WO2009046725A1 - Procédé de fabrication d'un article et article surmoulé - Google Patents

Procédé de fabrication d'un article et article surmoulé Download PDF

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Publication number
WO2009046725A1
WO2009046725A1 PCT/DK2008/050246 DK2008050246W WO2009046725A1 WO 2009046725 A1 WO2009046725 A1 WO 2009046725A1 DK 2008050246 W DK2008050246 W DK 2008050246W WO 2009046725 A1 WO2009046725 A1 WO 2009046725A1
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WO
WIPO (PCT)
Prior art keywords
item
substrate
producing
elastomer
plasma
Prior art date
Application number
PCT/DK2008/050246
Other languages
English (en)
Inventor
Maike Benter
Bahram Eshtehardi
Juan Jiang
Original Assignee
Nanon A/S
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 Nanon A/S filed Critical Nanon A/S
Publication of WO2009046725A1 publication Critical patent/WO2009046725A1/fr

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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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics

Definitions

  • the present invention relates to a method of producing an item comprising an elastomer, such as silicone rubber applied onto a substrate and an item.
  • a primer comprising an organic chemical compound onto the substrate surface (e.g. a silane, titanium or zirconium coupling agents).
  • the chemical compound has two types of functional groups, one type that is able to bond to the substrate and one type that is able to bond to the elastomer b) Surface activation by physical vapour deposition, chemical vapour deposition, plasma activation often followed by applying a primer c) Chemical modification of the elastomer (self-bonding compounds) that is able to bond directly to the substrate surface.
  • US 5,378,535 describes a primer system for silicone elastomers bonded to glass or plastic substrates.
  • the primer system is a two-layer system consisting of a first thin layer of a silica-based adhesion promoter which is applied to the substrate using PVD, CVD, evaporation or sputtering, and a second layer of an organosilane comprising silanol, and (ii) polymerizable alkene and/or silicon hydride functional groups applied by wet chemical methods.
  • the second layer may be from 0.1 to about 5 microns in thickness, it will in practice be impossibly to apply a layer with a thickness below 1 micron
  • EP 781 823 relates to a primer composition comprising an organic silicon compound.
  • the primer composition can be used to prime a substrate for promoting adhesion of silicone rubber to the substrate.
  • US 6,034,174 relates to a primer composition for incorporating into an addition curable polysiloxane resin and comprising an epoxy functional silane and an acid.
  • the addition curable polysiloxane resin is self-adhesive when cured on top of a substrate.
  • Other compositions of addition curable silicone compositions are disclosed in US 6,489,031 and US 5,085,894.
  • the object of the invention is to provide a novel method of producing an item comprising a substrate and an elastomer, which method is simple and provides an item with a strong bonding between the substrate and the elastomer.
  • Another object of the invention is to provide a novel item comprises an elastomer and a substrate which are bonded to each other with a strong bonding.
  • overmolding means herein to apply an elastomer or a precursor therefore to a substrate and cure the elastomer in contact with the substrate to bond the elastomer to the substrate.
  • overmolded elastomer means an elastomer, which has been applied to a substrate e.g. in the form of a precursor, and cured in contact with said substrate.
  • overmolded item means the item comprising the overmolded elastomer and the substrate.
  • the method of the invention comprises
  • the substrate and the elastomer forms a very strong and durable bonding to each other, even when the materials differs in hardness and/or stiffness. Furthermore the method is simple and fast and may be used on most any substrate.
  • the method of the invention has thus opened up for the production of completely new quality products, in particular products mainly composed of an elastomer and a non-elastomer.
  • the elastomer is overmolded onto the primer treated substrate.
  • the elastomer is overmolded onto the primer treated substrate and simultaneously at least partly into at least a part of the substrate, e.g. such as into a surface layer of the substrate where the surface layer e.g. have a thickness of 1 ⁇ m to 10 mm, such as 10 ⁇ m to 5 mm.
  • the thickness of the surface layer of the substrate depends largely of the porosity of the substrate.
  • the substrate is at least partly porous, e.g. in the form of a porous polymer or in the form of a woven or a non-woven fabric, and the method comprises overmolding the elastomer into at least a part of said substrate.
  • the overmolding of the elastomer into the substrate may e.g. include incorporating precursor(s) for the elastomer into the substrate using overpressure and/or liquid/supercritical CO 2 treatment as described in any one of applicants copending applications US 2006/0148985, DK PA 2006 01439 and DK PA 2006 01440 followed by cross-linking (curing) to provide the elastomer.
  • the substrate may in principle be any kind of substrate of any material and with any shape.
  • the substrate may be of a single material or it may be composed of two or more materials which may be composed in a homogenous fashion or an inhomogeneous fashion.
  • the substrate is of a material which is harder than the overmolded elastomer.
  • the substrate should preferably be a solid substrate at 20 0 C and 1 atms.
  • the substrate is a non-elastomer.
  • the substrate is a polymer or a combination of different polymers.
  • preferred polymers includes polymers selected from the group consisting polyethylene (PE) polypropylene (PP), polycarbonate (PC), polyamide (PA), poly(phenylene sulphide) (PPS), polymethylmethacrylate (PMMA), polystyrene (PS), polyethyleneterephthalate (PET), and fluoropolymers.
  • the substrate is one or more of carbon and aramide, preferably in the form of fibers or particles, such as fibers with an average diameter of 1 -100 ⁇ m and/or fibers/particles with a BET surface area of from 100 to 1500 m 2 /g.
  • Fibers comprising an overmolded elastomer may be used e.g. as fillers, in yarns and in other fiber based products.
  • the substrate is as mentioned above a porous material.
  • the substrate is a non woven fabric made of polymer fibres.
  • the elastomer may e.g. be applied in order to be impregnated into an outer layer of the fabric to provide membrane or barrier properties. Thereby a very strong membrane with pre-selected characteristics can be obtained.
  • the substrate is glass or a glass composition.
  • An overmolded item comprising glass and an elastomer may be constructed to have a unique combination of desired properties, such as a combination of strength, low permeability and relatively low hardness.
  • the substrate is a metal, such as iron, steel (stainless, duplex and other), aluminium and magnesium.
  • the elastomer may e.g. be applied in order to protect the metal against corrosion, to provide en electrically insulation or for other reasons.
  • the substrate is a ceramic material, such as oxide based ceramic materials, (alumina, zirconia), non-oxide based ceramic materials, (carbides, borides, nitrides, suicides).
  • oxide based ceramic materials alumina, zirconia
  • non-oxide based ceramic materials alumina, zirconia
  • carbides, borides, nitrides, suicides a ceramic material, such as oxide based ceramic materials, (alumina, zirconia), non-oxide based ceramic materials, (carbides, borides, nitrides, suicides).
  • the substrate is a composite of two or more of the above mentioned materials.
  • the substrate may have essentially plane surfaces or it may have a more curved shape.
  • the substrate may be in the form of particles and/or fibers irrespectively of the material e.g. fibers with an average diameter of 1 -100 ⁇ m and/or fibers/particles with a BET surface area of 100 to 1500 m 2 /g.
  • the fibre substrate may e.g. be of glass.
  • the substrate is a film, having an essentially even thickness, preferably of 2 mm or less, such as 1 mm or less, such as 0.5 mm or less, such as 0.1 mm or less, such as 0.05 mm or less.
  • the substrate is a non-porous film.
  • the substrate has at least one thickness larger than 0.5 mm, the item preferably has a non-plane surface section, such as a curved and/or edged surface section.
  • the substrate is essentially nonflexible, and preferably has an inherent stiffness of at least 100, such as between 103 and 1010 N/m, such as between 104 and 106 N/m.
  • the inherent stiffness may e.g. be measured using ASTM D 882.
  • the method of the invention comprises applying one or more primer layers where the total thickness of the primer layer(s) is up to 200 nm. It has been found that even thinner layer(s) of primer provide an even better result. It is therefore preferred that the total thickness of the at least one primer layer being in the interval between 1 and 150 nm, such as between 5 and 100 nm, such as between 10 and 70 nm.
  • the primer layer' in the following it should be interpreted to mean at least one primer layer and the term may though be interpreted to include one, two or several primer layers provided that the total thickness is not above 200 nm.
  • the primer layer should as mentioned be rather thin, namely about 200 nm or less in thickness.
  • the inventors of the present invention has thus found that by providing the primer layer as a rather thin layer a very strong bonding between the overmolded elastomer and the substrate can be obtained.
  • the primer layer is applied using vapour deposition.
  • a preferred method of applying the primer layer is by using plasma deposition of at least one monomer, the plasma preferably being a low (lower than atmosphere) pressure AC (alternating current) or DC (direct current) plasma, wherein the pressure in the plasma during deposition treatment preferably being is 50 Pa or below, below 35 Pa, such as between 1 and 30 Pa.
  • the primer layer being applied using plasma deposition.
  • any kind of plasma generating method may be used, but in order not to damage the substrate surface and/or the primer it is desired to use a relatively low power plasma.
  • the plasma being a low power plasma, preferably the applied power being 100 W/l plasma reactor or less, such as 50 W/l plasma reactor or less, such as 30 W/l plasma reactor or less, such as 20 W/l plasma reactor or less, such as 10 W/l plasma reactor or even less, such as 5 W/l plasma reactor or less, such as 3 W/l or less, such as 1 W/l or even less.
  • the volume of the plasma reactor is the volume in which the plasma is generated.
  • the primer layer being applied using plasma deposition where the plasma being a one phase plasma (one electrode or electrode group having same voltage and one grounded electrode/electrode group) preferably operating at a frequency of 50 Hz to 15 MHz, such as to 13.6 MHz.
  • the plasma being a one phase plasma (one electrode or electrode group having same voltage and one grounded electrode/electrode group) preferably operating at a frequency of 50 Hz to 15 MHz, such as to 13.6 MHz.
  • the primer layer being applied using plasma deposition where the plasma being a two or multi phase plasma (two or more electrode or electrode groups each group having same voltage) preferably operating at a frequency of 50 Hz to 15 MHz, such as to 13.6 MHz.
  • the plasma deposition may preferably be performed at atmospheric pressure or a reduced pressure.
  • the plasma deposition is performed at a low pressure, such as a pressure of 100 Pa or below, such as 50 Pa or below, such as 15 Pa or below.
  • the primer layer being applied using plasma deposition and the plasma deposition comprising applying the substrate in a plasma reactor, reducing the pressure in the plasma reactor, feeding the at least one monomer to the plasma reactor preferably together with a support gas selected from the group consisting of inert gases, oxidizing gasses or reducing gasses, the support gas preferably being selected from the group consisting of N2O, Ar, 02, H2, N2 and mixtures thereof.
  • the monomer or monomers in the form of gas may preferably feed into the reaction chamber in an amount of between 0.1 and 10 ml/min/l plasma reactor.
  • the deposition may e.g. be performed at any temperature but it is preferred that the deposition in the plasma reactor is performed at room temperature or at elevated temperature, more preferably at 15 - 100 °C.
  • the time for deposition depends largely on the deposition condition and the concentration of monomers. As example a deposition time of least 1 to 120 minutes may be used. Normally the deposition time will be 5-40 minutes
  • the at least one monomer being selected such that the deposited layer being essentially inorganic.
  • the deposited layer being essentially inorganic.
  • the at least one monomer being selected such that the deposited layer being organic.
  • the deposited layer being organic.
  • the one or more monomer(s) may preferably be selected in dependence on the type of substrate and the type of elastomer and its chemical curing (cross linking) reaction.
  • the at least one monomer comprises a Si containing monomer, preferably selected from the group consisting of silanes and/or organosilicon compositions such as hexamethyldisiloxane, methoxythmethylsilane, tetramethoxysilane, hexamethylcyclotrisiloxane, methyltriethoxysilane, or phenylthethoxysilane.
  • Si containing monomer preferably selected from the group consisting of silanes and/or organosilicon compositions such as hexamethyldisiloxane, methoxythmethylsilane, tetramethoxysilane, hexamethylcyclotrisiloxane, methyltriethoxysilane, or phenylthethoxysilane.
  • the one or more monomers comprising at least one monomer selected from silane, hexamethyldisiloxane, tetramethyoxysilane, tetraethoxysilane, the monomer being fed into the reaction chamber together with an oxidating composition such as O 2 .
  • the plasma deposition comprises, feeding the at least one monomer to the plasma reactor together with a support gas.
  • the support gas may preferably comprise an inert gas component and/or an oxidizing gas component.
  • the inert gas may in principle be any kind of gas, but for economically and safety reasons Ar gas is preferred.
  • Other useful inert gasses include helium, neon and krypton.
  • the oxidizing gas component may preferably be O 2 or N 2 O.
  • the monomer(s) may preferably be selected to form a glass layer in the form of an oxide network including Si atoms.
  • the Si based glass layer is provided using the method of applying a glass-barrier layer as described in WO07062665.
  • O 2 being fed to the reaction chamber in a molar ratio monomer: O 2 of from 20:1 to 1 :20, such as from 10:1 to 1 :10, such as from 5:1 to 1 :5, such as from 2:1 to 1 :2, such as about 1 :1.
  • Ar being fed to the reaction chamber in a molar ratio monomer: Ar of from 10:1 to 1 :10, such as from 5:1 to1 :5, such as from 3:1 to 1 :3, such as from 2:1 to 1 :2, such as about 1 :1.
  • the one or more monomers comprising at least one monomer selected from hexamethylsiloxane, tetramethoxysilane and tetraethoxysilane.
  • the primer layer may be essentially homogenous or its composition may vary.
  • the method of the invention comprises applying a graduated primer layer, the method comprising feeding at least two monomers in amounts which are varied relative to each other during the deposition treatment.
  • the method of the invention comprises applying one single primer layer only.
  • This single primer layer may be essentially homogenous or its composition may vary gradually along the thickness of the primer layer.
  • the method of the invention comprises applying two or more primer layers.
  • Each of these two or more primer layers may be essentially homogenous or its composition may vary gradually along the thickness of the primer layer.
  • At least one of the primer layers is a glass layer in the form of an oxide network including Si atoms, preferably all primer layers are in the form of glass layers comprising an oxide network including Si atoms.
  • the method may preferably comprise comprising applying alternating Si-oxide network and Si-C-oxide network layers, wherein the layers independently of each other optionally comprise up to 50 % by atom mol of the respective layer composition of carbon.
  • a second primer layer onto the first primer layer comprising feeding one or more of the monomers selected from the group of alkanes, alkenes, alkines, alcohols, amines, ammonia compounds with vinyl and/or allyl groups, compounds with ester and/or acid groups and compounds with flouro groups.
  • the two or more primer layers being applied immediately after each other in same plasma treating process.
  • the substrate or at least the surface segment of the substrate may preferably be subjected to a pre-treatment e.g. for cleaning the surface and/or for activating the surface.
  • the method comprising pre-treating the surface segment of the substrate using plasma treatment prior to applying the primer layer.
  • the plasma pre-treatment may preferably comprise subjecting the surface segment of the substrate to an oxidizing gas in the absence of monomer.
  • the oxidizing gas in the pre-treatment may preferably comprise one or more oxidizing components selected from the group consisting of O 2 , N 2 O and mixtures thereof.
  • the oxidizing gas comprises one or more oxidizing components in combination with one or more inert gasses selected from the group consisting of argon, helium, neon and krypton.
  • the pre-treatment comprises cleaning and or activation of the surface segment in a reduction gas plasma (e.g. using H 2 gas), optionally followed by a pre-treatment comprising subjecting the surface segment of the substrate to an oxidizing gas.
  • the pre-treatment comprises cleaning and or activation of the surface segment in a reduction gas plasma (e.g. using H 2 gas), optionally followed by applying a primer layer.
  • a reduction gas plasma e.g. using H 2 gas
  • the surface segment of the substrate may be all of the substrate or one or more parts of the substrate surface.
  • the surface segment may additionally be subjected to a post-treatment i.e. a treatment performed onto the applied primer layer but prior to applying the elastomer.
  • the post-treatment may preferably be a plasma treatment e.g. a plasma treatment with an oxidizing component in a plasma in the absence of monomer.
  • the oxidizing component may preferably be oxygen, N 2 O or CO 2 .
  • the post-treatment may e.g. be performed for up to 15 minutes, preferably between 0.5 and 5 minutes, such as between 1 and 3 minutes.
  • the method comprises overmolding an elastomer onto at least a part of the treated surface segment of the substrate.
  • the overmolding may preferably comprise applying the elastomer in non-cured or partly-cured condition onto the substrate and curing the elastomer.
  • the overmolding may in one embodiment comprise applying the substrate and the elastomer in a mould simultaneously or one after the other, followed by curing the elastomer preferably under pressure.
  • the elastomer may be applied to the substrate in partly-cured condition.
  • the obtained bonding between substrate and elastomer has shown to be very strong even when only the final curing is performed when the elastomer is in contact with the substrate.
  • the overmolding comprises applying the elastomer onto at least a part of the substrate surface, by spraying, brushing, dipping, printing, laminating or rolling, followed by curing the elastomer.
  • the overmolding comprises shaping and partly curing the elastomer, and applying the substrate in contact with the elastomer and allowing the elastomer to proceed curing.
  • the substrate and the partly cured elastomer is pressed together.
  • the pressure need not be maintained during the final curing process but it is desired that the pressure is maintained at least for 10 seconds, such as at least 20 seconds, such as at least 1 minutes.
  • the pressure may be applied manually or by machine.
  • the method comprises applying a pressure to hold together the substrate and the partly cures elastomer, the pressure preferably being at least 1 N per m 2 substrate segment, such as at least 5 N per m 2 substrate segment, such as at least 10 N per m 2 substrate segment.
  • the overmolding comprises - melting and applying the elastomer to the substrate by one or more of the methods pressing, extrusion, injection moulding, thermoforming, thermo moulding, calendaring, rotation moulding, compression moulding and transfer moulding and allowing the elastomer to cure.
  • the elastomer may be cured using any method e.g. using conventional heat and/or electromagnetic waves such as IR, micro wave, UV and combinations thereof.
  • the elastomer should prior to application onto the substrate be capable of curing.
  • the elastomer is a rubber.
  • Preferred rubbers includes rubbers selected from silicone rubber, fluoro elastomer rubber (e.g. based on hexafluoropropylene vinylidene fluoride), and acrylonitrile-butadiene rubber (NBR), polyacrylate rubber, hydrated NBR, styrene-butadiene-rubber (SBR), natural rubber (NR), ethylene-propylene-diene-rubber (EPDM), Isoprene- rubber (IR), polyester-urethane and polyether-urethane.
  • silicone rubber e.g. based on hexafluoropropylene vinylidene fluoride
  • NBR acrylonitrile-butadiene rubber
  • SBR styrene-butadiene-rubber
  • NR natural rubber
  • EPDM ethylene-propylene-diene-rubber
  • IR Isoprene- rubber
  • the rubber is silicone rubber, such as silicone rubber selected from liquid silicone elastomers (LSR), RTV- 1 silicone rubbers, RTV-2 silicone elastomers and HTV silicone elastomers, the silicone rubber preferably being selected from functionalized silicone rubbers such as fluoro silicone rubbers and self adhesive silicone rubbers.
  • LSR liquid silicone elastomers
  • RTV- 1 silicone rubbers RTV- 1 silicone rubbers
  • RTV-2 silicone elastomers and HTV silicone elastomers
  • the silicone rubber preferably being selected from functionalized silicone rubbers such as fluoro silicone rubbers and self adhesive silicone rubbers.
  • the elastomer is silicone rubber comprising one or more of the silicone components selected from the group consisting of dialkylsilicone elastomers wherein alkyl means hydrocarbon side groups of 1 -12 carbon atoms such as methyl, ethyl, hexyl, and octyl; vinyl silicone elastomers; phenyl silicone elastomers; nitrile silicone elastomers; fluorosilicone elastomers, room temperature vulcanising (RTV) silicone elastomers; liquid silicone elastomers (LSR); borosilicone elastomers, and dimethyl silicone elastomers.
  • dialkylsilicone elastomers wherein alkyl means hydrocarbon side groups of 1 -12 carbon atoms such as methyl, ethyl, hexyl, and octyl
  • vinyl silicone elastomers phenyl silicone elastomers
  • the silicone rubber may preferably be cross-linked using a method selected from the group of condensation reaction, addition reaction, peroxide assisted reaction, platinum catalyzed, rhodium catalyzed reaction and mixtures thereof.
  • the invention also relates an item obtainable using the method as described above.
  • the invention further relates to an overmolded item comprising a substrate and an elastomer bonded to each other and with an interface layer having a composition which is not merely a mixture of the composition of the substrate and the elastomer, wherein said interface layer has a thickness of 200 nm or less measured using SEM (Scanning electron microscope).
  • the substrate and the elastomer may be as described above.
  • the primer layer(s) may be obtainable by the method and using the materials as described above.
  • the interface layer has a thickness of 150 nm or less, such as a thickness 100 nm or less, such as a thickness of 50 nm or less.
  • the interface layer has a glasslike structure
  • the interface layer preferably comprises an oxide network of Si and optionally other atom(s).
  • the bonding between the substrate and the elastomer is stronger than the intrinsic strength of at least one of the substrate and the elastomer.
  • the plasma treatment was made in an equipment with a reaction chamber volume of around 290 L, and supplied with a 50 Hz power supplier.
  • Plasma treatment parameters Monomer: (Tetramethoxysilane)
  • the obtained primer layer is not pure inorganic, but contains some organic parts.
  • the treated substrates as well as 4 corresponding samples which were not treated by plasma (free of primer) were overmolded with an elastomer.
  • the elastomer was applied manually onto the substrate by an applicator to obtain a thickness of about 1 mm. Then the elastomer was covered by a PTFE and slightly pressed (about 200 g) and applied in a heating chamber where the elastomer was cured 5 min at 150°C.
  • the plasma treatment was made in equipment with a reaction chamber volume around 30 L, and a power supplier (Tantec) of 1 kW (30k Hz).
  • TMOS Tetramethoxysilane
  • the plasma treatment was initiated by applying a soft organic primer layer (silicon like coating) and by changing the energy and increasing the oxygen feeding, the primer layer becomes gradually more and more inorganic (glass coating). At the end the post treating will remove the organic part and make the surface pure inorganic glass coating.
  • a soft organic primer layer silicon like coating
  • inorganic glass coating
  • the treated substrates as well as 4 corresponding samples which were not treated by plasma (free of primer) were overmolded with an elastomer.
  • the elastomers were applied manually onto the respective substrates, LSR was covered with PTFE foil, slightly pressed (20Og) and applied in a heating chamber where the elastomer was cured 5 min at 150°C. RTV was applied in a thin layer on the substrate and cured 24 h at room temperature. Elastomers: 2K LSR from Wacker, and RTV silicone Dow corning 738 and 3140).
  • PC Polycarbonate
  • PET Polyethylene terephthalate
  • the plasma treatment was made in an equipment with a reaction chamber volume around 12 L, and power supplier (3 fazes) 50 Hz.
  • Plasma treatment parameters Monomer: Acrylnitrile (AN) from Aldrich
  • the obtained primer layer is pure organic.
  • the treated substrates as well as 4 corresponding samples which were not treated by plasma (free of primer) were overmolded with an elastomer.
  • the elastomer was applied manually onto the substrate and pressed together with 1000 N at 130 ° C for 2 min.
  • Elastomer TPU like silicone from Wacker.

Abstract

L'invention porte sur un procédé de fabrication d'un article comprenant les opérations consistant à se procurer un substrat, à traiter au moins une section de surface dudit substrat par application d'au moins une couche de primaire, l'épaisseur totale de la ou des couches de primaire allant jusqu'à 200 nm; et à surmouler un élastomère sur et/ou dans le substrat traité par le primaire. L'article produit selon l'invention comprend une liaison interfaciale très forte entre le substrat et la couche surmoulée. Le substrat et l'élastomère forment une liaison très forte et durable de l'une avec l'autre, même lorsque les matières diffèrent quant à la dureté et/ou la rigidité. Le procédé peut être utilisé avec de la silicone en tant qu'élastomère surmoulé.
PCT/DK2008/050246 2007-10-12 2008-10-06 Procédé de fabrication d'un article et article surmoulé WO2009046725A1 (fr)

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DKPA200701476 2007-10-12
DKPA200701476 2007-10-12

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WO2009046725A1 true WO2009046725A1 (fr) 2009-04-16

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US7785302B2 (en) 2005-03-04 2010-08-31 C. R. Bard, Inc. Access port identification systems and methods
US7947022B2 (en) 2005-03-04 2011-05-24 C. R. Bard, Inc. Access port identification systems and methods
US8025639B2 (en) 2005-04-27 2011-09-27 C. R. Bard, Inc. Methods of power injecting a fluid through an access port
US8029482B2 (en) 2005-03-04 2011-10-04 C. R. Bard, Inc. Systems and methods for radiographically identifying an access port
CN102285267A (zh) * 2011-06-03 2011-12-21 吕贵棠 基于硫化工艺的环保型橡胶专用转移膜以及硫化转印方法
US8177762B2 (en) 1998-12-07 2012-05-15 C. R. Bard, Inc. Septum including at least one identifiable feature, access ports including same, and related methods
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US8257325B2 (en) 2007-06-20 2012-09-04 Medical Components, Inc. Venous access port with molded and/or radiopaque indicia
USD676955S1 (en) 2010-12-30 2013-02-26 C. R. Bard, Inc. Implantable access port
USD682416S1 (en) 2010-12-30 2013-05-14 C. R. Bard, Inc. Implantable access port
US20130298344A1 (en) * 2010-12-21 2013-11-14 David Bachar Silicone Broom and a Manufacturing Method of Silicone Broom
US8641676B2 (en) 2005-04-27 2014-02-04 C. R. Bard, Inc. Infusion apparatuses and methods of use
US8715244B2 (en) 2009-07-07 2014-05-06 C. R. Bard, Inc. Extensible internal bolster for a medical device
US8932271B2 (en) 2008-11-13 2015-01-13 C. R. Bard, Inc. Implantable medical devices including septum-based indicators
US9079004B2 (en) 2009-11-17 2015-07-14 C. R. Bard, Inc. Overmolded access port including anchoring and identification features
US9265912B2 (en) 2006-11-08 2016-02-23 C. R. Bard, Inc. Indicia informative of characteristics of insertable medical devices
US9285584B2 (en) 2010-10-06 2016-03-15 3M Innovative Properties Company Anti-reflective articles with nanosilica-based coatings and barrier layer
US9474888B2 (en) 2005-03-04 2016-10-25 C. R. Bard, Inc. Implantable access port including a sandwiched radiopaque insert
US9517329B2 (en) 2007-07-19 2016-12-13 Medical Components, Inc. Venous access port assembly with X-ray discernable indicia
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US9579496B2 (en) 2007-11-07 2017-02-28 C. R. Bard, Inc. Radiopaque and septum-based indicators for a multi-lumen implantable port
US9610432B2 (en) 2007-07-19 2017-04-04 Innovative Medical Devices, Llc Venous access port assembly with X-ray discernable indicia
US9642986B2 (en) 2006-11-08 2017-05-09 C. R. Bard, Inc. Resource information key for an insertable medical device
US9896557B2 (en) 2010-04-28 2018-02-20 3M Innovative Properties Company Silicone-based material
US10066109B2 (en) 2010-04-28 2018-09-04 3M Innovative Properties Company Articles including nanosilica-based primers for polymer coatings and methods
US10307581B2 (en) 2005-04-27 2019-06-04 C. R. Bard, Inc. Reinforced septum for an implantable medical device
CN111922334A (zh) * 2020-07-02 2020-11-13 嘉善君圆新材料科技有限公司 一种基于微波的碳包覆粉体及其制备方法
CN112323040A (zh) * 2019-08-05 2021-02-05 通用汽车环球科技运作有限责任公司 将聚合物材料键合到基材上的方法
US11890443B2 (en) 2008-11-13 2024-02-06 C. R. Bard, Inc. Implantable medical devices including septum-based indicators

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US8177762B2 (en) 1998-12-07 2012-05-15 C. R. Bard, Inc. Septum including at least one identifiable feature, access ports including same, and related methods
US9603992B2 (en) 2005-03-04 2017-03-28 C. R. Bard, Inc. Access port identification systems and methods
US8029482B2 (en) 2005-03-04 2011-10-04 C. R. Bard, Inc. Systems and methods for radiographically identifying an access port
US10265512B2 (en) 2005-03-04 2019-04-23 Bard Peripheral Vascular, Inc. Implantable access port including a sandwiched radiopaque insert
US10905868B2 (en) 2005-03-04 2021-02-02 Bard Peripheral Vascular, Inc. Systems and methods for radiographically identifying an access port
US7959615B2 (en) 2005-03-04 2011-06-14 C. R. Bard, Inc. Access port identification systems and methods
US8202259B2 (en) 2005-03-04 2012-06-19 C. R. Bard, Inc. Systems and methods for identifying an access port
US10857340B2 (en) 2005-03-04 2020-12-08 Bard Peripheral Vascular, Inc. Systems and methods for radiographically identifying an access port
US8382724B2 (en) 2005-03-04 2013-02-26 C. R. Bard, Inc. Systems and methods for radiographically identifying an access port
US7785302B2 (en) 2005-03-04 2010-08-31 C. R. Bard, Inc. Access port identification systems and methods
US7947022B2 (en) 2005-03-04 2011-05-24 C. R. Bard, Inc. Access port identification systems and methods
US8382723B2 (en) 2005-03-04 2013-02-26 C. R. Bard, Inc. Access port identification systems and methods
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US8998860B2 (en) 2005-03-04 2015-04-07 C. R. Bard, Inc. Systems and methods for identifying an access port
US10179230B2 (en) 2005-03-04 2019-01-15 Bard Peripheral Vascular, Inc. Systems and methods for radiographically identifying an access port
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US9474888B2 (en) 2005-03-04 2016-10-25 C. R. Bard, Inc. Implantable access port including a sandwiched radiopaque insert
US10238850B2 (en) 2005-03-04 2019-03-26 Bard Peripheral Vascular, Inc. Systems and methods for radiographically identifying an access port
US10661068B2 (en) 2005-04-27 2020-05-26 Bard Peripheral Vascular, Inc. Assemblies for identifying a power injectable access port
US10307581B2 (en) 2005-04-27 2019-06-04 C. R. Bard, Inc. Reinforced septum for an implantable medical device
US10183157B2 (en) 2005-04-27 2019-01-22 Bard Peripheral Vascular, Inc. Assemblies for identifying a power injectable access port
US10052470B2 (en) 2005-04-27 2018-08-21 Bard Peripheral Vascular, Inc. Assemblies for identifying a power injectable access port
US8545460B2 (en) 2005-04-27 2013-10-01 C. R. Bard, Inc. Infusion apparatuses and related methods
US10016585B2 (en) 2005-04-27 2018-07-10 Bard Peripheral Vascular, Inc. Assemblies for identifying a power injectable access port
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US9421352B2 (en) 2005-04-27 2016-08-23 C. R. Bard, Inc. Infusion apparatuses and methods of use
US8805478B2 (en) 2005-04-27 2014-08-12 C. R. Bard, Inc. Methods of performing a power injection procedure including identifying features of a subcutaneously implanted access port for delivery of contrast media
US8025639B2 (en) 2005-04-27 2011-09-27 C. R. Bard, Inc. Methods of power injecting a fluid through an access port
US8641688B2 (en) 2005-04-27 2014-02-04 C. R. Bard, Inc. Assemblies for identifying a power injectable access port
US8641676B2 (en) 2005-04-27 2014-02-04 C. R. Bard, Inc. Infusion apparatuses and methods of use
US10780257B2 (en) 2005-04-27 2020-09-22 Bard Peripheral Vascular, Inc. Assemblies for identifying a power injectable access port
US10625065B2 (en) 2005-04-27 2020-04-21 Bard Peripheral Vascular, Inc. Assemblies for identifying a power injectable access port
US11878137B2 (en) 2006-10-18 2024-01-23 Medical Components, Inc. Venous access port assembly with X-ray discernable indicia
US10556090B2 (en) 2006-11-08 2020-02-11 C. R. Bard, Inc. Resource information key for an insertable medical device
US9642986B2 (en) 2006-11-08 2017-05-09 C. R. Bard, Inc. Resource information key for an insertable medical device
US10092725B2 (en) 2006-11-08 2018-10-09 C. R. Bard, Inc. Resource information key for an insertable medical device
US9265912B2 (en) 2006-11-08 2016-02-23 C. R. Bard, Inc. Indicia informative of characteristics of insertable medical devices
US8257325B2 (en) 2007-06-20 2012-09-04 Medical Components, Inc. Venous access port with molded and/or radiopaque indicia
US9533133B2 (en) 2007-06-20 2017-01-03 Medical Components, Inc. Venous access port with molded and/or radiopaque indicia
US11406808B2 (en) 2007-06-20 2022-08-09 Medical Components, Inc. Venous access port with molded and/or radiopaque indicia
US11478622B2 (en) 2007-06-20 2022-10-25 Medical Components, Inc. Venous access port with molded and/or radiopaque indicia
US8852160B2 (en) 2007-06-20 2014-10-07 Medical Components, Inc. Venous access port with molded and/or radiopaque indicia
US11938296B2 (en) 2007-06-20 2024-03-26 Medical Components, Inc. Venous access port with molded and/or radiopaque indicia
US10874842B2 (en) 2007-07-19 2020-12-29 Medical Components, Inc. Venous access port assembly with X-ray discernable indicia
US9610432B2 (en) 2007-07-19 2017-04-04 Innovative Medical Devices, Llc Venous access port assembly with X-ray discernable indicia
US9517329B2 (en) 2007-07-19 2016-12-13 Medical Components, Inc. Venous access port assembly with X-ray discernable indicia
US10639465B2 (en) 2007-07-19 2020-05-05 Innovative Medical Devices, Llc Venous access port assembly with X-ray discernable indicia
US10792485B2 (en) 2007-11-07 2020-10-06 C. R. Bard, Inc. Radiopaque and septum-based indicators for a multi-lumen implantable port
US11638810B2 (en) 2007-11-07 2023-05-02 C. R. Bard, Inc. Radiopaque and septum-based indicators for a multi-lumen implantable port
US10086186B2 (en) 2007-11-07 2018-10-02 C. R. Bard, Inc. Radiopaque and septum-based indicators for a multi-lumen implantable port
US9579496B2 (en) 2007-11-07 2017-02-28 C. R. Bard, Inc. Radiopaque and septum-based indicators for a multi-lumen implantable port
US10773066B2 (en) 2008-11-13 2020-09-15 C. R. Bard, Inc. Implantable medical devices including septum-based indicators
US8932271B2 (en) 2008-11-13 2015-01-13 C. R. Bard, Inc. Implantable medical devices including septum-based indicators
US11890443B2 (en) 2008-11-13 2024-02-06 C. R. Bard, Inc. Implantable medical devices including septum-based indicators
US10052471B2 (en) 2008-11-13 2018-08-21 C. R. Bard, Inc. Implantable medical devices including septum-based indicators
US8715244B2 (en) 2009-07-07 2014-05-06 C. R. Bard, Inc. Extensible internal bolster for a medical device
US9079004B2 (en) 2009-11-17 2015-07-14 C. R. Bard, Inc. Overmolded access port including anchoring and identification features
US9717895B2 (en) 2009-11-17 2017-08-01 C. R. Bard, Inc. Overmolded access port including anchoring and identification features
US11759615B2 (en) 2009-11-17 2023-09-19 Bard Peripheral Vascular, Inc. Overmolded access port including anchoring and identification features
US10912935B2 (en) 2009-11-17 2021-02-09 Bard Peripheral Vascular, Inc. Method for manufacturing a power-injectable access port
US9248268B2 (en) 2009-11-17 2016-02-02 C. R. Bard, Inc. Overmolded access port including anchoring and identification features
US10155101B2 (en) 2009-11-17 2018-12-18 Bard Peripheral Vascular, Inc. Overmolded access port including anchoring and identification features
US10066109B2 (en) 2010-04-28 2018-09-04 3M Innovative Properties Company Articles including nanosilica-based primers for polymer coatings and methods
US9896557B2 (en) 2010-04-28 2018-02-20 3M Innovative Properties Company Silicone-based material
US9285584B2 (en) 2010-10-06 2016-03-15 3M Innovative Properties Company Anti-reflective articles with nanosilica-based coatings and barrier layer
US8887344B2 (en) * 2010-12-21 2014-11-18 David Bachar Silicone broom and a manufacturing method of silicone broom
US20130298344A1 (en) * 2010-12-21 2013-11-14 David Bachar Silicone Broom and a Manufacturing Method of Silicone Broom
USD682416S1 (en) 2010-12-30 2013-05-14 C. R. Bard, Inc. Implantable access port
USD676955S1 (en) 2010-12-30 2013-02-26 C. R. Bard, Inc. Implantable access port
CN102285267A (zh) * 2011-06-03 2011-12-21 吕贵棠 基于硫化工艺的环保型橡胶专用转移膜以及硫化转印方法
US9573843B2 (en) 2013-08-05 2017-02-21 Corning Incorporated Polymer edge-covered glass articles and methods for making and using same
US20210040608A1 (en) * 2019-08-05 2021-02-11 GM Global Technology Operations LLC Method for bonding a polymeric material to a substrate
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