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WO2000001528A1 - Procede de modification au plasma de substrats - Google Patents

Procede de modification au plasma de substrats Download PDF

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Publication number
WO2000001528A1
WO2000001528A1 PCT/US1999/015346 US9915346W WO0001528A1 WO 2000001528 A1 WO2000001528 A1 WO 2000001528A1 US 9915346 W US9915346 W US 9915346W WO 0001528 A1 WO0001528 A1 WO 0001528A1
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WO
WIPO (PCT)
Prior art keywords
functionalities
atom
modified
substrate
oxygen
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.)
Ceased
Application number
PCT/US1999/015346
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English (en)
Inventor
Karl Gregory Reimer
Jeffrey R. Dykhouse
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.)
METROLINE INDUSTRIES Inc
Original Assignee
METROLINE INDUSTRIES Inc
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 METROLINE INDUSTRIES Inc filed Critical METROLINE INDUSTRIES Inc
Priority to AU49737/99A priority Critical patent/AU4973799A/en
Publication of WO2000001528A1 publication Critical patent/WO2000001528A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/12—Soles with several layers of different materials
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B9/00—Footwear characterised by the assembling of the individual parts
    • A43B9/12—Stuck or cemented footwear
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D25/00—Devices for gluing shoe parts
    • A43D25/20—Arrangements for activating or for accelerating setting of adhesives, e.g. by using heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties

Definitions

  • the invention is directed to methods of plasma modification and to the use of plasma modification of plastics and monomers, such as used in the footwear industry.
  • the components is typically made of an elastomeric material.
  • the surfaces are cleaned using a solvent and then modified using a solvent-based or water-based primer.
  • the primer modifies the surface of the component to contain additional or different chemical functionalities. These functionalities facilitate migration of the adhesive into the substrate, providing molecular mechanical locking and/or chemical bonding of the substrate with the adhesive.
  • primers are chlorinated primers, which are highly undesirable for environmental reasons. Additionally, it has been found that some primers make the surface more brittle, resulting in microcracks in the surface. Moreover, certain primers can discolor the surface, turning, for example, a white surface into a yellow surface. Another disadvantage of using a primer is that it is difficult to determine where and how much primer has been applied. Additionally, it has been found that primers can only provide a limited number of functionalities on the surface, namely, only up to about 8% based on the total number of atoms on the surface of the substrate, as determined by ESCA.
  • the present invention is directed to methods for modifying particular surfaces using plasma surface modification.
  • the invention is directed to a method for making footwear having at least two components.
  • the surface of a component is chemically modified using plasma surface modification.
  • the modified component surface is then adhered to another component composition.
  • Functionalities that are added to the component surface by this technique include, but are not limited to, chlorine, oxygen, carboxyl, hydroxyl, carbonyl, nitrogen and amine functionalities.
  • the invention is directed to a method for enhancing the adhesion of a substrate. At least one surface of the substrate is modified using plasma surface modification to include chlorine and oxygen-containing functionalities, chlorine and amine functionalities, or amine and oxygen-containing functionalities.
  • the invention is also directed to a composition having at least one surface comprising chlorine and oxygen-containing functionalities, chlorine and amine functionalities, or amine and oxygen-containing functionalities bonded to its surface by plasma surface modification.
  • the invention is directed to footwear having at least two components that are adhered to each other.
  • the adhered surface of at least one component contains functionalities chemically bonded to it by plasma surface modification.
  • FIG. 1 is an illustration of a shoe according to the invention.
  • FIG. 2 is a schematic depiction of plasma modification equipment useful for the methods of the invention.
  • the present invention is directed to methods for modifying particular surfaces using plasma surface modification.
  • plasma refers to an ionized gas containing positive and negative charges, free radicals and electrons.
  • plasma surface modification generally refers to the process of affecting chemical changes in a substrate surface by exposing it to low pressure and/or low temperature plasma.
  • the plasma treatment of the invention provides excellent wettability of the polymeric surface with various adhesives, such as epoxies, urethanes and hot melts.
  • various adhesives such as epoxies, urethanes and hot melts.
  • Wettability is essential for reactive adhesives such as contact (pressure-sensitive adhesives) and hot melt adhesives.
  • Non-reactive adhesive systems rely predominantly on several adhesion mechanisms, including mechanical interlocking, molecular diffusion and electrostatic interactions between the adhesive and polymer surface.
  • the adhesive Another key feature for optimum adhesion, particularly for reactive adhesives such as epoxy and isocyanate cure systems, is the adhesive 's ability to chemically bond to the substrate.
  • the substrate must have the correct chemistry to chemically react with the adhesive.
  • the epoxy portion of the system chemically reacts with the amine forming a covalent bond between the carbon formerly bonded to the epoxide oxygen and the nitrogen of the amine.
  • the reaction forms a strong three-dimensional molecular structure providing excellent cohesive strength.
  • the resulting product of the chemical reaction of the adhesive and substrate will include the amine functionalities on the surface, which will be incorporated into the molecular network of the adhesive.
  • This molecular network enhances the adhesion between the substrate and the adhesive.
  • the present invention provides methods for enhancing the ability of substrates to adhere to other compositions, particularly to adhesives.
  • Particularly suitable substrates that can be modified in accordance with the invention include elastomeric substrates, thermoplastic substrates, and thermoset plastics.
  • elastomeric substrates include styrene-butyl-styrene rubber (SBS), styrene butyl rubber (SBR), polyvinylchloride (PVC), ethylene vinyl acetate (EVA), polyurethane rubber
  • PU polybutadiene rubber
  • CLR chlorobutyl rubber
  • IR synthetic polyisoprene rubber
  • CR neoprene rubber
  • EPDM ethylene propylene rubber
  • NBR nitrile rubber
  • ACM polyacrylic rubber
  • fluoroelastomers polyolefin thermoplastic elastomers, polyolefin thermoset elastomers, such as EngageTM commercially available from DuPont Dow, and halogenated polyolefin thermoplastic elastomers.
  • thermoplastic substrates include polyolefins, fluoropolymers, polystyrene and styrene copolymers, polyvinylchlorides, polyvinylacetates, acrylic thermoplastics, aliphatic polyethers, polyesters, polyurethanes, silicones, polydienes, phenolic polymers, polycarbonates, polyamides, poly(ethylene terephthalate), polyformaldehydes, poly(methyl methacrylate), and acrylonitrile-butadiene-styrene copolymers.
  • Suitable thermoset plastics include, but are limited to, epoxies, polyurethanes, and cyanoacrylates.
  • Other substrates frequently used in the footwear industry can also be modified by the methods of the invention, such as nylon, Kevlar, and imitation and natural leather.
  • FIG. 1 illustrates a shoe according to the invention having multiple components, namely an out sole 1. mid soles 2, 3 and 4, and an upper 6. each having surfaces 5.
  • the out sole 1 is made of a durable rubber material.
  • the mid soles 2, 3 and 4 are typically made of a foam material.
  • the upper 6 can be made of any suitable material such as nylon, canvas, leather and other naturally-occurring and synthetic polymers. Any of the component surfaces 5 can be modified in accordance with the invention.
  • the components can then be adhered to one another, either directly or using an adhesive. When the components are adhered to one another, they can be in any suitable form, including both solid and liquid forms.
  • the out sole could be composed of a solid polyurethane and the mid sole composed of a solid foam, in which case one or both components could be modified and an adhesive would be used to adhere the components.
  • the out sole could be composed of a solid polyurethane and the mid sole composed of a liquid material that is capable of curing into a foam, in which case the out sole is modified and the mid sole is formed onto the out sole by pouring the liquid preformed material onto the out sole and subsequently curing the liquid material.
  • the resulting construction comprises a substantially solid foam mid sole adhered to the out sole.
  • a third possibility would involve a liquid composition cured onto a solid plasma treated mid sole adhered to form an out sole.
  • the plasma-modified substrates can be bonded using a wide variety of adhesives.
  • Suitable adhesives include, but are not limited to, isocyanate-type polyurethane hot melt, isocyanate-type water base polyurethane, silicone-based, polysulfide, cyanoacrylate, epoxy, polyurethane, polyamide, polyimide, polyamide-imide, polyamide-epichlorohydrin, acrylic, polyester, butadiene-acrylonitrile, butadiene-styrene, neoprene, butyl rubber, polyisobutylene, latex, ethylenevinylacetate, epoxy-nitrile, phenolic nitrile-phenolic, resorcinol, and poly vinyl adhesives.
  • the methods of the invention can be carried out using any known type of plasma surface modification equipment, such as the apparatus depicted in FIG. 2.
  • the apparatus comprises a reactor vessel 10 having a reaction chamber 11 into which is placed a substrate 12 to be modified. If desired, one or more shelves 13 can be provided within the reaction chamber 11 for placement of one or more substrates 12 within the chamber.
  • the reaction chamber 11 is made of metal, such as aluminum, but can also be made of other suitable materials such as quartz.
  • the reaction vessel 10 can be designed for batch operation or for continuous operation as desired.
  • the reaction chamber 11 is capable of being substantially evacuated, i.e., to a pressure within the range of about 10 "3 to about 700 Torr, preferably about 10 "2 to about 0.5 Torr.
  • One or more gas sources 14 are provided, from which one or more gases flow into the reaction chamber 11 through mass flow controllers 16. If desired, different gases from different gas sources 14 can be mixed in a mixer 15 prior to introduction to the reaction chamber 11. In addition, different gases or combinations of gases can be introduced into the plasma reactor at different times during the processing or treatment.
  • the electrode 18 is a barrel-type electrode having a generally cylindrical shape. If desired, the shelves 13 can be electrified in place of or in addition to the barrel-type electrode 18.
  • the electrode 18 acts as a cathode and is connected to a variable frequency power source 22.
  • the reactor vessel 10, which is electrically isolated from the electrode 18, acts as an anode and is grounded. Any other suitable electrode configuration could also be used.
  • the electrode can include magnetic confinement.
  • An example of such an electrode is described in U.S. Patent No. 5,433,786, the disclosure of which is incorporated herein by reference.
  • the variable frequency power source 22 furnishes the electrical power necessary to generate the plasma. If desired, the plasma power can be turned on and off rapidly or “pulsed" during the processing or treatment.
  • the power source 22 should be capable of generating alternating current electrical power in the range of 50 to 5000 watts with a frequency of 1000 Hz to 5 GHz, and preferably generates radio frequency energy, low frequency energy or microwave frequency energy. Examples of suitable power sources 22 for use in the present invention are 13.56 MHz power generators and 40 KHz power generators.
  • the reaction chamber 11 is first evacuated by means of a vacuum pump 24.
  • a vacuum pump 24 Any suitable vacuum pump 24 can be used, preferably a pump that can accommodate an ultimate vacuum of 5 millitorr.
  • a suitable vacuum pump 24 for use with the present invention is sold under the trade designation 2033C by Alcatel International
  • One or more gases are then introduced into the reaction chamber 11 at a predetermined flow rate, preferably from about 50 to 1000 seem (standard cubic centimeters per minute), more preferably from about 50 to about 250 seem, and still more preferably from about 80 to about 125 seem, through supply line 26.
  • the flowrate of the gases is adjusted to achieve a predetermined pressure, preferably from about 0.020 to about 1.000 torr, more preferably from about 0.100 to about 0.500 torr, even more preferably from about 0.080 to about 0.500 torr, still more preferably from about 0.140 to about 0.250 torr, and yet more preferably from about 0.170 to about 0.200 torr.
  • variable frequency power source 22 When the desired pressure is achieved, the variable frequency power source 22 is turned on to generate an electric field under preselected frequency and power conditions to ionize the gases, thereby forming a plasma.
  • Methods of generating an electric field between electrodes are well-known in the art.
  • the electric field is maintained for a predetermine time period, preferably from about 15 seconds to about 90 minutes, more preferably 30 seconds to about 30 minutes, still more preferably from about 2 to about 12 minutes, and yet more preferably from about 8 to about 12 minutes, so that the substrate is explosed to the plasma for that time period.
  • the plasma creates a high density of free radicals, ions and electrons, both in the gas phase and on the surface of the substrate.
  • the surface free radicals are created by direct attack of the gas-phase free radicals, ions, electrons and/or by photodecomposition of the surface by vacuum-ultraviolet light generated by the plasma.
  • the surface free radicals are then able to react either with each other or with free radicals in the plasma environment.
  • functional groups are formed on the surface of the substrate.
  • the modification generally affects only the top few molecular layers of the substrate (approximately 50 to 100 A), and thus the bulk properties of the substrate are not altered. This surface modification technique enhances the chemical reactivity of the surface of the substrate.
  • the gases used in the inventive methods depend on the particular application, namely the substrate and adhesive to be used.
  • the substrate should be modified to contain functionalities that enhance the wettability of the adhesive to the substrate.
  • functionalities that enhance the wettability of the adhesive to the substrate.
  • an epoxy adhesive is used, amine functionalities are preferred.
  • a hot melt adhesive such as a moisture-cured (isocyanate) hot melt, is used, preferably the substrate surface is modified to include chlorine or oxygen functionalities, and more preferably to contain both chlorine and oxygen functionalities.
  • the plasma can comprise carbon tetrachloride, chloroform or any other organic volatile material that contains chlorine.
  • oxygen functionalities are desired, the plasma can contain any volatile compound containing oxygen, for example, nitrous oxide, carbon dioxide, oxygen or air. If the substrate already contains oxygen functionalities, it may be further modified to a lower oxidation state, such as from a carbonyl functionality to a hydroxyl functionality, using hydrogen gas. If amine functionalities are desired, the plasma can contain any organic volatile composition that contains nitrogen, such as ammonia or nitrogen. Other functionalities could also be added to the substrate surface in accordance with the invention.
  • the lifetime of the chemical functionalities on substrate surfaces are typically short, ranging from only a few minutes to several days, resulting in a decrease of functionalities at the top molecular level of the surface.
  • One approach to address this problem is to increase the amount of functionalities on the surface.
  • chlorine functionalities preferably the surface is modified to contain from about 0.5% to about 25%, more preferably from about 5% to about 20%, still more preferably from about 15% to about 20%, chlorine functionalities.
  • oxygen functionalities including carboxyl groups, hydroxyl groups and carbonyl groups
  • the surface is modified to contain from about 1% to about 30%. more preferably from about
  • the surface is modified to contain from about 0.1% to about 30%, more preferably 0.5% to about 20%, even more preferably from about 2% to about 10%, and still more preferably from about 8% to about 10%, amine functionalities.
  • the substrate is modified to contain from about 4% to about 15%, more preferably from about 12% to about 15%, chlorine functionalities and from about 5% to about 15%, more preferably from about 7% to about 9%, oxygen functionalities.
  • the substrate is modified to contain from about 5% to about 15%. more preferably from about 12% to about 15%, chlorine functionalities and from about 3% to about
  • the substrate is modified to contain from about 3% to about 10% amine functionalities and from about 5% to about 15%. more preferably from about 7% to about 9%, oxygen functionalities.
  • the identified percentages of functionalities are atom percentages, excluding hydrogen, as determined by electron spectroscopy for chemical analysis (ESCA).
  • ESA electron spectroscopy for chemical analysis
  • Another approach to increase the lifetime of the functionalities is by crosslinking the substrate by including one or more inert gases, such as helium and argon, in the plasma, as described in Schonhorn, H. et al. 1967 J. App. Polym. Sci. ⁇ , p. 1461, and Schonhorn, H. et al., 1966 J. Polym. Sci. B4, p. 203, the disclosures of which are incorporated herein by reference.
  • the gases for use in the present invention can be vaporized from liquid form if necessary prior to entry into the reactor chamber.
  • the liquid outside of the chamber is heated isothermally such that sufficient vapor is supplied constantly to the chamber.
  • an inert carrier gas such as helium or argon can be transported through the liquid to obtain a diluted vapor mixture of desired composition.
  • Gaseous reactants such as oxygen are suitable for reaction in plasma, alone or with an inert carrier gas to insure proper metering into the reaction chamber.
  • Gaseous reactants may be supplied from an external source through a series of inlet pipes into the reactor chamber.
  • each gas conduit may be connected to a central feed line that carries the gases into the reaction chamber.
  • the gaseous reactants can be mixed with a carrier gas such as argon to improve their flow into the reaction chamber.
  • a carrier gas has been found to improve the uniformity of plasma density and gas pressure within the reaction chamber.
  • the carrier gas may be premixed with the gaseous reactants or may be fed into the supply line by a separate inlet.
  • the flow of carrier and reactant gases into the reaction chamber may be governed by mass flow controller valves, which are well known in the art, and which serve to both measure and control the flow of gases. After passing over the substrate surface, any gases that have not reacted with the surface may be directed out of the reaction chamber through an exit valve and then to a gas pumping and exhaust system (not shown). Means for expelling these excess materials from the reaction chamber are well-known in the art.
  • the substrate surface may be cleaned by washing with water or an organic solvent, such as isopropanol, acetone, methanol, or the like. This washing step removes dirt, contaminants, and additives such as wetting agents from the surface. However, in some cases it has been found that the plasma treatment may achieve the required cleaning.
  • an organic solvent such as isopropanol, acetone, methanol, or the like.
  • Examples 1 to 16 the surfaces of several substrates, styrene-butyl-styrene rubber (SBS), ethylene vinyl acetate (EVA), EngageTM (ENG), styrene butyl rubber (SBR), polyvinylchloride (PVC), synthetic leather (SLR), and natural leather (NLR), were modified by plasma surface modification.
  • SBS styrene-butyl-styrene rubber
  • EVA ethylene vinyl acetate
  • EngageTM ENG
  • SBR styrene butyl rubber
  • PVC polyvinylchloride
  • SLR synthetic leather
  • NLR natural leather
  • the modified substrates were bonded together or to canvas, as indicated, using a hot melt moisture cure adhesive system sold under the name RapidexTM (H.B. Fuller Co., St. Paul. Minnesota). During adhesive cooling, 45 psi of pressure were applied to the bonded samples. Mechanical testing was conducted on the samples approximately 72 to 120 hours after bonding. Namely, a Tee Peel tension pull test was conducted on each sample pursuant to ASTM D412-97. The pull rate was 4 inches per minute. Using this test, preferably the bonded samples are able to withstand at least about 14 ppi (about 6.3 Kg/in 2 ), and more preferably at least about 35 ppi (about 15.9 Kg/in 2 ).
  • Table 1 describes the plasma process conditions and the mechanical tests results for each sample.
  • the surfaces of two SBS substrates are modified by plasma surface modification.
  • the plasma contains chloroform (CHC1 3 ) and is provided at a flow rate sufficient to achieve a pressure of 0.125 torr. 700 watts are provided to generate an electric field for 10 minutes.
  • the modified surfaces of the substrates are bonded together using a hot melt moisture cure adhesive system sold under the name RapidexTM.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des procédés de modification chimique de surfaces particulières, par modification de surface au plasma. Un procédé de préparation d'article chaussant possédant au moins deux composants (1, 2, 3, 4), consiste à modifier chimiquement la surface d'un composant (5) par modification de surface au plasma. La surface modifiée du composant est ensuite collée à une surface d'un autre composant. Les fonctionnalités qui sont conférées à la surface du composant par cette technique, sont, entre autres, des fonctionnalités chlorure, oxygène et amine. L'adhésion d'un substrat est accrue par la modification chimique d'une surface du substrat par modification de surface au plasma, de sorte que cette dernière possède des fonctionnalités oxygène et chlorure, chlorure et amine ou amine et oxygène.
PCT/US1999/015346 1998-07-07 1999-07-07 Procede de modification au plasma de substrats Ceased WO2000001528A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49737/99A AU4973799A (en) 1998-07-07 1999-07-07 Methods for plasma modification of substrates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9190198P 1998-07-07 1998-07-07
US60/091,901 1998-07-07

Publications (1)

Publication Number Publication Date
WO2000001528A1 true WO2000001528A1 (fr) 2000-01-13

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001022843A1 (fr) * 1999-09-29 2001-04-05 Henkel Kommanditgesellschaft Auf Aktien Procede pour produire une chaussure
KR20010106606A (ko) * 2000-05-22 2001-12-07 박차철 신발용 중창의 표면처리 방법
KR100328700B1 (ko) * 2000-02-23 2002-03-28 손명호 플라즈마 표면처리에 의한 신발창의 접착방법
WO2002070234A1 (fr) * 2001-03-01 2002-09-12 Siemens Aktiengesellschaft Procede pour appliquer une couche superficielle et un film adhesif sur un corps solide et corps solide obtenu selon ce procede
KR20040021955A (ko) * 2002-09-06 2004-03-11 사단법인 고등기술연구원 연구조합 상압 플라즈마를 이용한 폴리머 표면 개질장치 및 방법
EP1299183A4 (fr) * 2000-04-14 2005-11-16 Karl Reimer Appareil et procede permettant la modification continue de la surface de substrats
FR2922478A1 (fr) * 2007-10-22 2009-04-24 Arkema France Procede de fabrication de stratifie polymere comportant une etape d'activation par traitement plasma
RU2356482C2 (ru) * 2006-07-20 2009-05-27 Государственное образовательное учреждение высшего профессионального образования "Казанский государственный технологический университет" Способ обработки заготовки верха обуви из натуральной кожи после обтяжно-затяжных операций
WO2011160939A1 (fr) 2010-06-25 2011-12-29 Carnehammer, Lars Bertil Traitement superficiel de caoutchouc au plasma basse pression
US20160064195A1 (en) * 2014-09-02 2016-03-03 Nike, Inc. Plasma Treatment Of An Elastomeric Material For Adhesion
US20190177912A1 (en) * 2017-12-13 2019-06-13 Nike, Inc. Method and system for plasma treatment
US11272758B2 (en) 2018-01-24 2022-03-15 Nike, Inc. Sole structures including polyolefin plates and articles of footwear formed therefrom
US11503875B2 (en) 2019-07-19 2022-11-22 Nike, Inc. Sole structures including polyolefin plates and articles of footwear formed therefrom
US11696620B2 (en) 2019-07-19 2023-07-11 Nike, Inc. Articles of footwear including sole structures and rand
CN117567862A (zh) * 2023-12-27 2024-02-20 天茂石化江苏有限公司 一种疏水的尼龙复合材料及其制备方法
US12022909B2 (en) 2021-08-30 2024-07-02 Nike, Inc. Polyolefin-based resins, sole structures, and articles of footwear and sporting equipment formed therefrom
US12286563B2 (en) 2019-06-18 2025-04-29 Avery Dennison Corporation Butyl rubber based pressure sensitive adhesives

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US4870129A (en) * 1986-09-04 1989-09-26 Bayer Aktiengesellschaft Adhesive and use of the adhesive for the formation of bonds
US5466424A (en) * 1992-12-28 1995-11-14 Bridgestone Corporation Corona discharge surface treating method

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US4128950A (en) * 1977-02-07 1978-12-12 Brs, Inc. Multilayered sole athletic shoe with improved foam mid-sole
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