamp. Of these, 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. In general, 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.
In another embodiment, the 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).
In yet another embodiment, the 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.
For maximum efficiency, 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.
Likewise, in the case of reflective powders, the electromagnetic radiation spectrum is preferably most intense in spectral regions in which the powder is least reflective, although this is not a requirement.
Preferably, 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. These conditions assure that the sufficient heat is absorbed to effect increased adhesion of the powder particles to the film. However, the combination of intensity and fluence should not be so great/high as to cause ablation, excessive degradation, or volatilization of the thermally-softenable film. Selection of appropriate conditions is within the capability of one of ordinary skill in the art.
To minimize heating of interior portions of the thermally-softenable film that cannot interact with the powder particles, 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.
To achieve high line speed in continuous manufacturing processes, not only should 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).
Advantageously, 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). After, 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). SELECT EMBODIMENTS OF THE PRESENT DISCLOSURE
In a first embodiment, 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 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.
In a second embodiment, the present disclosure provides a method according to the first embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
In a third embodiment, the present disclosure provides a method according to the first or second embodiment, wherein the particle coating consists essentially of graphite.
In a fourth embodiment, the present disclosure provides a method according to any one of the first to third embodiments, wherein the modulated source of electromagnetic radiation comprises a flashlamp.
In a fifth embodiment, the present disclosure provides a method according to any one of the first to third embodiments, wherein the modulated source of electromagnetic radiation comprises a pulsed laser.
In a sixth embodiment, the present disclosure provides a method according to any one of the first to third embodiments, wherein the particle coating comprises a powder-rubbed coating.
In a seventh embodiment, the present disclosure provides a method according to any one of the first to sixth embodiments, wherein the particle coating is exposed to the pulsed electromagnetic radiation according to a predetermined pattern.
In an eighth embodiment, the present disclosure provides an article made according to the method of any one of the first to seventh embodiments.
In a ninth embodiment, the present disclosure provides an article comprising 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.
In a tenth embodiment, the present disclosure provides an article according to the ninth embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
In an eleventh embodiment, the present disclosure provides an article according to the ninth or tenth embodiment, wherein the particle coating consists essentially of graphite.
In a twelfth embodiment, the present disclosure provides an article according to any one of the ninth to eleventh embodiments, wherein the thermally-softenable film comprises polyethylene terephthalate.
In a twelfth embodiment, the present disclosure provides an article according to any one of the ninth to eleventh embodiments, wherein the thermally-softenable film comprises polyethylene terephthalate.
In a thirteenth embodiment, the present disclosure provides an article according to any one of the ninth to twelfth embodiments, wherein the predetermined pattern comprises a circuit trace.
In a fourteenth embodiment, the present disclosure provides an article according to any one of the ninth to thirteenth embodiments, wherein the at least one portion of the particle coating that is not disposed within the predetermined pattern comprises a powder-rubbed coating.
In a fifteenth embodiment, the present disclosure provides an article comprising 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.
In a sixteenth embodiment, the present disclosure provides an article according to the fifteenth embodiment, wherein the particle coating comprises a powder-rubbed coating.
In a seventeenth embodiment, the present disclosure provides an article according to the fifteenth or sixteenth embodiment, 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.
Objects and advantages of this disclosure are further illustrated by the following non-limiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.
EXAMPLES
Unless otherwise noted, all parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight. All reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, Missouri, or may be synthesized by conventional methods. MATERIALS USED IN THE EXAMPLES
GENERAL METHOD FOR COATING GRAPHITE ON SUBSTRATES
To make Examples and Comparative Examples described below, 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 lOPMC 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.
For Examples EX-1 to EX- 12 and Comparative Examples CEX-A to CEX-C, visible light transmittance was measured using a HAZE-GARD PLUS haze meter from BYK Additives and
Instruments, Wesel, Germany.
For Examples EX-6 to EX-8, surface resistivity was measured using an RC2175 R-CHEK Surface Resistivity Meter form EDTM, Inc, Toledo, Ohio.
For Comparative Examples CEX-D to CEX-L, light transmittance was measured using a Flame- T-XR1-ES spectrophotometer from Ocean Optics, Dunedin, Florida. These transmittance measurements were recorded over the range of wavelengths from 325 to 1000 nm and averaged.
If thicker coatings were desired, more graphite was applied and the coating step was repeated.
GENERAL METHODS FOR DETERMINING DURABILITY
The samples prepared according to the Examples and Comparative Examples, described below, were tested for durability (resilience of coatings).
Durability of graphite-coated film specimens was evaluated using a Model 5750 Linear Abrader from Taber Industries, North Tonawanda, New York. For CEX-A, CEX-B, EX-1 to EX-9, and CEX-D to CEX-L, a 25mm flat head on the linear abrader was covered with an L40 WYPALL all-purpose wiper from Kimberly-Clark and saturated with isopropanol. The films were then subjected to 60 cycles/minute of abrasion using the 5750 Linear Abrader for a total of one minute, with a total mass loading of 350 g on the head. 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.
All reported percent changes in transmittance were calculations from the following equation:
Where Tfflmis the transmittance of the underlying polymer film, Tc is the transmittance of that same film after the coating and treatments had been applied, and Tabraded 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 (ΔΤ, %) are indicative of higher retention of the total fraction of carbon on the original film.
EXAMPLES EX-1 to EX- 12 and COMPARATIVE EXAMPLES CEX-A to CEX-C 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. In all cases of IPL, the source used was a SINTERON S-2100 Xe flashlamp equipped with Type C bulb from Xenon
Corporation, Wilmington, Massachusetts.
For CEX-A and EX-1, 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/cm2.
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/cm2.
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/cm2 (EX-3) and 1.0 J/cm2 (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.
Table 1, below, reports the IPL effects on Bare PET and Melinex PET. TABLE 1
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/cm2. Table 2, below, reports the change in transmittance ΔΤ in %.
TABLE 2
For EX-9, the substrate coated with graphite was Bare PET. Prior to exposure to IPL, a chromium/glass patterned photomask (shown in Fig. 2) was situated between the flashlamp and the graphite. 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. Additionally, 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.
TABLE 3
For CEX-C to EX- 10, 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/cm2.
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/cm2.
Table 4, below, reports the change in transmittance ΔΤ in %.
TABLE 4
COMPARATIVE EXAMPLES CEX-D to CEX-L
For CEX-D to CEX-L, several sheets of Bare PET were coated with graphite as described above and subjected to several different methods to induce particle retention.
For CEX-D to CEX-F, graphite coated Bare PET films were subjected to blowing heat from a temperature controlled heat gun (Steinel Electronic Heat Gun, Model HL 2010 E, Type 3482 from Steinel America Inc., Bloomington, Minnesota). With the heat gun setting on level II, the end of the nozzle was situated 2 inches (about 5 cm) above and normal to the film surface, which was secured to the bench top with tape at each end, and applied heat to the film for a given amount of time. For CEX-G to CEX-J, graphite coated Bare PET films were subject to e-beam irradiation, carried out using an electron beam system (MODEL CB-300 ELECTRON BEAM SYSTEM from Energy Sciences, Inc., Wilmington, Massachusetts). The coated PET specimens were taped on to a moving PET web and conveyed through the e-beam processor at a voltage of 110 keV. The web speed and e-beam current applied to the cathode were varied to ensure delivery of the targeted dose.
For CEX-K to CEX-L, graphite coated Bare PET films were subject to biaxial strain using a laboratory stretching machine (Briickner Maschinenbau, Model Karo IV Biaxial Stretcher from Briickner Maschinenbau GmbH & Co. KG, Siegsdorf, Germany). The machine's oven was set to 150°C, and the sample was placed in the oven for 5 minutes before being stretched biaxially at a constant rate of 1% per second.
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 (ΔΤ, %, average normalized change in transmission). For heat gun, an output greater than 232°C and/or for longer than 10 minutes was also applied, but was found to result in both excessive thermal degradation of the polymer or unrealistic processing conditions for manufacturing. For biaxial stretching, stretching larger than 5% was also applied, but was found to result in excessive tension of the polymer leading to film fracture.
TABLE 5

Claims

What is claimed is:
1. A method of making an article, the method comprising exposing a particle coating disposed on a thermally-softenable film to a modulated source of electromagnetic radiation, 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.
2. The method of claim 1, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
3. The method of claim 1 or 2, wherein the particle coating consists essentially of graphite.
4. The method of any one of claims 1 to 3, wherein the modulated source of electromagnetic radiation comprises a flashlamp.
5. The method of any one of claims 1 to 3, wherein the modulated source of electromagnetic radiation comprises a pulsed laser.
6. The method of any one of claims 1 to 3, wherein the particle coating comprises a powder-rubbed coating.
7. The method of any one of claims 1 to 6, wherein the particle coating is exposed to the pulsed electromagnetic radiation according to a predetermined pattern.
8. An article made according to the method of any one of claims 1 to 7.
9. An article comprising 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.
10. The article of claim 9, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride .
11. The article of claim 9 or 10, wherein the particle coating consists essentially of graphite.
12. The article of any one of claims 9 to 11, wherein the thermally-softenable film comprises polyethylene terephthalate.
13. The article of any one of claims 9 to 12, wherein the predetermined pattern comprises a circuit trace.
14. The article of any one of claims 9 to 13, wherein the at least one portion of the particle coating that is not disposed within the predetermined pattern comprises a powder-rubbed coating.
15. An article comprising 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.
16. The article of claim 15, wherein the particle coating comprises a powder-rubbed coating.
17. The article of claim 15 or 16, 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.
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 making the same

Publications (2)

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

Family

ID=63207795

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18755304.5A Active EP3645769B1 (en) 2017-06-29 2018-06-27 Method of making an article

Country Status (5)

Country Link
US (1) US20200115804A1 (en)
EP (1) EP3645769B1 (en)
JP (1) JP7170677B2 (en)
CN (1) CN110832116B (en)
WO (1) WO2019003153A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11241711B2 (en) 2017-03-22 2022-02-08 3M Innovative Properties Company Buff-coated article and method of making the same
WO2019003056A1 (en) 2017-06-29 2019-01-03 3M Innovative Properties Company Article and methods of making the same
KR102461992B1 (en) * 2020-12-30 2022-11-03 마이크로컴퍼지트 주식회사 Coating method of coating solution comprising hexagonal boron nitride particles and heat dissipation member manufactured thereby

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (en) * 2000-06-16 2005-03-23 三菱重工業株式会社 Manufacturing method of thermal barrier coating material
FR2832736B1 (en) * 2001-11-28 2004-12-10 Eppra IMPROVED METHOD FOR COATING A SUPPORT WITH A MATERIAL
JP3979464B2 (en) * 2001-12-27 2007-09-19 株式会社荏原製作所 Electroless plating pretreatment apparatus and method
US7569174B2 (en) * 2004-12-07 2009-08-04 3D Systems, Inc. Controlled densification of fusible powders in laser sintering
JP2009124029A (en) * 2007-11-16 2009-06-04 Shinshu Univ Method of manufacturing electronic circuit board by inkjet
JP2015507560A (en) * 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 Carbon coated article and method for producing the same
US9744559B2 (en) * 2014-05-27 2017-08-29 Paul W Harrison High contrast surface marking using nanoparticle materials
US20170145554A1 (en) * 2014-06-26 2017-05-25 Shell Oil Company Coating method and coated substrate

Also Published As

Publication number Publication date
JP2020525271A (en) 2020-08-27
CN110832116B (en) 2023-01-13
JP7170677B2 (en) 2022-11-14
US20200115804A1 (en) 2020-04-16
WO2019003153A1 (en) 2019-01-03
CN110832116A (en) 2020-02-21
EP3645769B1 (en) 2025-04-30

Similar Documents

Publication Publication Date Title
Rancourt Optical thin films: user handbook
JP7170677B2 (en) Articles and manufacturing methods thereof
LV12080B (en) METHOD OF SELECTIVE REMOVAL OF UNDESIRABLE MATERIAL FROM THE SURFACE TO BE TREATED BY POLARIZED RADIATION
Seifert et al. Self-organized structure formation on the bottom of femtosecond laser ablation craters in glass
Ursu et al. High-intensity laser irradiation of metallic surfaces covered by periodic structures
Allen et al. Contaminant and defect analysis of optical surfaces by infrared laser induced desorption
EP3645776B1 (en) Nonwoven article and method of making the same
Ritsko et al. Laser‐assisted chemical etching of copper
Shimomura et al. Neutral debris mitigation in laser produced extreme ultraviolet light source by the use of minimum-mass tin target
CN114040820A (en) Method for removing particles from a surface using laser energy
Arnold et al. Ablative thresholds in laser cleaning of substrates from particulates
Rodriguez-Navarro et al. Role of marble microstructure in near-infrared laser-induced damage during laser cleaning
Song et al. Laser-induced desorption and etching at surfaces
Zimmer et al. Mechanism of backside etching of transparent materials with nanosecond UV-lasers
Chkhalo et al. Influence of annealing on the structural and optical properties of thin multilayer EUV filters containing Zr, Mo, and silicides of these metals
Kondo et al. Strongly enhanced optical absorption in quench-deposited amorphous AgI films
Dyer et al. VUV F2 laser ablation of sodium chloride
Mori et al. Optical properties of self-ion-implanted Si (100) studied by spectroscopic ellipsometry
Yamamoto et al. Nanostructure and optical nonlinearity of Cobalt oxide thin films
Wu et al. Study on the UV FEL single-shot damage threshold of an Au thin film
Lazare et al. New surface modifications of polymer films with the excimer laser radiation
Barreca et al. Optical constants of CNx thin films from reflection electron energy loss spectroscopy
Jiang et al. Polarized electroabsorption spectra and light soaking of solar cells based on hydrogenated amorphous silicon
Matthias et al. Non-destructive reading of laser-induced single-shot incubation in dielectric coatings
Yamamoto et al. Reflectance degradation of soft X-ray multilayer filters upon exposure to synchrotron radiation

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200107

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20201105

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20241129

P01 Opt-out of the competence of the unified patent court (upc) registered

Free format text: CASE NUMBER: APP_2104/2025

Effective date: 20250113

P01 Opt-out of the competence of the unified patent court (upc) registered

Free format text: CASE NUMBER: APP_2104/2025

Effective date: 20250113

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018081511

Country of ref document: DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250520

Year of fee payment: 8

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20250430

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1790080

Country of ref document: AT

Kind code of ref document: T

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250901

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250731

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

REG Reference to a national code

Ref country code: CH

Ref legal event code: H13

Free format text: ST27 STATUS EVENT CODE: U-0-0-H10-H13 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250430

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018081511

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250627

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20250630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: CH

Ref legal event code: L10

Free format text: ST27 STATUS EVENT CODE: U-0-0-L10-L00 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260311

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20250730

26N No opposition filed

Effective date: 20260202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250630