CA2446142A1 - Fluoropolymer bonding composition and method - Google Patents
Fluoropolymer bonding composition and method Download PDFInfo
- Publication number
- CA2446142A1 CA2446142A1 CA 2446142 CA2446142A CA2446142A1 CA 2446142 A1 CA2446142 A1 CA 2446142A1 CA 2446142 CA2446142 CA 2446142 CA 2446142 A CA2446142 A CA 2446142A CA 2446142 A1 CA2446142 A1 CA 2446142A1
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- compound
- fluoropolymer
- bonding composition
- bonding
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31536—Including interfacial reaction product of adjacent layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
- Y10T428/31544—Addition polymer is perhalogenated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
- Y10T428/31649—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31699—Ester, halide or nitrile of addition polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Adhesive Tapes (AREA)
- Dental Preparations (AREA)
Abstract
A multi-layer structure includes a fluoropolymer bonded to a substrate. The structure is prepared by exposing a bonding composition to actinic radiation , such as ultraviolet radiation, to form the bond. The bonding composition includes a light-absorbing compound and an electron donor. The bonding composition includes non-adhesive materials.
Description
FLUOROPOLYMER BONDING COMPOSITION AND METHOD
TECHNICAL FIELD
This invention relates to methods and compositions for bonding a fluoropolymer to a substrate.
BACKGROUND
Fluorine-containing polymers (also known as "fluoropolymers") are a commercially useful class of materials. Fluoropolymers include, for example, crosslinked fluoroelastomers and semi-crystalline or glassy fluoropolymers. Fluoropolymers are generally of high thermal stability and are particularly useful at high temperatures. They may also exhibit extreme toughness and flexibility at very low temperatures. Many of these fluoropolymers are almost totally insoluble in a wide variety of solvents and are generally chemically resistant. Some have extremely low dielectric loss and high dielectric strength, and may have unique non-adhesive and low friction properties. Fluoroelastomers, particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers such as hexafluoropropylene, have particular utility in high temperature applications such as seals, gaskets, and linings.
Multi-layer constructions containing a fluoropolymer enjoy wide industrial application.
Such constructions find utility, for example, in fuel line hoses and related containers and hoses or gaskets in the chemical processing field. Adhesion between the layers of a multi-layered article may need to meet various performance standards depending on the use of the finished article. However, it is often difficult to establish high bond strengths when one of the layers is a fluoropolymer, in part, because of the non-adhesive qualities of fluoropolymers. Various methods have been proposed to address this problem. One approach is to use an adhesive layer or tie layer between the fluoropolymer layer and the second polymer layer.
Surface treatments for the fluoropolymer layer, including the use of powerful reducing agents (e,g., sodium naphthalide) and corona discharge, have also been employed to enhance adhesion. In the case of fluoropolymers containing interpolymerized units derived from vinylidene fluoride, exposure of the fluoropolymer to a dehydrofluorinating agent such as a base has been used, as well as polyamine reagents applied to the fluoropolymer surface or incorporated within the fluoropolymer itself.
SUMMARY
A multi-layer structure includes a fluoropolymer bonded to a substrate. The structure is prepared by exposing a bonding composition to actinic radiation, such as ultraviolet radiation, with optional heating, pressure, or combination thereof, to form the bond. The bonding composition includes a light-absorbing compound and an electron donor. The bonding composition may be free of adhesive materials.
1n one aspect, a method of bonding a fluoropolymer to a substrate includes providing a bonding composition between a fluoropolymer and a substrate, and exposing the bonding composition to actinic radiation.
In another aspect, a method of bonding a fluoropolymer to a substrate includes providing a first substrate including a bonding composition, contacting the treated surface of the first substrate with a surface of a second substrate, and exposing the bonding composition to actinic radiation. The method may include applying heat, pressure, or a combination thereof, to form the bond. Each of the first substrate and the second substrate, independently, includes a matrix material. The matrix material can be a metal, a glass, an organic-inorganic composite, a fluoropolymer, and a non-fluorinated polymer with the proviso that at least one of the first substrate and the second substrate is a fluoropolymer.
The bonding composition may be provided between the fluoropolymer and the substrate in different ways. For example, a surface of the fluoropolymer may be treated with the bonding composition and the treated surface of the fluoropolymer may be contacted with a surface of the substrate, or a surface of the substrate may be treated with the bonding composition and the treated surface of the substrate may be contacted with a surface of the fluoropolymer. In certain embodiments, a mixture of the fluoropolymer and the bonding composition may be extruded and a surface of the extruded mixture may be contacted with a surface of the substrate. In other embodiments, the substrate or the fluoropolymer may be cast from solution or polymerized from a monomer. The bonding composition may be exposed to actinic radiation before contacting.
In another aspect, a composite article includes a fluoropolymer having a surface, a substrate having a surface, and a bonding composition interposed between the surface of the fluoropolymer and the surface of the substrate.
In yet another aspect, a treated fluoropolymer substrate suitable for bonding to a polymeric substrate includes a surface exposed to a combination of a light-absorbing compound and an electron donor and actinic radiation.
In still another aspect, a laminated article including a fluoropolymer is bonded to a substrate by a bonding composition including a light-absorbing compound and an electron donor exposed to actinic radiation.
In another aspect, a composition includes a fluoroalkylamine, such as a 2,2,2-trifluoroethylamine.
The bonding composition includes a light-absorbing compound and an electron donor.
I0 The light-absorbing compound may be an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, or combinations thereof. The ammonium compound or phosphonium compound may include a benzyl moiety. The electron donor may be an amine, a phosphine, a thioether, or combinations thereof. The amine may be a primary amine, an amino-substituted organosilane, I S or combinations thereof. The amine may be a mono-, di- or tri-alkylamine.
The alkylamine can be a fluoroalkylamine. The amino-substituted organosilane may have a hydrolyzable substituent. The bonding composition may include a vinylsilane. The bonding composition may be exposed to actinic radiation through the fluoropolymer or the substrate.
The fluoropolymer may be a perfluorinated polymer or a partially fluorinated polymer.
20 The substrate may include an inorganic substrate, such as a metal and a glass, or an organic substrate, such as a non-fluorinated polymer or fluoropolymer, or an organic-inorganic composite.
Bonded multi-layer materials may have combined physical and chemical properties possessed by both fluoropolymers and non-fluorinated polymers, resulting in less expensive, 25 well-performing articles. For example, the fluoropolymer component may be used in automotive hose and container constructions, anti-soiling films, low energy surface PSA tapes and coatings for aircraft. The bonding process is a mild photochemical lamination that may promote adhesion between a fluoropolymer and a substrate. The bonding composition may be used to form a composite article having a fluoropolymer cladding on a conductive and lustrous 30 metal to protect it from corrosion, a fluoropolymer cladding on glass fibers to enhance their physical strength and chemical resistance for telecommunication, or a fluoropolymer layer bonded to a hydrocarbon substrate in a multi-layer materials.
TECHNICAL FIELD
This invention relates to methods and compositions for bonding a fluoropolymer to a substrate.
BACKGROUND
Fluorine-containing polymers (also known as "fluoropolymers") are a commercially useful class of materials. Fluoropolymers include, for example, crosslinked fluoroelastomers and semi-crystalline or glassy fluoropolymers. Fluoropolymers are generally of high thermal stability and are particularly useful at high temperatures. They may also exhibit extreme toughness and flexibility at very low temperatures. Many of these fluoropolymers are almost totally insoluble in a wide variety of solvents and are generally chemically resistant. Some have extremely low dielectric loss and high dielectric strength, and may have unique non-adhesive and low friction properties. Fluoroelastomers, particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers such as hexafluoropropylene, have particular utility in high temperature applications such as seals, gaskets, and linings.
Multi-layer constructions containing a fluoropolymer enjoy wide industrial application.
Such constructions find utility, for example, in fuel line hoses and related containers and hoses or gaskets in the chemical processing field. Adhesion between the layers of a multi-layered article may need to meet various performance standards depending on the use of the finished article. However, it is often difficult to establish high bond strengths when one of the layers is a fluoropolymer, in part, because of the non-adhesive qualities of fluoropolymers. Various methods have been proposed to address this problem. One approach is to use an adhesive layer or tie layer between the fluoropolymer layer and the second polymer layer.
Surface treatments for the fluoropolymer layer, including the use of powerful reducing agents (e,g., sodium naphthalide) and corona discharge, have also been employed to enhance adhesion. In the case of fluoropolymers containing interpolymerized units derived from vinylidene fluoride, exposure of the fluoropolymer to a dehydrofluorinating agent such as a base has been used, as well as polyamine reagents applied to the fluoropolymer surface or incorporated within the fluoropolymer itself.
SUMMARY
A multi-layer structure includes a fluoropolymer bonded to a substrate. The structure is prepared by exposing a bonding composition to actinic radiation, such as ultraviolet radiation, with optional heating, pressure, or combination thereof, to form the bond. The bonding composition includes a light-absorbing compound and an electron donor. The bonding composition may be free of adhesive materials.
1n one aspect, a method of bonding a fluoropolymer to a substrate includes providing a bonding composition between a fluoropolymer and a substrate, and exposing the bonding composition to actinic radiation.
In another aspect, a method of bonding a fluoropolymer to a substrate includes providing a first substrate including a bonding composition, contacting the treated surface of the first substrate with a surface of a second substrate, and exposing the bonding composition to actinic radiation. The method may include applying heat, pressure, or a combination thereof, to form the bond. Each of the first substrate and the second substrate, independently, includes a matrix material. The matrix material can be a metal, a glass, an organic-inorganic composite, a fluoropolymer, and a non-fluorinated polymer with the proviso that at least one of the first substrate and the second substrate is a fluoropolymer.
The bonding composition may be provided between the fluoropolymer and the substrate in different ways. For example, a surface of the fluoropolymer may be treated with the bonding composition and the treated surface of the fluoropolymer may be contacted with a surface of the substrate, or a surface of the substrate may be treated with the bonding composition and the treated surface of the substrate may be contacted with a surface of the fluoropolymer. In certain embodiments, a mixture of the fluoropolymer and the bonding composition may be extruded and a surface of the extruded mixture may be contacted with a surface of the substrate. In other embodiments, the substrate or the fluoropolymer may be cast from solution or polymerized from a monomer. The bonding composition may be exposed to actinic radiation before contacting.
In another aspect, a composite article includes a fluoropolymer having a surface, a substrate having a surface, and a bonding composition interposed between the surface of the fluoropolymer and the surface of the substrate.
In yet another aspect, a treated fluoropolymer substrate suitable for bonding to a polymeric substrate includes a surface exposed to a combination of a light-absorbing compound and an electron donor and actinic radiation.
In still another aspect, a laminated article including a fluoropolymer is bonded to a substrate by a bonding composition including a light-absorbing compound and an electron donor exposed to actinic radiation.
In another aspect, a composition includes a fluoroalkylamine, such as a 2,2,2-trifluoroethylamine.
The bonding composition includes a light-absorbing compound and an electron donor.
I0 The light-absorbing compound may be an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, or combinations thereof. The ammonium compound or phosphonium compound may include a benzyl moiety. The electron donor may be an amine, a phosphine, a thioether, or combinations thereof. The amine may be a primary amine, an amino-substituted organosilane, I S or combinations thereof. The amine may be a mono-, di- or tri-alkylamine.
The alkylamine can be a fluoroalkylamine. The amino-substituted organosilane may have a hydrolyzable substituent. The bonding composition may include a vinylsilane. The bonding composition may be exposed to actinic radiation through the fluoropolymer or the substrate.
The fluoropolymer may be a perfluorinated polymer or a partially fluorinated polymer.
20 The substrate may include an inorganic substrate, such as a metal and a glass, or an organic substrate, such as a non-fluorinated polymer or fluoropolymer, or an organic-inorganic composite.
Bonded multi-layer materials may have combined physical and chemical properties possessed by both fluoropolymers and non-fluorinated polymers, resulting in less expensive, 25 well-performing articles. For example, the fluoropolymer component may be used in automotive hose and container constructions, anti-soiling films, low energy surface PSA tapes and coatings for aircraft. The bonding process is a mild photochemical lamination that may promote adhesion between a fluoropolymer and a substrate. The bonding composition may be used to form a composite article having a fluoropolymer cladding on a conductive and lustrous 30 metal to protect it from corrosion, a fluoropolymer cladding on glass fibers to enhance their physical strength and chemical resistance for telecommunication, or a fluoropolymer layer bonded to a hydrocarbon substrate in a multi-layer materials.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
FIG. 1 is a cross-sectional view of a multi-layer article.
DETAILED DESCRIPTION
A fluoropolymer layer may be bonded on one surface of a substrate to form, for example, a laminate. The laminate may contain two or more layers. Referring to Fig. 1, the laminate 10 includes fluoropolymer layer 20 and the substrate 30. Bonding composition 40 contacts the interface between fluoropolymer layer 20 and substrate 30. Actinic radiation applied to the bonding composition promotes bonding between fluoropolymer layer 20 and substrate 30.
The bonding composition includes a light-absorbing compound and an electron donor.
The bonding composition may include a solvent to facilitate applying a coating of the composition to a surface of the fluoropolymers or the substrate, or both. The solvent may be removed, for example, by drying, prior to contacting the substrate and fluoropolymers surfaces.
Any solvent, if used may be a fluorinated solvent, for example, a fluorinated solvent having at least one fluorinated moiety. Fluorinated solvents may be effective at promoting wetting of the bonding composition onto either substrate. Preferred fluorinated solvents include, for example, hexafluoroxylene, hexafluorobenzene, and the like.
Actinic radiation is electromagnetic radiation having a wavelength capable of affecting bonding between the fluoropolymer and the substrate in the presence of the bonding composition. The actinic radiation has an intensity at a wavelength capable of affecting bonding within a reasonable amount of time. The actinic radiation may have a wavelength between 190 nm and 700 nm, preferably between 200 nm and 400 nm, more preferably between 205 nm and 320 nm, even more preferably between 210 nm and 290 nm, and even more preferably between 240 nm and 260 nm.
The actinic radiation has a wavelength that is absorbed by the light-absorbing compound.
The light-absorbing compound may have an absorbing moiety capable of being excited by the actinic radiation, such as, for example, a benzyl moiety or other aromatic moiety. The light-absorbing compound may be an ammonium compound, a phosphine, a phosphonium compound, an aromatic hydrocarbon compound, a thioether compound, an ether compound, a phenolic compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, or combinations thereof. Specific examples include triphenylphosphine, benzyltriphenylphosphonium chloride, benzyltributylammonium chloride, an arylammonium salt, tetraphenylarsonium chloride, diphenyl sulfide, biphenyl, 4,4'-dihydroxybiphenyl and triarylsulfonium chloride. Other examples of light-absorbing compounds are described, e.g., in Fukushi, U.S. Patent No. 5,658,671, "Fluoroelastomer Coating Composition,"
hereby incorporated by reference. The light-absorbing compound may have a molar absorptivity of at least 100, preferably at least 500, more preferably at least 1,500, even more preferably at least 5,000 at a wavelength when exposed to actinic radiation. In some embodiments, the light-absorbing compound may include individual components that do not significantly absorb actinic radiation in a purified state, but absorbs light when the components are combined. For example, a component of the composite may form a charge-transfer complex with the donor, fluoropolymer, substrate or other added ingredient, resulting in a compound that absorbs actinic radiation.
The electron donor is a compound capable of reducing the excited state of the light-absorbing compound. For example, the electron donor may be an amine, a phosphine, a thiol, a thioether, phenol, thiophenol, phenolate, thiophenolate or combinations thereof. The amine may be a primary amine, such as an alkylamine, e.g., a monoalkylamine, a dialkylamine, or a trialkylamine, such as a fluoroalkylamine. The electron donor may be polymerizable, for example, a polymerizable amine such as an aminoalkene or a vinylaniline. The amine may be an amino-substituted organosilane. The amino-substituted organosilane may have a hydrolyzable substituent; for example, it may be a trialkoxysilane. For example, the amino-substituted organosilane may have the formula R' RZN-L-S iXX'X"
where each of R' and Rz, independently, is H, C1-12 alkyl, C1-12 alkenyl, C1-12 alkynyl, or aryl, and L is a divalent straight chain Cl-12 alkylene, C3-8 cycloalkylene, 3-8 membered ring heterocycloalkylene, C1-12 alkenylene, C3-8 cycloalkenylene, 3-8 membered ring heterocycloalkenylene, arylene, or heteroarylene. L is optionally substituted with C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, C1-4 alkoxy, hydroxyl, halo, carboxyl, amino, nitro, cyano, C3-6 cycloalkyl, 3-6 membered heterocycloalkyl, aryl, 5-6 membered ring heteroaryl, alkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4 alkylcarbonyl, formyl, C1-4 alkylcarbonylamino, or C1-4 aminocarbonyl. L is further optionally interrupted by -O-, -S-, -N(Rc)-, -N(Rc)-C(O)-, -N(Rc)-C(O)-O-, -O-C(O)-N(Rc)-, -N(Rc)-C(O)-N(Rd)-, -O-C(O)-, -C(O)-O-, or -O-C(O)-O-. Each of Rc and Rd, independently, is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxylalkyl, hydroxyl, or haloalkyl. Each of X, X' and X"
is a C1-18 alkyl, halogen, C1-8 alkoxy, C1-8 alkylcarbonyloxy, or amino group. When the amino-substituted organosilane has a hydrolyzable substituent, at least one of X, X', and X" is not alkyl. Further, any two of X, X' and X" may be joined through a covalent bond. The amino group may be an alkylamino group.
The bonding composition may include other additives, for example, a vinylsilane, such as an alkoxyvinylsilane, polyhydroxy aromatic compounds, or a thermosetting resin such as an epoxy resin, a urethane resin, a urea resin, or an acrylate resin.
The fluoropolymer may be a perfluorinated polymer or a partially fluorinated polymer.
For example, the fluoropolymer may be either melt-processible such as in the case of a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THVT"'), a tetrafluoroethylene-hexafluoropropene copolymer (FEP), and other melt-processible fluoroplastics, or may be non-melt processable such as in the case of polytetrafluoroethylene (PTFE), modified PTFE copolymers, such as a copolymer of TFE and low levels of fluorinated vinyl ethers and fluoroelastomers. Fluoroelastomers may be processed before they are cured by injection or compression molding or other methods normally associated with thermoplastics.
Fluoroelastomers after curing or crosslinking may not be not able to be further processed.
Fluoroelastomers may also be coated out of solvent in their uncross linked form.
Fluoropolymers may also be coated from an aqueous dispersion form. In preferred embodiments, the fluoropolymer may be FEP, a tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (PFA), perfluoroelastomer, or mixtures thereof.
Preferably, the fluoropolymer is a material that is capable of being extruded or solvent coated. Such fluoropolymers typically are fluoroplastics that have melting temperatures ranging from about 100 to about 330°C, more preferably from about 150 to about 270°C. Preferred fluoroplastics include interpolymerized units derived from VDF and fluoroethylene and may further include interpolymerized units derived from other fluorine-containing monomers, non-fluorine-containing monomers, or a combination thereof.
Examples of suitable fluorine-containing monomers include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), 3-chloropentafluoropropene, perfluorinated vinyl ethers (e.g., perfluoroalkoxy vinyl ethers such as CF30CFzCF2CF20CF=CFZ and perfluoroalkyl vinyl ethers such as CF30CF=CFZ and CF3CFZCFZOCF=CFZ), and fluorine-containing di-olefins such as perfluorodiallyl ether and perfluoro-1,3-butadiene. Examples of suitable non-fluorine-containing monomers include olefin monomers such as ethylene, propylene, and the like.
The VDF-containing fluoropolymer may be prepared using emulsion polymerization techniques as described, e.g., in Sulzbach et al., U.S. Patent No. 4,338,237 or Grootaert, U.S.
Patent No. 5,285,002, hereby incorporated by reference. Useful commercially available VDF-containing fluoroplastics include, for example, DyneonT"' THVT"' 200, THVTM
400, THVTM
SOOG, THVT"' 610X fluoropolymers (available from Dyneon LLC, St. Paul, MN), KYNART"' 740 fluoropolymer (available from Atochem North America, Philadelphia, PA), HYLART"' 700 (available from Ausimont USA, Tnc., Morristown, NJ), and FLUORELT"' FC-2178 (available from Dyneon, LLC).
A particularly useful fluoropolymer includes interpolymerized units derived from at least TFE and VDF in which the amount of VDF is at least 0.1 % by weight, but less than 20% by weight. Preferably, the amount of VDF ranges from 3-15% by weight, more preferably from 10-15% by weight.
Examples of suitable fluoroelastomers include VDF-HFP copolymers, VDF-HFP-TFE
terpolymers, TFE-propylene copolymers, and the like.
The substrate may include an inorganic substrate, such as a metal or an inorganic glass, or an organic substrate, such as a fluoropolymer or a non-fluorinated polymer.
Alternatively, the substrate may be an organic-inorganic composite. The metal may be copper or stainless steel.
The inorganic glass may be a silicate. The non-fluorinated polymer may be a polyamide, a polyolefin, a polyurethane, a polyester, a polyimide, a polyimide, a polystyrene, a polycarbonate, a polyketone, a polyurea, a polyacrylate, and a polymethylmethacrylate, or a mixture thereof.
For example, the non-fluorinated polymer may be a non-fluorinated elastomer, such as acrylonitrile butadiene (NBR), butadiene rubber, chlorinated and chlorosulfonated polyethylene, chloroprene, ethylene-propylene monomer (EPM) rubber, ethylene-propylene-diene monomer (EPDM) rubber, epichlorohydrin (ECO) rubber, polyisobutylene, polyisoprene, polysulfide, polyurethane, silicone rubber, blends of polyvinyl chloride and NBR, styrene butadiene (SBR) rubber, ethylene-acrylate copolymer rubber, and ethylene-vinyl acetate rubber.
Suitable 7_ ethylene-vinyl acetate copolymers include ELVAXTM available from E.I DuPont de Nemours Co.,Wilmington, DE.
Polyamides useful as the non-fluorinated polymer are generally commercially available.
For example, polyamides such as any of the well-known nylons are available from a number of sources. Particularly preferred polyamides are nylon-6, nylon-6,6, nylon-1 l, and nylon-12. It should be noted that the selection of a particular polyamide material should be based upon the physical requirements of the particular application for the multi-layer article. For example, nylon-6 and nylon-6,6 offer better heat resistance properties than nylon-11 and nylon-12, whereas nylon-11 and nylon-12 offer better chemical resistance properties. In addition, other nylon materials such as nylon-6,12, nylon-6,9, nylon-4, nylon-4,2, nylon-4,6, nylon-7, and nylon-8 may be used, as well as ring-containing polyamides such as nylon-6,T
and nylon-6,1.
Suitable nylons include VESTAMIDTM L2140, a nylon-12 available from Creanova, Inc. of Somerset, NJ. Polyether-containing polyamides, such as PEBAXTM polyamides (Atochem North America, Philadelphia, PA), may also be used.
Useful polyurethane polymers include aliphatic, cycloaliphatic, aromatic, and polycyclic polyurethanes. These polyurethanes are typically produced by reaction of a polyfunctional isocyanate with a polyol according to well-known reaction mechanisms. Useful diisocyanates for employment in the production of a polyurethane include dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexyl diisocyanate, and diphenylmethane diisocyanate. Combinations of one or more polyfunctional isocyanates may also be used. Useful polyols include polypentyleneadipate glycol, polytetramethylene ether glycol, polyethylene glycol, polycaprolactone diol, poly-1,2-butylene oxide glycol, and combinations thereof. Chain extenders such as butanediol or hexandiol may also be used in the reaction. Useful commercially available urethane polymers include MORTHANETM L424.167 (MI=9.7), PN-04 or 3429 from Morton International, Seabrook, NH
and X-4107 from B.F. Goodrich Co., Cleveland, OH.
Useful polyolefin polymers include homopolymers of ethylene, propylene, and the like, as well as copolymers of these monomers with, for example, acrylic monomers and other ethylenically unsaturated monomers such as vinyl acetate and higher alpha-olefins. Such polymers and copolymers may be prepared by conventional free radical polymerization or catalysis of such ethylenically unsaturated monomers. The degree of crystallinity of the polymer may vary. The polymer may, for example, be a semi-crystalline high density polyethylene or _g_ may be an elastomeric copolymer of ethylene and propylene. Carboxyl, anhydride, or imide functionalities may be incorporated into the polymer by polymerizing or copolymerizing functional monomers such as acrylic acid or malefic anhydride, or by modifying the polymer after polymerization, e.g., by grafting, by oxidation, or by forming ionomers.
Examples include acid modified ethylene acrylate copolymers, anhydride modified ethylene vinyl acetate copolymers, anhydride modified polyethylene polymers, and anhydride modified polypropylene polymers. Such polymers and copolymers generally are commercially available, for example, as ENGAGETM (Dow-DuPont Elastomers, Wilmington, DE) or EXACTTM (ExxonMobil, Linden, NJ). For example, anhydride modified polyethylene polymers are commercially available from E.I. DuPont de Nemours & Co., Wilmington, DE, under the trade designation BYNELTM co-extrudable adhesive resins.
Useful polyacrylates and polymethacrylates include polymers of acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, and the like. An example of a polymethacrylate is EMACTM (Chevron Chemical Co., Houston, TX).
Useful polycarbonate polymers include aliphatic polycarbonates such as polyester carbonates, polyether carbonates, and bisphenol A-derived polycarbonates, and the like.
Useful polyimide polymers include polyimide polymers made from the anhydride of pyromellitic acid and 4,4'-diaminodiphenyl ether available from E.l. DuPont de Nemours and Company under the tradename KAPTONTM. Variations include KAPTONT"' H, KAPTONT"' E
and KAPTONTM V, among others.
Additional examples of useful non-fluorinated polymers, as noted above, include polyesters, polycarbonates, polyketones, and polyureas. Commercially available examples of such polymers include SELARTM polyester (E.I. DuPont de Nemours & Co., Wilmington, DE), LEXANTM polycarbonate (General Electric, Pittsfield, MA), KADELTM polyketone (Amoco, Chicago, IL), and SPECTRIMTM polyurea (Dow Chemical Co., Midland, MI).
Commercially available elastomers include NIPOLTM 1052 NBR (Zeon Chemical, Louisville, KY), HYDRINTM C2000 epichlorohydrin-ethylene oxide rubber (Zeon Chemical, Louisville, KY), HYPALONTM 48 chlorosulfonated polyethylene rubber (E.I.
DuPont de Nemours & Co., Wilmington, DE), NORDELTM EPDM (R.T. Vanderbilt Co., Inc., Norwalk, CT), VAMACTM ethylene-acrylate elastomer (E.I. DuPont de Nemours & Co.
Wilmington, DE), KRYNACTM NBR (Bayer Corp., Pittsburgh, PA), PERBUNANTM NBR/PVC blend (Bayer Corp., Pittsburgh, PA), THERBANTM hydrogenated NBR (Bayer Corp., Pittsburgh, PA), ZETPOLTM hydrogenated NBR (Zeon Chemical, Louisville, KY), SANTOPRENETM
thermoplastic elastomer (Advanced Elastomer Systems, Akron, OH), and KELTAN'~M
EPDM
(DSM Elastomers Americas, Addis, LA).
The substrate may include a second fluoropolymer.
The substrate may have one or more surface polar functionality present thereon to enhance bonding, such as, for example, an amino, carboxyl and hydroxyl functionality.
The bonding composition may be deposited on a surface of the fluoropolymer, the substrate or both. In certain embodiments, the bonding composition may be incorporated into the fluoropolymer, the substrate, or both, such that when the surfaces contact each other, the bonding composition contacts the fluoropolymer and the substrate simultaneously. The bonding composition may be incorporated into the fluoropolymer or the substrate by melt mixing or extruding a mixture including the bonding composition. Alternatively, the bonding composition may be applied to a surface of the fluoropolymer or substrate by a process such as, for example, spray coating, curtain coating, immersion coating, dip coating, flood coating, and the like.
The fluoropolymer and substrate may contact each other under pressure, with optional heating, to form a precursor that is subsequently exposed to actinic radiation. In certain situations, more than one fluoropolymer layer may contact more than one surface of the substrate. In still other situations, two substrates may contact two surfaces of a fluoropolymer.
Each of the fluoropolymer and the substrate, independently, may be provided as a film or as a molded or shaped article. Preferably either the fluoropolymer or the substrate is substantially transmissive to the actinic radiation.
The fluoropolymer is bonded to the substrate by exposing the bonding composition to actinic radiation. The bonding composition may be exposed to actinic radiation through the fluoropolymer, through the substrate, or both. In certain situations, the exposure to actinic radiation may be before the substrate contacts the fluoropolymer. In other situations, the exposure to actinic radiation may occur after the substrate and fluoropolymer contact each other.
In still other situations, exposure to actinic radiation occurs simultaneously upon contacting the substrate and the fluoropolymer.
Suitable sources of actinic radiation include arc lamps, such as xenon-arc lamps, mercury arc lamps (including low and medium pressure mercury arc lamps), fluorescent blacklights, microwave-driven lamps, such as those sold by Fusion UV Systems of Rockville, MD
(including H-type and D-type bulbs), lasers and the like. Lamps that emit enriched amounts of ultraviolet or blue light, such as, for example, low pressure mercury (e.g., germicidal) lamps, are preferred.
In many cases, heat, pressure, or combinations thereof, may be desired during bonding.
Suitable heat sources include, but are not limited to, ovens, heated rollers, heated presses, infrared radiation sources, flame, and the like. Suitable pressure sources are well known and include presses, nip rollers, and the like.
The invention will now be described further by way of the following examples.
EXAMPLES
In the following examples, the term "wt%" means weight percent based on total weight.
"THVTM 500" refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 165°C; "THVT"' 400" refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 150°C; "THVT"' 200" refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 120°C; "FEP" refers to FEP X6307 which is a copolymer of tetrafluorethylene and hexafluoropropylene, 85/15 by weight; "HTE" is a terpolymer of hexafluoropropylene, teterafluoroethylene and ethylene, all available from Dyneon, L.L.C. of Oakdale, MN.
"PVDF-HV" refers to "PVDF 11010" which is a tradename for a copolymer of hexafluoropropylene and vinylidene fluoride having a melting point of 160°C; "PVDF-CV"
refers to SOLEFT"' PVDF-CV which is a copolymer of chlorotrifluoroethylene and vinylidene fluoride, both commercially available from Soltex Polymer Corp. of Houston, TX.
"BYNELTM 3101" is an acid modified ethylene-vinyl acetate copolymer; "ELVAXTM
450" is an ethylene-vinyl acetate copolymer havingl8 wt% vinyl acetate and a Vicat softening temperature of 61°C; "polyimide" refers to KaptonTM 100HN film, all commercially available from E.I. du Pont de Nemours of Wilmington DE.
"EMACTM 2202T" is a copolymer of ethylene and methyl acrylate, 80/20 by weight available from Chevron Chemical Co. of Houston, TX.
"MORTHANETM L424.167 (MI=9.7)" is an aliphatic polyurethane available from Morton, International of Chicago, IL.
"VESTAMID~rM L2140" refers to nylon 12 having a Vicat softening point of 140°C
commercially available from Creanova, Inc. of Somerset, NJ.
"Copper-coated polyimide" refers to KaptonT"' 100HN film that has been metallized with copper. "Gold-coated polyimide" refers to KaptonTM 100HN film that has been metallized with gold.
"Polycarbonate film" refers to polyethylene terephthalate film of about 10 mils (0.25 mm) thickness.
Unless otherwise specified, additional materials used in the examples were readily available from general commercial vendors such Sigma-Aldrich Chemical Co. of Milwaukee, WI.
Example 1 Polymer films (i.e., substrates) were prepared by placing polymer granules indicated in Tables 1A and 1B were placed between two sheets of polytetrafluoroethylene having a thickness of 0.38 mm and softening them for 2-3 minutes at 200°C. Subsequently, the softened materials were pressed for about 5 to 10 seconds between two heated platens of a Wabash hydraulic press (Wabash Metal Products Company, Inc., Hydraulic Division, Wabash, IN) and immediately transferred to a cold Wabash hydraulic press at 13-15°C and 2-4 psi (0.014 - 0.028 MPas). After cooling to room temperature in the cold press, round-shaped films of polymer having a thickness of 1.5 mm were obtained. Small pieces of the pressed films were then placed between two stainless steel plates lined with polyethylene terephthalate-silicone coated release liners and pressed for 2-3 minutes at 200°C with pressure and applied between two heated platens of a Wabash hydraulic press. The films produced in this manner were thin smooth films of 0.08 to 0.15 mm in thickness. The substrate films thus prepared were cut to dimensions of approximately 2.5 cm by 5 cm for use in lamination.
Two bonding compositions were prepared. Bonding composition (BC 1) was prepared by mixing 0.2 g allylamine and 0.1 g benzyltriphenylphosphonium chloride in 2 g methanol. A
second bonding composition (BC 2) was prepared by mixing 0.2 g allylamine and 0.1 g triphenylphosphine in 2 g methanol. All the above chemicals were available from Sigma-Aldrich Chemical Co., Milwaukee, WI.
The cut film was flood-coated with the bonding composition. It was not necessary to dry the bonding composition before forming the bond. Samples were prepared by contacting a fluoropolymer film surface with the bonding composition-coated substrate surface to form a laminate precursor. Comparative samples were prepared by omitting the bonding composition.
The laminate precursor was then placed vertically in the center of a 254 nm photoreactor (Rayonet chamber reactor, model RPR-100 equipped with sixteen low pressure mercury bulbs available from The Southern New England Ultraviolet, Inc. of New Haven, CT.
These samples were irradiated for periods of time indicated in Tables 1 A and 1 B.
After irradiation samples were subjected to hot lamination onto thicker films (1-1.5 mm) of their respective materials for 2 minutes at 200°C in order to obtain accurate adhesion measurement because the irradiated samples were too thin and film stretching/rupturing would be expected during the measurement.
Peel strength was used to determine the degree of bonding. Peel strength was determined in accordance with ASTM D-1876 (T peel test). An InstronT"' model 1125 tester, available from Instron Corp., Canton, MA set at a 4 inch (10.2 cm) per minute crosshead speed was used as the test device. The peel strength was calculated as the average load measured during the peel test. The measured peel strength is shown in Tables 1 A and I
B. Comparative experiments showed that no adhesion between substrates and fluoropolymer films was observed prior to irradiation with the bonding composition present.
Example 2 Glass microscope slides and stainless steel panels (1 inch (2.54 cm) by 2 inch (5.08 cm) pieces were cleaned with acetone. A surface of the glass or steel substrate was coated with a bonding composition, and a piece of fluoropolymer film was subsequently laminated onto the coated substrate in a good surface contact. A strip of silicone liner was inserted along the short edge between the substrate surface and the fluoropolymer film to provide tabs for the peel test.
The laminated sample was positioned vertically in the center of a 254 nm photoreactor as described in Example 1 and irradiated for a period of time as shown in Tables IA and 1B. The measured peel strength is shown in Tables 1 A and 1 B.
Example 3 Instead of fluoropolymer film, a solution of 25% fluoroelastomer FLUORELT~' FC-2145, a raw gum dipolymer of VDF and HFP, (available from Dyneon, LLC) in methanol was coated onto the side of a glass slide having the bonding composition. The fluoroelastomer-coated glass was then subjected to irradiation at 254 nm in a photoreactor as described in Example 1 for a period of time as shown in Tables 1A and 1B. Adhesion between the fluoroelastomer and glass was found.
Table 1A
Laminate Comparative BC 1 BC 2 BC 3 Adhesion Irrad. Adhesion brad. Adhesion brad. Adhesion time time Time (N/cm) (min) (N/cm) (min) (N/cm) (min) (N/cm) ELVAXTM 0 10 18.9 10 25.3 20 4.9 ELVAXTM 0 5 19.0 ELVAXTM 0 45 14.4 B YNEL~ 0 10 14 10 13 BYNELTM 0 5 14.4 VT"'S00 BYNELT"'~ 0 45 17 VT"'200 EMACTM 0 10 17 10 25.2 2220/THVTM400 15 6.7 EMACTM 0 5 19.8 EMAC~ 0 45 5.8 EMACTM 0 45 5.8 VESTAMIDTM 0 15 24.3 15 19.0 MORTI-IANETM0 15 8.8 15 20.4 L424.167, MI=9.7/THVTM40 ENGAGETM 0 20 5.1 20 0 ENGAGETM 0 20 33.1 EXACTT"'i 0 20 10 EXACTT"'' 0 20 4.4 Polyester/THV400 0 30 3.2 TABLE
Laminate Comparative BC 1 BC 2 Adhesion Irrad.AdhesionIrrad.Adhesion time time (N/cm) (min)(N/cm) (min)(N/cm) ELVA 0.4 15 24.7 15 18.6 ELVAXTM 0.4 10 19.2 ELVAXTM 0.4 5 2.8 BYNEL~ 1 15 19.7 15 36.0 BYNEL~ 1 15 6.7 10 26.6 EMAC~ 0 15 23.2 15 26.6 V DF
EMACTM 0 10 17.8 EMACTM 0 5 9.0 HV
BYNEL~ 0 20 28.0 3101/SOLEFTm HV
EMACTM 0 20 25.4 2220/SOLEF~
HV
BYNEL~ 0 20 21.2 3101/SOLEFTm CV
EMACT"' 0 20 26.1 2220/SOLEF~' CV
Glass/THVTM4000 45 Good 45 Good Steel/THVT"'4000 45 Good 45 Good Glass/FluorelT"'0 45 Good Examule 4 The procedure of Example 1 was followed using the bonding composition (BC) and comparative compositions (COMP) listed in Tables 2A and 2B, except that cut fluoropolymer film was coated with the bonding composition or comparative compositions.
Subsequently, a second fluoropolymer film was placed on the bonding composition to form a laminate precursor.
The precursor was then placed vertically in the center of a 254 nm photoreactor (Rayonet -IS-chamber reactor, model RPR-100 equipped with sixteen low pressure mercury bulbs. Samples were irradiated for periods of time indicated in Tables 3A-4. After irradiation, the two pieces of fluoropolymer films were peeled apart and individually laminated to bonding substrates to form the final multiplayer articles. A strip of a silicon liner was inserted about 0.6 cm into the space between the layers along the short edge for peel testing. The article was hot pressed at 200°C
for 2 minutes and immediately transferred to a cold Wabash hydraulic press 13-I S°C. After cooling to room temperature in the cold press, the sample was ready for peel testing.
Composition Ingredients BC4 Diphenyliodonium chloride (0.02g) + allylamine (0.2g) +
acetonitrile (2.g) COMP4 Diphenyliodonium chloride saturated in acetonitrile (2.0g) (comparative) BCS Tetraphenylarsonium chloride (0.03g) + allylamine (0.2g) +
acetonitrile (2.0g) COMPS Tetraphenylarsonium chloride (0.03g) +
acetonitrile (2.0g) (comparative) BC6 Tetraphenylarsonium chloride (O.OSg) +
ethylenediamine (0.2g) + acetonitrile (2.0g) COMP6 Tetraphenylarsonium chloride (O.OSg) +
acetonitrile (2.0g) (comparative) BC7 Triphenylsulfonium chloride (O.OSg) + allylamine (0.2g) +
acetonitrile (2.0g) COMP7 Triphenylsulfonium chloride (O.OSg) + acetonitrile (2.0g) (comparative) BC8 Triphenylsulfonium chloride (O.OSg) + n-butylamine (0.2g) +
acetonitrile (2.0g) BC9 Triphenylsulfonium chloride (O.OSg) + diallylamine (0.2g) +
acetonitrile (2.0g) BC10 Phenyltrimethylammonium chloride(saturated) + allylamine (0.2g) + acetonitrile (2.0g) COMP10 Phenyltrimethylammonium chloride(saturated) +
(comparative)acetonitrile(2.Og) BC 11 Tetraphenylphosphonium chloride (0.1 g) + allylamine (0.2g) +
acetonitrile (2.0g) COMP11 Tetraphenylphosphonium chloride (0.1g) + acetonitrile (2.0g) (comparative) BC12 Tetrabutylphosphonium chloride (0.1g) + allylamine (0.2g) +
acetonitrile (2.0g) COMP12 Tetrabutylphosphonium chloride (0.1g) + acetonitrile (2.0g) (comparative) BC 13 biphenyl sulfide (0.1 g) + allylamine (0.2g) in + acetonitrile (2.0g) COMP13 biphenyl sulfide (0.1 g) + acetonitrile (2.0g) (comparative) Composition Ingredients BC14 biphenyl sulfone (0.1g) + allylamine (0.2g) + acetonitrile (2.0g) COMP14 (comparative)biphenyl sulfone (0.1g) + acetonitrile (2.0g) BC 15 Anisole (0.1 g) + allylamine (0.2g) + acetonitrile (2.0g) COMP15 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC 16 Biphenyl (0.1 g) + allylamine (0.2g) +acetonitrile (2.0) COMP16 (comparative)Biphenyl (0.1g) + acetonitrile (2.0g) BC 17 4, 4'-dihydroxybiphenyl (0.1g) + allylamine (0.2g) + acetonitrile (2.0g) COMP17 (comparative)4, 4'-dihydroxybiphenyl (0.1g) + acetonitrile (2.0g) BC 18 biphenyl ether (0.1 g) + allylamine (0.2g) + acetonitrile (2.0g) COMP18 (comparative)biphenyl ether (0.1g) + acetonitrile (2.0g) BC 19 Anisole (0.1 g) + aniline (0.2g) + acetonitrile (2.0g) COMP19 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC20 Chlorobenzene (0.1 g) + allylamine (0.2g) + acetonitrile (2.0g) COMP20 (comparative)Chlorobenzene (0.1 g) + acetonitrile (2.0g) BC21 Biphenyl (0.1 g) + n-butylamine (0.2g) + acetonitrile (2.0g) COMP21 (comparative)Biphenyl (0.1 g) + acetonitrile (2.0g) BC22 Pyrene (0.1 g) + n-butylamine (0.2g) + acetonitrile (2.0g) COMP22 (comparative)Pyrene (0.1 g) + acetonitrile (2.0g) BC23 Anisole (0.1g) + 3-aminopropyltriethoxysilane (0.2g) + acetonitrile (2.0g) COMP23 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC24 biphenyl sulfide (0.1 g) + 3-aminopropyltriethoxysilane (0.2g) + acetonitrile (2.0g) COMP24 (comparative)biphenyl sulfide (0.1 g) + acetonitrile (2.0g) BC25 Anisole (0.1g) + 3-aminopropyltriethoxysilane (0.2g) + acetonitrile (2.0g) COMP25 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC26 Anisole (0.1g) + ethylenediamine (0.2g) +
acetonitrile (2.0g) BC27 Anisole (0.1g) + aminoethanol (0.2g) + acetonitrile (2.0g) COMP27 (comparative)Anisole (0.1 g) + acetonitrile (2.0g) BC28 Tetraphenylarsonium chloride (O.OSg) + allylamine (0.2g) + acetonitrile (2.0g) Sample BC Irradiation Peel Strength time at 254 nm (N/cm) (min) FEP/VESTAMIDT"'BC4 10 15.84 FEP/VESTAMIDT"'COMP4 10 0 FEPNESTAMIDT"'BC5 10 14.08 FEP/BYNELT"' BC5 10 21.12 FEPBYNELT"' COMPS 10 0 FEPNESTAMIDT~'BC6 5 14.08 FEPBYNELT"' BC6 5 8.8 FEP/VESTAMIDT"~COMP6 5 0 FEPBYNELT"' COMP6 5 0 FEPNESTAMIDTM BC7 5 cohesive FEP
L2140 failure FEPBYNELT"' BC7 5 5.28 FEP/VESTAMIDT"~COMP? 5 0 FEPBYNELT"' COMP7 5 0 PEP/VESTAMIDT"'BC8 10 8.8 FEPBYNELT"~ BC8 10 11.44 FEP/VESTAMIDT"'BC9 10 cohesive FEP
L2140 failure FEPBYNELT"' BC9 10 cohesive failure FEP/VES1'AMIDTMBC10 15 cohesive FEP
L2140 failure FEPBYNELT"' BC10 15 10.56 FEP/VESTAMIDT"'COMP10 15 0 FEPBYNELT"' COMP10 15 0 FEPNESTAMIDT"'BC11 5 cohesive FEP
L2140 failure FEPBYNELT"' BC11 5 14.08 FEP/VESTAMIDT"'COMP11 5 0 FEPBYNELT"' COMP11 5 0 FEPNESTAMIDT"'BC12 10 cohesive FEP
L2140 failure FEP/BYNELT"' BC12 10 8.8 FEPBYNELT"' COMP12 10 0 Sample BC Irradiation Peel Strength time at 254 nm (N/cm) (min) FEP/VESTAMID BC13 5 >22.8 FEP/BYNELTM 3101BC13 5 15.8 FEP/VESTAMIDTM BC14 5 >12.3 FEP/BYNELTM 3101BC14 5 12.3 FEP/VESTAMIDTM BC15 5 6.1 FEP/BYNELTM 3101BC15 S 7.0 FEP/VESTAMIDTM BC16 5 >22.8 FEP/BYNELTM 3101BC16 5 12.3 FEP/VESTAMIDTM BC 17 5 > 19.3 FEP/BYNELT"' BC 17 5 7.9 FEP/VESTAMIDT"' COMP17 5 1.8 FEP/VESTAMIDTM BC 18 5 7.9 FEP/BYNELTM 3101BC18 5 9.7 FEP/VESTAMIDTM BC19 5 24.6 FEP/BYNELT"' BC 19 5 8.8 FEP/VESTAMIDTM BC20 5 >22.8 FEP/BYNELTM 3101BC20 5 12.3 Sample BC Irradiation Peel Strength time at 254 nm (N/cm) (min) FEP/VESTAMID BC21 5 8.8 "' FEP/BYNELTM BC21 S 30.7 FEP/VESTAMIDTMBC22 5 >22.8 FEP/BYNELTM BC22 5 12.3 FEP/VESTAMIDTMBC23 10 26.3 FEPBYNELTM BC23 10 30.7 FEPBYNELT"' COMP23 5 0 FEP/VESTAMIDTMBC24 5 17.5 FEPBYNELTM BC24 5 29.8 FEP/VESTAMIDTMBC25 5 14.9 FEP/BYNELTM BC25 5 13.2 FEP/VES1'AMIDTMCOMP25 5 0 PEP/VESTAMIDTMBC26 5 7.0 FEP/BYNELTM BC26 5 33.3 FEP/EXACT'T" BC27 10 6.1 FEP/ VESTAMIDTMBC28 5 > 15.8 Example 5 This comparative example shows that electron donors are not effective at promoting bonding according to the invention. Table 4 shows the bonding results obtained when electron donors were used as a 10 weight percent solution in methanol according to the procedure of Example 1.
Sample Electron Donor IrradiationPeel (N/cm) as a 10 wt% in Time at Methanol nm (min) FEP/VESTAMIAllylamine 5 0 DT~' L2140 FEP/Byne13101Allylamine 5 0 FEP/VESTAMIn-butylamine 5 0 FEP/Byne13101n-butylamine 5 0 FEP/VESTAMI3-aminopropyl- 5 0 DTM L2140 triethoxysilane FEP/Byne131013-aminopropyl- 5 <1.75 triethoxysilane FEP/VESTAMI2-aminoethanol 5 <1.75 DT"' L2140 FEP/Byne131012-aminoethanol 5 <I .75 FEP/VESTAMI1,2-ethylenediamine5 <1.75 FEP/Byne131011,2-ethylenediamine5 <1.75 Other embodiments are within the scope of the following claims.
DESCRIPTION OF DRAWINGS
FIG. 1 is a cross-sectional view of a multi-layer article.
DETAILED DESCRIPTION
A fluoropolymer layer may be bonded on one surface of a substrate to form, for example, a laminate. The laminate may contain two or more layers. Referring to Fig. 1, the laminate 10 includes fluoropolymer layer 20 and the substrate 30. Bonding composition 40 contacts the interface between fluoropolymer layer 20 and substrate 30. Actinic radiation applied to the bonding composition promotes bonding between fluoropolymer layer 20 and substrate 30.
The bonding composition includes a light-absorbing compound and an electron donor.
The bonding composition may include a solvent to facilitate applying a coating of the composition to a surface of the fluoropolymers or the substrate, or both. The solvent may be removed, for example, by drying, prior to contacting the substrate and fluoropolymers surfaces.
Any solvent, if used may be a fluorinated solvent, for example, a fluorinated solvent having at least one fluorinated moiety. Fluorinated solvents may be effective at promoting wetting of the bonding composition onto either substrate. Preferred fluorinated solvents include, for example, hexafluoroxylene, hexafluorobenzene, and the like.
Actinic radiation is electromagnetic radiation having a wavelength capable of affecting bonding between the fluoropolymer and the substrate in the presence of the bonding composition. The actinic radiation has an intensity at a wavelength capable of affecting bonding within a reasonable amount of time. The actinic radiation may have a wavelength between 190 nm and 700 nm, preferably between 200 nm and 400 nm, more preferably between 205 nm and 320 nm, even more preferably between 210 nm and 290 nm, and even more preferably between 240 nm and 260 nm.
The actinic radiation has a wavelength that is absorbed by the light-absorbing compound.
The light-absorbing compound may have an absorbing moiety capable of being excited by the actinic radiation, such as, for example, a benzyl moiety or other aromatic moiety. The light-absorbing compound may be an ammonium compound, a phosphine, a phosphonium compound, an aromatic hydrocarbon compound, a thioether compound, an ether compound, a phenolic compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, or combinations thereof. Specific examples include triphenylphosphine, benzyltriphenylphosphonium chloride, benzyltributylammonium chloride, an arylammonium salt, tetraphenylarsonium chloride, diphenyl sulfide, biphenyl, 4,4'-dihydroxybiphenyl and triarylsulfonium chloride. Other examples of light-absorbing compounds are described, e.g., in Fukushi, U.S. Patent No. 5,658,671, "Fluoroelastomer Coating Composition,"
hereby incorporated by reference. The light-absorbing compound may have a molar absorptivity of at least 100, preferably at least 500, more preferably at least 1,500, even more preferably at least 5,000 at a wavelength when exposed to actinic radiation. In some embodiments, the light-absorbing compound may include individual components that do not significantly absorb actinic radiation in a purified state, but absorbs light when the components are combined. For example, a component of the composite may form a charge-transfer complex with the donor, fluoropolymer, substrate or other added ingredient, resulting in a compound that absorbs actinic radiation.
The electron donor is a compound capable of reducing the excited state of the light-absorbing compound. For example, the electron donor may be an amine, a phosphine, a thiol, a thioether, phenol, thiophenol, phenolate, thiophenolate or combinations thereof. The amine may be a primary amine, such as an alkylamine, e.g., a monoalkylamine, a dialkylamine, or a trialkylamine, such as a fluoroalkylamine. The electron donor may be polymerizable, for example, a polymerizable amine such as an aminoalkene or a vinylaniline. The amine may be an amino-substituted organosilane. The amino-substituted organosilane may have a hydrolyzable substituent; for example, it may be a trialkoxysilane. For example, the amino-substituted organosilane may have the formula R' RZN-L-S iXX'X"
where each of R' and Rz, independently, is H, C1-12 alkyl, C1-12 alkenyl, C1-12 alkynyl, or aryl, and L is a divalent straight chain Cl-12 alkylene, C3-8 cycloalkylene, 3-8 membered ring heterocycloalkylene, C1-12 alkenylene, C3-8 cycloalkenylene, 3-8 membered ring heterocycloalkenylene, arylene, or heteroarylene. L is optionally substituted with C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, C1-4 alkoxy, hydroxyl, halo, carboxyl, amino, nitro, cyano, C3-6 cycloalkyl, 3-6 membered heterocycloalkyl, aryl, 5-6 membered ring heteroaryl, alkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4 alkylcarbonyl, formyl, C1-4 alkylcarbonylamino, or C1-4 aminocarbonyl. L is further optionally interrupted by -O-, -S-, -N(Rc)-, -N(Rc)-C(O)-, -N(Rc)-C(O)-O-, -O-C(O)-N(Rc)-, -N(Rc)-C(O)-N(Rd)-, -O-C(O)-, -C(O)-O-, or -O-C(O)-O-. Each of Rc and Rd, independently, is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxylalkyl, hydroxyl, or haloalkyl. Each of X, X' and X"
is a C1-18 alkyl, halogen, C1-8 alkoxy, C1-8 alkylcarbonyloxy, or amino group. When the amino-substituted organosilane has a hydrolyzable substituent, at least one of X, X', and X" is not alkyl. Further, any two of X, X' and X" may be joined through a covalent bond. The amino group may be an alkylamino group.
The bonding composition may include other additives, for example, a vinylsilane, such as an alkoxyvinylsilane, polyhydroxy aromatic compounds, or a thermosetting resin such as an epoxy resin, a urethane resin, a urea resin, or an acrylate resin.
The fluoropolymer may be a perfluorinated polymer or a partially fluorinated polymer.
For example, the fluoropolymer may be either melt-processible such as in the case of a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THVT"'), a tetrafluoroethylene-hexafluoropropene copolymer (FEP), and other melt-processible fluoroplastics, or may be non-melt processable such as in the case of polytetrafluoroethylene (PTFE), modified PTFE copolymers, such as a copolymer of TFE and low levels of fluorinated vinyl ethers and fluoroelastomers. Fluoroelastomers may be processed before they are cured by injection or compression molding or other methods normally associated with thermoplastics.
Fluoroelastomers after curing or crosslinking may not be not able to be further processed.
Fluoroelastomers may also be coated out of solvent in their uncross linked form.
Fluoropolymers may also be coated from an aqueous dispersion form. In preferred embodiments, the fluoropolymer may be FEP, a tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (PFA), perfluoroelastomer, or mixtures thereof.
Preferably, the fluoropolymer is a material that is capable of being extruded or solvent coated. Such fluoropolymers typically are fluoroplastics that have melting temperatures ranging from about 100 to about 330°C, more preferably from about 150 to about 270°C. Preferred fluoroplastics include interpolymerized units derived from VDF and fluoroethylene and may further include interpolymerized units derived from other fluorine-containing monomers, non-fluorine-containing monomers, or a combination thereof.
Examples of suitable fluorine-containing monomers include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), 3-chloropentafluoropropene, perfluorinated vinyl ethers (e.g., perfluoroalkoxy vinyl ethers such as CF30CFzCF2CF20CF=CFZ and perfluoroalkyl vinyl ethers such as CF30CF=CFZ and CF3CFZCFZOCF=CFZ), and fluorine-containing di-olefins such as perfluorodiallyl ether and perfluoro-1,3-butadiene. Examples of suitable non-fluorine-containing monomers include olefin monomers such as ethylene, propylene, and the like.
The VDF-containing fluoropolymer may be prepared using emulsion polymerization techniques as described, e.g., in Sulzbach et al., U.S. Patent No. 4,338,237 or Grootaert, U.S.
Patent No. 5,285,002, hereby incorporated by reference. Useful commercially available VDF-containing fluoroplastics include, for example, DyneonT"' THVT"' 200, THVTM
400, THVTM
SOOG, THVT"' 610X fluoropolymers (available from Dyneon LLC, St. Paul, MN), KYNART"' 740 fluoropolymer (available from Atochem North America, Philadelphia, PA), HYLART"' 700 (available from Ausimont USA, Tnc., Morristown, NJ), and FLUORELT"' FC-2178 (available from Dyneon, LLC).
A particularly useful fluoropolymer includes interpolymerized units derived from at least TFE and VDF in which the amount of VDF is at least 0.1 % by weight, but less than 20% by weight. Preferably, the amount of VDF ranges from 3-15% by weight, more preferably from 10-15% by weight.
Examples of suitable fluoroelastomers include VDF-HFP copolymers, VDF-HFP-TFE
terpolymers, TFE-propylene copolymers, and the like.
The substrate may include an inorganic substrate, such as a metal or an inorganic glass, or an organic substrate, such as a fluoropolymer or a non-fluorinated polymer.
Alternatively, the substrate may be an organic-inorganic composite. The metal may be copper or stainless steel.
The inorganic glass may be a silicate. The non-fluorinated polymer may be a polyamide, a polyolefin, a polyurethane, a polyester, a polyimide, a polyimide, a polystyrene, a polycarbonate, a polyketone, a polyurea, a polyacrylate, and a polymethylmethacrylate, or a mixture thereof.
For example, the non-fluorinated polymer may be a non-fluorinated elastomer, such as acrylonitrile butadiene (NBR), butadiene rubber, chlorinated and chlorosulfonated polyethylene, chloroprene, ethylene-propylene monomer (EPM) rubber, ethylene-propylene-diene monomer (EPDM) rubber, epichlorohydrin (ECO) rubber, polyisobutylene, polyisoprene, polysulfide, polyurethane, silicone rubber, blends of polyvinyl chloride and NBR, styrene butadiene (SBR) rubber, ethylene-acrylate copolymer rubber, and ethylene-vinyl acetate rubber.
Suitable 7_ ethylene-vinyl acetate copolymers include ELVAXTM available from E.I DuPont de Nemours Co.,Wilmington, DE.
Polyamides useful as the non-fluorinated polymer are generally commercially available.
For example, polyamides such as any of the well-known nylons are available from a number of sources. Particularly preferred polyamides are nylon-6, nylon-6,6, nylon-1 l, and nylon-12. It should be noted that the selection of a particular polyamide material should be based upon the physical requirements of the particular application for the multi-layer article. For example, nylon-6 and nylon-6,6 offer better heat resistance properties than nylon-11 and nylon-12, whereas nylon-11 and nylon-12 offer better chemical resistance properties. In addition, other nylon materials such as nylon-6,12, nylon-6,9, nylon-4, nylon-4,2, nylon-4,6, nylon-7, and nylon-8 may be used, as well as ring-containing polyamides such as nylon-6,T
and nylon-6,1.
Suitable nylons include VESTAMIDTM L2140, a nylon-12 available from Creanova, Inc. of Somerset, NJ. Polyether-containing polyamides, such as PEBAXTM polyamides (Atochem North America, Philadelphia, PA), may also be used.
Useful polyurethane polymers include aliphatic, cycloaliphatic, aromatic, and polycyclic polyurethanes. These polyurethanes are typically produced by reaction of a polyfunctional isocyanate with a polyol according to well-known reaction mechanisms. Useful diisocyanates for employment in the production of a polyurethane include dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexyl diisocyanate, and diphenylmethane diisocyanate. Combinations of one or more polyfunctional isocyanates may also be used. Useful polyols include polypentyleneadipate glycol, polytetramethylene ether glycol, polyethylene glycol, polycaprolactone diol, poly-1,2-butylene oxide glycol, and combinations thereof. Chain extenders such as butanediol or hexandiol may also be used in the reaction. Useful commercially available urethane polymers include MORTHANETM L424.167 (MI=9.7), PN-04 or 3429 from Morton International, Seabrook, NH
and X-4107 from B.F. Goodrich Co., Cleveland, OH.
Useful polyolefin polymers include homopolymers of ethylene, propylene, and the like, as well as copolymers of these monomers with, for example, acrylic monomers and other ethylenically unsaturated monomers such as vinyl acetate and higher alpha-olefins. Such polymers and copolymers may be prepared by conventional free radical polymerization or catalysis of such ethylenically unsaturated monomers. The degree of crystallinity of the polymer may vary. The polymer may, for example, be a semi-crystalline high density polyethylene or _g_ may be an elastomeric copolymer of ethylene and propylene. Carboxyl, anhydride, or imide functionalities may be incorporated into the polymer by polymerizing or copolymerizing functional monomers such as acrylic acid or malefic anhydride, or by modifying the polymer after polymerization, e.g., by grafting, by oxidation, or by forming ionomers.
Examples include acid modified ethylene acrylate copolymers, anhydride modified ethylene vinyl acetate copolymers, anhydride modified polyethylene polymers, and anhydride modified polypropylene polymers. Such polymers and copolymers generally are commercially available, for example, as ENGAGETM (Dow-DuPont Elastomers, Wilmington, DE) or EXACTTM (ExxonMobil, Linden, NJ). For example, anhydride modified polyethylene polymers are commercially available from E.I. DuPont de Nemours & Co., Wilmington, DE, under the trade designation BYNELTM co-extrudable adhesive resins.
Useful polyacrylates and polymethacrylates include polymers of acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, and the like. An example of a polymethacrylate is EMACTM (Chevron Chemical Co., Houston, TX).
Useful polycarbonate polymers include aliphatic polycarbonates such as polyester carbonates, polyether carbonates, and bisphenol A-derived polycarbonates, and the like.
Useful polyimide polymers include polyimide polymers made from the anhydride of pyromellitic acid and 4,4'-diaminodiphenyl ether available from E.l. DuPont de Nemours and Company under the tradename KAPTONTM. Variations include KAPTONT"' H, KAPTONT"' E
and KAPTONTM V, among others.
Additional examples of useful non-fluorinated polymers, as noted above, include polyesters, polycarbonates, polyketones, and polyureas. Commercially available examples of such polymers include SELARTM polyester (E.I. DuPont de Nemours & Co., Wilmington, DE), LEXANTM polycarbonate (General Electric, Pittsfield, MA), KADELTM polyketone (Amoco, Chicago, IL), and SPECTRIMTM polyurea (Dow Chemical Co., Midland, MI).
Commercially available elastomers include NIPOLTM 1052 NBR (Zeon Chemical, Louisville, KY), HYDRINTM C2000 epichlorohydrin-ethylene oxide rubber (Zeon Chemical, Louisville, KY), HYPALONTM 48 chlorosulfonated polyethylene rubber (E.I.
DuPont de Nemours & Co., Wilmington, DE), NORDELTM EPDM (R.T. Vanderbilt Co., Inc., Norwalk, CT), VAMACTM ethylene-acrylate elastomer (E.I. DuPont de Nemours & Co.
Wilmington, DE), KRYNACTM NBR (Bayer Corp., Pittsburgh, PA), PERBUNANTM NBR/PVC blend (Bayer Corp., Pittsburgh, PA), THERBANTM hydrogenated NBR (Bayer Corp., Pittsburgh, PA), ZETPOLTM hydrogenated NBR (Zeon Chemical, Louisville, KY), SANTOPRENETM
thermoplastic elastomer (Advanced Elastomer Systems, Akron, OH), and KELTAN'~M
EPDM
(DSM Elastomers Americas, Addis, LA).
The substrate may include a second fluoropolymer.
The substrate may have one or more surface polar functionality present thereon to enhance bonding, such as, for example, an amino, carboxyl and hydroxyl functionality.
The bonding composition may be deposited on a surface of the fluoropolymer, the substrate or both. In certain embodiments, the bonding composition may be incorporated into the fluoropolymer, the substrate, or both, such that when the surfaces contact each other, the bonding composition contacts the fluoropolymer and the substrate simultaneously. The bonding composition may be incorporated into the fluoropolymer or the substrate by melt mixing or extruding a mixture including the bonding composition. Alternatively, the bonding composition may be applied to a surface of the fluoropolymer or substrate by a process such as, for example, spray coating, curtain coating, immersion coating, dip coating, flood coating, and the like.
The fluoropolymer and substrate may contact each other under pressure, with optional heating, to form a precursor that is subsequently exposed to actinic radiation. In certain situations, more than one fluoropolymer layer may contact more than one surface of the substrate. In still other situations, two substrates may contact two surfaces of a fluoropolymer.
Each of the fluoropolymer and the substrate, independently, may be provided as a film or as a molded or shaped article. Preferably either the fluoropolymer or the substrate is substantially transmissive to the actinic radiation.
The fluoropolymer is bonded to the substrate by exposing the bonding composition to actinic radiation. The bonding composition may be exposed to actinic radiation through the fluoropolymer, through the substrate, or both. In certain situations, the exposure to actinic radiation may be before the substrate contacts the fluoropolymer. In other situations, the exposure to actinic radiation may occur after the substrate and fluoropolymer contact each other.
In still other situations, exposure to actinic radiation occurs simultaneously upon contacting the substrate and the fluoropolymer.
Suitable sources of actinic radiation include arc lamps, such as xenon-arc lamps, mercury arc lamps (including low and medium pressure mercury arc lamps), fluorescent blacklights, microwave-driven lamps, such as those sold by Fusion UV Systems of Rockville, MD
(including H-type and D-type bulbs), lasers and the like. Lamps that emit enriched amounts of ultraviolet or blue light, such as, for example, low pressure mercury (e.g., germicidal) lamps, are preferred.
In many cases, heat, pressure, or combinations thereof, may be desired during bonding.
Suitable heat sources include, but are not limited to, ovens, heated rollers, heated presses, infrared radiation sources, flame, and the like. Suitable pressure sources are well known and include presses, nip rollers, and the like.
The invention will now be described further by way of the following examples.
EXAMPLES
In the following examples, the term "wt%" means weight percent based on total weight.
"THVTM 500" refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 165°C; "THVT"' 400" refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 150°C; "THVT"' 200" refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 120°C; "FEP" refers to FEP X6307 which is a copolymer of tetrafluorethylene and hexafluoropropylene, 85/15 by weight; "HTE" is a terpolymer of hexafluoropropylene, teterafluoroethylene and ethylene, all available from Dyneon, L.L.C. of Oakdale, MN.
"PVDF-HV" refers to "PVDF 11010" which is a tradename for a copolymer of hexafluoropropylene and vinylidene fluoride having a melting point of 160°C; "PVDF-CV"
refers to SOLEFT"' PVDF-CV which is a copolymer of chlorotrifluoroethylene and vinylidene fluoride, both commercially available from Soltex Polymer Corp. of Houston, TX.
"BYNELTM 3101" is an acid modified ethylene-vinyl acetate copolymer; "ELVAXTM
450" is an ethylene-vinyl acetate copolymer havingl8 wt% vinyl acetate and a Vicat softening temperature of 61°C; "polyimide" refers to KaptonTM 100HN film, all commercially available from E.I. du Pont de Nemours of Wilmington DE.
"EMACTM 2202T" is a copolymer of ethylene and methyl acrylate, 80/20 by weight available from Chevron Chemical Co. of Houston, TX.
"MORTHANETM L424.167 (MI=9.7)" is an aliphatic polyurethane available from Morton, International of Chicago, IL.
"VESTAMID~rM L2140" refers to nylon 12 having a Vicat softening point of 140°C
commercially available from Creanova, Inc. of Somerset, NJ.
"Copper-coated polyimide" refers to KaptonT"' 100HN film that has been metallized with copper. "Gold-coated polyimide" refers to KaptonTM 100HN film that has been metallized with gold.
"Polycarbonate film" refers to polyethylene terephthalate film of about 10 mils (0.25 mm) thickness.
Unless otherwise specified, additional materials used in the examples were readily available from general commercial vendors such Sigma-Aldrich Chemical Co. of Milwaukee, WI.
Example 1 Polymer films (i.e., substrates) were prepared by placing polymer granules indicated in Tables 1A and 1B were placed between two sheets of polytetrafluoroethylene having a thickness of 0.38 mm and softening them for 2-3 minutes at 200°C. Subsequently, the softened materials were pressed for about 5 to 10 seconds between two heated platens of a Wabash hydraulic press (Wabash Metal Products Company, Inc., Hydraulic Division, Wabash, IN) and immediately transferred to a cold Wabash hydraulic press at 13-15°C and 2-4 psi (0.014 - 0.028 MPas). After cooling to room temperature in the cold press, round-shaped films of polymer having a thickness of 1.5 mm were obtained. Small pieces of the pressed films were then placed between two stainless steel plates lined with polyethylene terephthalate-silicone coated release liners and pressed for 2-3 minutes at 200°C with pressure and applied between two heated platens of a Wabash hydraulic press. The films produced in this manner were thin smooth films of 0.08 to 0.15 mm in thickness. The substrate films thus prepared were cut to dimensions of approximately 2.5 cm by 5 cm for use in lamination.
Two bonding compositions were prepared. Bonding composition (BC 1) was prepared by mixing 0.2 g allylamine and 0.1 g benzyltriphenylphosphonium chloride in 2 g methanol. A
second bonding composition (BC 2) was prepared by mixing 0.2 g allylamine and 0.1 g triphenylphosphine in 2 g methanol. All the above chemicals were available from Sigma-Aldrich Chemical Co., Milwaukee, WI.
The cut film was flood-coated with the bonding composition. It was not necessary to dry the bonding composition before forming the bond. Samples were prepared by contacting a fluoropolymer film surface with the bonding composition-coated substrate surface to form a laminate precursor. Comparative samples were prepared by omitting the bonding composition.
The laminate precursor was then placed vertically in the center of a 254 nm photoreactor (Rayonet chamber reactor, model RPR-100 equipped with sixteen low pressure mercury bulbs available from The Southern New England Ultraviolet, Inc. of New Haven, CT.
These samples were irradiated for periods of time indicated in Tables 1 A and 1 B.
After irradiation samples were subjected to hot lamination onto thicker films (1-1.5 mm) of their respective materials for 2 minutes at 200°C in order to obtain accurate adhesion measurement because the irradiated samples were too thin and film stretching/rupturing would be expected during the measurement.
Peel strength was used to determine the degree of bonding. Peel strength was determined in accordance with ASTM D-1876 (T peel test). An InstronT"' model 1125 tester, available from Instron Corp., Canton, MA set at a 4 inch (10.2 cm) per minute crosshead speed was used as the test device. The peel strength was calculated as the average load measured during the peel test. The measured peel strength is shown in Tables 1 A and I
B. Comparative experiments showed that no adhesion between substrates and fluoropolymer films was observed prior to irradiation with the bonding composition present.
Example 2 Glass microscope slides and stainless steel panels (1 inch (2.54 cm) by 2 inch (5.08 cm) pieces were cleaned with acetone. A surface of the glass or steel substrate was coated with a bonding composition, and a piece of fluoropolymer film was subsequently laminated onto the coated substrate in a good surface contact. A strip of silicone liner was inserted along the short edge between the substrate surface and the fluoropolymer film to provide tabs for the peel test.
The laminated sample was positioned vertically in the center of a 254 nm photoreactor as described in Example 1 and irradiated for a period of time as shown in Tables IA and 1B. The measured peel strength is shown in Tables 1 A and 1 B.
Example 3 Instead of fluoropolymer film, a solution of 25% fluoroelastomer FLUORELT~' FC-2145, a raw gum dipolymer of VDF and HFP, (available from Dyneon, LLC) in methanol was coated onto the side of a glass slide having the bonding composition. The fluoroelastomer-coated glass was then subjected to irradiation at 254 nm in a photoreactor as described in Example 1 for a period of time as shown in Tables 1A and 1B. Adhesion between the fluoroelastomer and glass was found.
Table 1A
Laminate Comparative BC 1 BC 2 BC 3 Adhesion Irrad. Adhesion brad. Adhesion brad. Adhesion time time Time (N/cm) (min) (N/cm) (min) (N/cm) (min) (N/cm) ELVAXTM 0 10 18.9 10 25.3 20 4.9 ELVAXTM 0 5 19.0 ELVAXTM 0 45 14.4 B YNEL~ 0 10 14 10 13 BYNELTM 0 5 14.4 VT"'S00 BYNELT"'~ 0 45 17 VT"'200 EMACTM 0 10 17 10 25.2 2220/THVTM400 15 6.7 EMACTM 0 5 19.8 EMAC~ 0 45 5.8 EMACTM 0 45 5.8 VESTAMIDTM 0 15 24.3 15 19.0 MORTI-IANETM0 15 8.8 15 20.4 L424.167, MI=9.7/THVTM40 ENGAGETM 0 20 5.1 20 0 ENGAGETM 0 20 33.1 EXACTT"'i 0 20 10 EXACTT"'' 0 20 4.4 Polyester/THV400 0 30 3.2 TABLE
Laminate Comparative BC 1 BC 2 Adhesion Irrad.AdhesionIrrad.Adhesion time time (N/cm) (min)(N/cm) (min)(N/cm) ELVA 0.4 15 24.7 15 18.6 ELVAXTM 0.4 10 19.2 ELVAXTM 0.4 5 2.8 BYNEL~ 1 15 19.7 15 36.0 BYNEL~ 1 15 6.7 10 26.6 EMAC~ 0 15 23.2 15 26.6 V DF
EMACTM 0 10 17.8 EMACTM 0 5 9.0 HV
BYNEL~ 0 20 28.0 3101/SOLEFTm HV
EMACTM 0 20 25.4 2220/SOLEF~
HV
BYNEL~ 0 20 21.2 3101/SOLEFTm CV
EMACT"' 0 20 26.1 2220/SOLEF~' CV
Glass/THVTM4000 45 Good 45 Good Steel/THVT"'4000 45 Good 45 Good Glass/FluorelT"'0 45 Good Examule 4 The procedure of Example 1 was followed using the bonding composition (BC) and comparative compositions (COMP) listed in Tables 2A and 2B, except that cut fluoropolymer film was coated with the bonding composition or comparative compositions.
Subsequently, a second fluoropolymer film was placed on the bonding composition to form a laminate precursor.
The precursor was then placed vertically in the center of a 254 nm photoreactor (Rayonet -IS-chamber reactor, model RPR-100 equipped with sixteen low pressure mercury bulbs. Samples were irradiated for periods of time indicated in Tables 3A-4. After irradiation, the two pieces of fluoropolymer films were peeled apart and individually laminated to bonding substrates to form the final multiplayer articles. A strip of a silicon liner was inserted about 0.6 cm into the space between the layers along the short edge for peel testing. The article was hot pressed at 200°C
for 2 minutes and immediately transferred to a cold Wabash hydraulic press 13-I S°C. After cooling to room temperature in the cold press, the sample was ready for peel testing.
Composition Ingredients BC4 Diphenyliodonium chloride (0.02g) + allylamine (0.2g) +
acetonitrile (2.g) COMP4 Diphenyliodonium chloride saturated in acetonitrile (2.0g) (comparative) BCS Tetraphenylarsonium chloride (0.03g) + allylamine (0.2g) +
acetonitrile (2.0g) COMPS Tetraphenylarsonium chloride (0.03g) +
acetonitrile (2.0g) (comparative) BC6 Tetraphenylarsonium chloride (O.OSg) +
ethylenediamine (0.2g) + acetonitrile (2.0g) COMP6 Tetraphenylarsonium chloride (O.OSg) +
acetonitrile (2.0g) (comparative) BC7 Triphenylsulfonium chloride (O.OSg) + allylamine (0.2g) +
acetonitrile (2.0g) COMP7 Triphenylsulfonium chloride (O.OSg) + acetonitrile (2.0g) (comparative) BC8 Triphenylsulfonium chloride (O.OSg) + n-butylamine (0.2g) +
acetonitrile (2.0g) BC9 Triphenylsulfonium chloride (O.OSg) + diallylamine (0.2g) +
acetonitrile (2.0g) BC10 Phenyltrimethylammonium chloride(saturated) + allylamine (0.2g) + acetonitrile (2.0g) COMP10 Phenyltrimethylammonium chloride(saturated) +
(comparative)acetonitrile(2.Og) BC 11 Tetraphenylphosphonium chloride (0.1 g) + allylamine (0.2g) +
acetonitrile (2.0g) COMP11 Tetraphenylphosphonium chloride (0.1g) + acetonitrile (2.0g) (comparative) BC12 Tetrabutylphosphonium chloride (0.1g) + allylamine (0.2g) +
acetonitrile (2.0g) COMP12 Tetrabutylphosphonium chloride (0.1g) + acetonitrile (2.0g) (comparative) BC 13 biphenyl sulfide (0.1 g) + allylamine (0.2g) in + acetonitrile (2.0g) COMP13 biphenyl sulfide (0.1 g) + acetonitrile (2.0g) (comparative) Composition Ingredients BC14 biphenyl sulfone (0.1g) + allylamine (0.2g) + acetonitrile (2.0g) COMP14 (comparative)biphenyl sulfone (0.1g) + acetonitrile (2.0g) BC 15 Anisole (0.1 g) + allylamine (0.2g) + acetonitrile (2.0g) COMP15 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC 16 Biphenyl (0.1 g) + allylamine (0.2g) +acetonitrile (2.0) COMP16 (comparative)Biphenyl (0.1g) + acetonitrile (2.0g) BC 17 4, 4'-dihydroxybiphenyl (0.1g) + allylamine (0.2g) + acetonitrile (2.0g) COMP17 (comparative)4, 4'-dihydroxybiphenyl (0.1g) + acetonitrile (2.0g) BC 18 biphenyl ether (0.1 g) + allylamine (0.2g) + acetonitrile (2.0g) COMP18 (comparative)biphenyl ether (0.1g) + acetonitrile (2.0g) BC 19 Anisole (0.1 g) + aniline (0.2g) + acetonitrile (2.0g) COMP19 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC20 Chlorobenzene (0.1 g) + allylamine (0.2g) + acetonitrile (2.0g) COMP20 (comparative)Chlorobenzene (0.1 g) + acetonitrile (2.0g) BC21 Biphenyl (0.1 g) + n-butylamine (0.2g) + acetonitrile (2.0g) COMP21 (comparative)Biphenyl (0.1 g) + acetonitrile (2.0g) BC22 Pyrene (0.1 g) + n-butylamine (0.2g) + acetonitrile (2.0g) COMP22 (comparative)Pyrene (0.1 g) + acetonitrile (2.0g) BC23 Anisole (0.1g) + 3-aminopropyltriethoxysilane (0.2g) + acetonitrile (2.0g) COMP23 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC24 biphenyl sulfide (0.1 g) + 3-aminopropyltriethoxysilane (0.2g) + acetonitrile (2.0g) COMP24 (comparative)biphenyl sulfide (0.1 g) + acetonitrile (2.0g) BC25 Anisole (0.1g) + 3-aminopropyltriethoxysilane (0.2g) + acetonitrile (2.0g) COMP25 (comparative)Anisole (0.1g) + acetonitrile (2.0g) BC26 Anisole (0.1g) + ethylenediamine (0.2g) +
acetonitrile (2.0g) BC27 Anisole (0.1g) + aminoethanol (0.2g) + acetonitrile (2.0g) COMP27 (comparative)Anisole (0.1 g) + acetonitrile (2.0g) BC28 Tetraphenylarsonium chloride (O.OSg) + allylamine (0.2g) + acetonitrile (2.0g) Sample BC Irradiation Peel Strength time at 254 nm (N/cm) (min) FEP/VESTAMIDT"'BC4 10 15.84 FEP/VESTAMIDT"'COMP4 10 0 FEPNESTAMIDT"'BC5 10 14.08 FEP/BYNELT"' BC5 10 21.12 FEPBYNELT"' COMPS 10 0 FEPNESTAMIDT~'BC6 5 14.08 FEPBYNELT"' BC6 5 8.8 FEP/VESTAMIDT"~COMP6 5 0 FEPBYNELT"' COMP6 5 0 FEPNESTAMIDTM BC7 5 cohesive FEP
L2140 failure FEPBYNELT"' BC7 5 5.28 FEP/VESTAMIDT"~COMP? 5 0 FEPBYNELT"' COMP7 5 0 PEP/VESTAMIDT"'BC8 10 8.8 FEPBYNELT"~ BC8 10 11.44 FEP/VESTAMIDT"'BC9 10 cohesive FEP
L2140 failure FEPBYNELT"' BC9 10 cohesive failure FEP/VES1'AMIDTMBC10 15 cohesive FEP
L2140 failure FEPBYNELT"' BC10 15 10.56 FEP/VESTAMIDT"'COMP10 15 0 FEPBYNELT"' COMP10 15 0 FEPNESTAMIDT"'BC11 5 cohesive FEP
L2140 failure FEPBYNELT"' BC11 5 14.08 FEP/VESTAMIDT"'COMP11 5 0 FEPBYNELT"' COMP11 5 0 FEPNESTAMIDT"'BC12 10 cohesive FEP
L2140 failure FEP/BYNELT"' BC12 10 8.8 FEPBYNELT"' COMP12 10 0 Sample BC Irradiation Peel Strength time at 254 nm (N/cm) (min) FEP/VESTAMID BC13 5 >22.8 FEP/BYNELTM 3101BC13 5 15.8 FEP/VESTAMIDTM BC14 5 >12.3 FEP/BYNELTM 3101BC14 5 12.3 FEP/VESTAMIDTM BC15 5 6.1 FEP/BYNELTM 3101BC15 S 7.0 FEP/VESTAMIDTM BC16 5 >22.8 FEP/BYNELTM 3101BC16 5 12.3 FEP/VESTAMIDTM BC 17 5 > 19.3 FEP/BYNELT"' BC 17 5 7.9 FEP/VESTAMIDT"' COMP17 5 1.8 FEP/VESTAMIDTM BC 18 5 7.9 FEP/BYNELTM 3101BC18 5 9.7 FEP/VESTAMIDTM BC19 5 24.6 FEP/BYNELT"' BC 19 5 8.8 FEP/VESTAMIDTM BC20 5 >22.8 FEP/BYNELTM 3101BC20 5 12.3 Sample BC Irradiation Peel Strength time at 254 nm (N/cm) (min) FEP/VESTAMID BC21 5 8.8 "' FEP/BYNELTM BC21 S 30.7 FEP/VESTAMIDTMBC22 5 >22.8 FEP/BYNELTM BC22 5 12.3 FEP/VESTAMIDTMBC23 10 26.3 FEPBYNELTM BC23 10 30.7 FEPBYNELT"' COMP23 5 0 FEP/VESTAMIDTMBC24 5 17.5 FEPBYNELTM BC24 5 29.8 FEP/VESTAMIDTMBC25 5 14.9 FEP/BYNELTM BC25 5 13.2 FEP/VES1'AMIDTMCOMP25 5 0 PEP/VESTAMIDTMBC26 5 7.0 FEP/BYNELTM BC26 5 33.3 FEP/EXACT'T" BC27 10 6.1 FEP/ VESTAMIDTMBC28 5 > 15.8 Example 5 This comparative example shows that electron donors are not effective at promoting bonding according to the invention. Table 4 shows the bonding results obtained when electron donors were used as a 10 weight percent solution in methanol according to the procedure of Example 1.
Sample Electron Donor IrradiationPeel (N/cm) as a 10 wt% in Time at Methanol nm (min) FEP/VESTAMIAllylamine 5 0 DT~' L2140 FEP/Byne13101Allylamine 5 0 FEP/VESTAMIn-butylamine 5 0 FEP/Byne13101n-butylamine 5 0 FEP/VESTAMI3-aminopropyl- 5 0 DTM L2140 triethoxysilane FEP/Byne131013-aminopropyl- 5 <1.75 triethoxysilane FEP/VESTAMI2-aminoethanol 5 <1.75 DT"' L2140 FEP/Byne131012-aminoethanol 5 <I .75 FEP/VESTAMI1,2-ethylenediamine5 <1.75 FEP/Byne131011,2-ethylenediamine5 <1.75 Other embodiments are within the scope of the following claims.
Claims (23)
1. A method of bonding a fluoropolymer to a substrate comprising:
providing a bonding composition between a fluoropolymer and a substrate, the bonding composition including a light-absorbing compound and an electron donor; and exposing the bonding composition to actinic radiation.
providing a bonding composition between a fluoropolymer and a substrate, the bonding composition including a light-absorbing compound and an electron donor; and exposing the bonding composition to actinic radiation.
2. A method of bonding a fluoropolymer to a substrate comprising:
treating a surface of the fluoropolymer with a bonding composition, the bonding composition including an amine and a light-absorbing compound selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound and combinations thereof;
contacting the treated surface of the fluoropolymer with a surface of a substrate, the substrate being selected from the group consisting of a metal, a glass, an organic-inorganic composite, a fluoropolymer and a non-fluorinated polymer; and exposing the bonding composition to actinic radiation.
treating a surface of the fluoropolymer with a bonding composition, the bonding composition including an amine and a light-absorbing compound selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound and combinations thereof;
contacting the treated surface of the fluoropolymer with a surface of a substrate, the substrate being selected from the group consisting of a metal, a glass, an organic-inorganic composite, a fluoropolymer and a non-fluorinated polymer; and exposing the bonding composition to actinic radiation.
3. A method of bonding a fluoropolymer to a substrate comprising:
forming a mixture including a fluoropolymer and a bonding composition, the bonding composition including an amine and a light-absorbing compound selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, and combinations thereof; and contacting a surface of the mixture with a surface of a second component; and exposing the bonding composition to actinic radiation.
forming a mixture including a fluoropolymer and a bonding composition, the bonding composition including an amine and a light-absorbing compound selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, and combinations thereof; and contacting a surface of the mixture with a surface of a second component; and exposing the bonding composition to actinic radiation.
4. A method of bonding a fluoropolymer to a substrate comprising:
providing a first substrate including a bonding composition, the bonding composition including an amine and a light-absorbing compound selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, and combinations thereof;
contacting the surface of the first substrate with a surface of a second substrate; and exposing the bonding composition to actinic radiation, wherein each of the first substrate and the second substrate includes a matrix material selected from the group consisting of a metal, a glass, an organic-inorganic composite, a fluoropolymer, and a non-fluorinated polymer with the proviso that one of the first substrate and the second substrate is a fluoropolymer.
providing a first substrate including a bonding composition, the bonding composition including an amine and a light-absorbing compound selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, and combinations thereof;
contacting the surface of the first substrate with a surface of a second substrate; and exposing the bonding composition to actinic radiation, wherein each of the first substrate and the second substrate includes a matrix material selected from the group consisting of a metal, a glass, an organic-inorganic composite, a fluoropolymer, and a non-fluorinated polymer with the proviso that one of the first substrate and the second substrate is a fluoropolymer.
5. The method of claim 1, wherein the light-absorbing compound is selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, and combinations thereof.
6. The method of claim 1, wherein the electron donor is selected from the group consisting of an amine, a phosphine, phenol, thiophenol, phenolate, thiophenolate or thioether, and combinations thereof.
7. The method of claim 1 or 2, further comprising applying heat or pressure to the bonding composition between a fluoropolymer and a substrate.
8. The method of claim 1, wherein the electron donor includes an amine.
9. The method of claim 2, 3, 4 or 11, wherein the amine is selected from the group consisting of a primary amine, an amino-substituted organosilane, and combinations thereof.
10. The method of claim 1, 2 or 3, wherein the bonding composition includes one or more of a vinylsilane, a perfluorinated polymer, or a partially fluorinated polymer.
11. The method of claim 1, wherein providing includes (a) treating a surface of the fluoropolymer with the bonding composition and contacting the surface of the fluoropolymer with a surface of the substrate, (b) treating a surface of the substrate with the bonding composition and contacting the surface of the substrate with a surface of the fluoropolymer, (c) forming a mixture of the fluoropolymer and the bonding composition and contacting a surface of the mixture with a surface of the substrate, or (d) forming a mixture of the substrate and the bonding composition and contacting a surface of the mixture with a surface of a fluoropolymer.
12. The method of claim 1 or 3, wherein the substrate includes either an inorganic or an organic substrate.
13. The method of claim 1, 2 or 3, wherein the banding composition is exposed to actinic radiation (a) through the fluoropolymer, (b) through the substrate, (c) through the fluoropolymer and the substrate, or (d) before contacting.
14. The method of claim 13, wherein the actinic radiation has a wavelength maximum of between 190 nm and 400 nm.
15. A composite article comprising:
a fluoropolymer having a surface;
a substrate having a surface; and a bonding composition interposed between the surface of the fluoropolymer and the surface of the substrate, the bonding composition including a light-absorbing compound and an electron donors, the bonding composition having been exposed to active radiation.
a fluoropolymer having a surface;
a substrate having a surface; and a bonding composition interposed between the surface of the fluoropolymer and the surface of the substrate, the bonding composition including a light-absorbing compound and an electron donors, the bonding composition having been exposed to active radiation.
16. The article of claim 15, wherein the light-absorbing compound is selected from the group consisting of an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, and combinations thereof, and the electron donor is selected from the group consisting of an amine, a phosphine, a thioether, and combinations thereof.
17. The article of claim 15, wherein the bonding composition further includes a vinyl silane, or a perfluorinated polymer, or a partially fluorinated polymer.
18. The article of claim 15, wherein the substrate includes an inorganic substrate.
19. The article of claim 15, wherein the substrate includes an organic substrate.
20. A treated fluoropolymer substrate suitable for bonding to a polymeric substrate comprising a surface exposed to a combination of a light-absorbing compound and an electron donor and actinic radiation.
21. A laminated article comprising a fluoropolymer bonded to a substrate by a bonding composition including a light-absorbing compound and an electron donor exposed to actinic radiation.
22. A composition comprising a 2,2,2-trifluoroethylamine.
23. The method of claim 1, wherein the electron donor is polymerizable.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/862,022 US6630047B2 (en) | 2001-05-21 | 2001-05-21 | Fluoropolymer bonding composition and method |
US09/862,022 | 2001-05-21 | ||
PCT/US2002/007951 WO2002094912A1 (en) | 2001-05-21 | 2002-03-13 | Fluoropolymer bonding composition and method |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2446142A1 true CA2446142A1 (en) | 2002-11-28 |
Family
ID=25337423
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2446142 Abandoned CA2446142A1 (en) | 2001-05-21 | 2002-03-13 | Fluoropolymer bonding composition and method |
Country Status (8)
Country | Link |
---|---|
US (3) | US6630047B2 (en) |
EP (1) | EP1401926B1 (en) |
JP (1) | JP4711603B2 (en) |
CN (1) | CN1250616C (en) |
AT (1) | ATE335782T1 (en) |
CA (1) | CA2446142A1 (en) |
DE (1) | DE60213811T2 (en) |
WO (1) | WO2002094912A1 (en) |
Families Citing this family (560)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7485371B2 (en) * | 2004-04-16 | 2009-02-03 | 3M Innovative Properties Company | Bonding compositions |
US6630047B2 (en) * | 2001-05-21 | 2003-10-07 | 3M Innovative Properties Company | Fluoropolymer bonding composition and method |
US6753087B2 (en) * | 2001-05-21 | 2004-06-22 | 3M Innovative Properties Company | Fluoropolymer bonding |
US20050208308A1 (en) * | 2001-05-21 | 2005-09-22 | 3M Innovative Properties Company | Bonding compositions |
US6752894B2 (en) * | 2001-12-14 | 2004-06-22 | 3M Innovative Properties Company | Process for modifying a polymeric surface |
US6844030B2 (en) * | 2001-12-14 | 2005-01-18 | 3M Innovative Properties Company | Process for modifying a polymeric surface |
DE10311500A1 (en) * | 2003-03-15 | 2004-09-30 | Cooper-Standard Automotive (Deutschland) Gmbh | Pipe, especially flexible cooling water pipe |
US20070084897A1 (en) | 2003-05-20 | 2007-04-19 | Shelton Frederick E Iv | Articulating surgical stapling instrument incorporating a two-piece e-beam firing mechanism |
US9060770B2 (en) | 2003-05-20 | 2015-06-23 | Ethicon Endo-Surgery, Inc. | Robotically-driven surgical instrument with E-beam driver |
US6986947B2 (en) * | 2003-10-09 | 2006-01-17 | 3M Innovative Properties Company | Method of modifying a fluoropolymer and articles thereby |
US7273531B2 (en) * | 2003-11-05 | 2007-09-25 | 3M Innovative Properties Company | Method of modifying a fluoropolymeric substrate and composite articles thereby |
US20050100712A1 (en) * | 2003-11-12 | 2005-05-12 | Simmons Blake A. | Polymerization welding and application to microfluidics |
US7267865B2 (en) * | 2004-02-20 | 2007-09-11 | Saint-Gobain Performance Plastics Corporation | Draw resonant resistant multilayer films |
US7297391B2 (en) * | 2004-02-20 | 2007-11-20 | Saint-Gobain Performance Plastics Corporation | Draw resonance resistant multilayer films |
US20050276985A1 (en) * | 2004-06-09 | 2005-12-15 | Muggli Mark W | Composite article having a tie layer and method of making the same |
US20050276945A1 (en) * | 2004-06-09 | 2005-12-15 | Muggli Mark W | Composite articles and methods of making the same |
US20050276944A1 (en) * | 2004-06-09 | 2005-12-15 | Muggli Mark M | Composite articles and methods of making the same |
US8215531B2 (en) | 2004-07-28 | 2012-07-10 | Ethicon Endo-Surgery, Inc. | Surgical stapling instrument having a medical substance dispenser |
US11890012B2 (en) | 2004-07-28 | 2024-02-06 | Cilag Gmbh International | Staple cartridge comprising cartridge body and attached support |
US20060105285A1 (en) * | 2004-11-17 | 2006-05-18 | Naiyong Jing | Nonelastomeric dental article with a protective fluoropolymer layer |
US20060105179A1 (en) * | 2004-11-17 | 2006-05-18 | Hofman Gerald R A | Elastomeric dental article with a protective fluoropolymer layer |
US7638186B2 (en) * | 2005-06-13 | 2009-12-29 | 3M Innovative Properties Company | Fluoropolymer containing laminates |
US7669746B2 (en) | 2005-08-31 | 2010-03-02 | Ethicon Endo-Surgery, Inc. | Staple cartridges for forming staples having differing formed staple heights |
US7934630B2 (en) | 2005-08-31 | 2011-05-03 | Ethicon Endo-Surgery, Inc. | Staple cartridges for forming staples having differing formed staple heights |
US11484312B2 (en) | 2005-08-31 | 2022-11-01 | Cilag Gmbh International | Staple cartridge comprising a staple driver arrangement |
US9237891B2 (en) | 2005-08-31 | 2016-01-19 | Ethicon Endo-Surgery, Inc. | Robotically-controlled surgical stapling devices that produce formed staples having different lengths |
US11246590B2 (en) | 2005-08-31 | 2022-02-15 | Cilag Gmbh International | Staple cartridge including staple drivers having different unfired heights |
US10159482B2 (en) | 2005-08-31 | 2018-12-25 | Ethicon Llc | Fastener cartridge assembly comprising a fixed anvil and different staple heights |
US8800838B2 (en) | 2005-08-31 | 2014-08-12 | Ethicon Endo-Surgery, Inc. | Robotically-controlled cable-based surgical end effectors |
US20070194079A1 (en) | 2005-08-31 | 2007-08-23 | Hueil Joseph C | Surgical stapling device with staple drivers of different height |
US20070190307A1 (en) * | 2005-10-12 | 2007-08-16 | Hongwei Li | Foamed fluoroelastic gasket material |
US20070106317A1 (en) | 2005-11-09 | 2007-05-10 | Shelton Frederick E Iv | Hydraulically and electrically actuated articulation joints for surgical instruments |
US7901778B2 (en) * | 2006-01-13 | 2011-03-08 | Saint-Gobain Performance Plastics Corporation | Weatherable multilayer film |
US8820603B2 (en) | 2006-01-31 | 2014-09-02 | Ethicon Endo-Surgery, Inc. | Accessing data stored in a memory of a surgical instrument |
US9861359B2 (en) | 2006-01-31 | 2018-01-09 | Ethicon Llc | Powered surgical instruments with firing system lockout arrangements |
US11278279B2 (en) | 2006-01-31 | 2022-03-22 | Cilag Gmbh International | Surgical instrument assembly |
US8161977B2 (en) | 2006-01-31 | 2012-04-24 | Ethicon Endo-Surgery, Inc. | Accessing data stored in a memory of a surgical instrument |
US7845537B2 (en) | 2006-01-31 | 2010-12-07 | Ethicon Endo-Surgery, Inc. | Surgical instrument having recording capabilities |
US20110024477A1 (en) | 2009-02-06 | 2011-02-03 | Hall Steven G | Driven Surgical Stapler Improvements |
US20120292367A1 (en) | 2006-01-31 | 2012-11-22 | Ethicon Endo-Surgery, Inc. | Robotically-controlled end effector |
US8186555B2 (en) | 2006-01-31 | 2012-05-29 | Ethicon Endo-Surgery, Inc. | Motor-driven surgical cutting and fastening instrument with mechanical closure system |
US11793518B2 (en) | 2006-01-31 | 2023-10-24 | Cilag Gmbh International | Powered surgical instruments with firing system lockout arrangements |
US7753904B2 (en) | 2006-01-31 | 2010-07-13 | Ethicon Endo-Surgery, Inc. | Endoscopic surgical instrument with a handle that can articulate with respect to the shaft |
US20110290856A1 (en) | 2006-01-31 | 2011-12-01 | Ethicon Endo-Surgery, Inc. | Robotically-controlled surgical instrument with force-feedback capabilities |
US8708213B2 (en) | 2006-01-31 | 2014-04-29 | Ethicon Endo-Surgery, Inc. | Surgical instrument having a feedback system |
US8763879B2 (en) | 2006-01-31 | 2014-07-01 | Ethicon Endo-Surgery, Inc. | Accessing data stored in a memory of surgical instrument |
US11224427B2 (en) | 2006-01-31 | 2022-01-18 | Cilag Gmbh International | Surgical stapling system including a console and retraction assembly |
US20070225562A1 (en) | 2006-03-23 | 2007-09-27 | Ethicon Endo-Surgery, Inc. | Articulating endoscopic accessory channel |
US8992422B2 (en) | 2006-03-23 | 2015-03-31 | Ethicon Endo-Surgery, Inc. | Robotically-controlled endoscopic accessory channel |
US8322455B2 (en) | 2006-06-27 | 2012-12-04 | Ethicon Endo-Surgery, Inc. | Manually driven surgical cutting and fastening instrument |
US7598302B2 (en) | 2006-08-30 | 2009-10-06 | Veyance Technologies, Inc | Adhesion promoter for bonding fluoropolymer layers in a multi-layered article |
US20080070182A1 (en) * | 2006-09-20 | 2008-03-20 | 3M Innovative Properties Company | Orthodontic elements and other medical devices with a fluorinated polymer, and methods |
US10568652B2 (en) | 2006-09-29 | 2020-02-25 | Ethicon Llc | Surgical staples having attached drivers of different heights and stapling instruments for deploying the same |
US20080078802A1 (en) | 2006-09-29 | 2008-04-03 | Hess Christopher J | Surgical staples and stapling instruments |
US10130359B2 (en) | 2006-09-29 | 2018-11-20 | Ethicon Llc | Method for forming a staple |
US8459520B2 (en) | 2007-01-10 | 2013-06-11 | Ethicon Endo-Surgery, Inc. | Surgical instrument with wireless communication between control unit and remote sensor |
US11291441B2 (en) | 2007-01-10 | 2022-04-05 | Cilag Gmbh International | Surgical instrument with wireless communication between control unit and remote sensor |
US8652120B2 (en) | 2007-01-10 | 2014-02-18 | Ethicon Endo-Surgery, Inc. | Surgical instrument with wireless communication between control unit and sensor transponders |
US8684253B2 (en) | 2007-01-10 | 2014-04-01 | Ethicon Endo-Surgery, Inc. | Surgical instrument with wireless communication between a control unit of a robotic system and remote sensor |
US20080169332A1 (en) | 2007-01-11 | 2008-07-17 | Shelton Frederick E | Surgical stapling device with a curved cutting member |
US11039836B2 (en) | 2007-01-11 | 2021-06-22 | Cilag Gmbh International | Staple cartridge for use with a surgical stapling instrument |
US20090018275A1 (en) | 2007-01-26 | 2009-01-15 | Greene, Tweed Of Delaware, Inc. | Method of Bonding Perfluoroelastomeric Materials to a Surface |
US20090001121A1 (en) | 2007-03-15 | 2009-01-01 | Hess Christopher J | Surgical staple having an expandable portion |
US8893946B2 (en) | 2007-03-28 | 2014-11-25 | Ethicon Endo-Surgery, Inc. | Laparoscopic tissue thickness and clamp load measuring devices |
US8534528B2 (en) | 2007-06-04 | 2013-09-17 | Ethicon Endo-Surgery, Inc. | Surgical instrument having a multiple rate directional switching mechanism |
US8931682B2 (en) | 2007-06-04 | 2015-01-13 | Ethicon Endo-Surgery, Inc. | Robotically-controlled shaft based rotary drive systems for surgical instruments |
US11672531B2 (en) | 2007-06-04 | 2023-06-13 | Cilag Gmbh International | Rotary drive systems for surgical instruments |
US7905380B2 (en) | 2007-06-04 | 2011-03-15 | Ethicon Endo-Surgery, Inc. | Surgical instrument having a multiple rate directional switching mechanism |
US7832408B2 (en) | 2007-06-04 | 2010-11-16 | Ethicon Endo-Surgery, Inc. | Surgical instrument having a directional switching mechanism |
US8408439B2 (en) | 2007-06-22 | 2013-04-02 | Ethicon Endo-Surgery, Inc. | Surgical stapling instrument with an articulatable end effector |
US7753245B2 (en) | 2007-06-22 | 2010-07-13 | Ethicon Endo-Surgery, Inc. | Surgical stapling instruments |
US11849941B2 (en) | 2007-06-29 | 2023-12-26 | Cilag Gmbh International | Staple cartridge having staple cavities extending at a transverse angle relative to a longitudinal cartridge axis |
US7905381B2 (en) | 2008-09-19 | 2011-03-15 | Ethicon Endo-Surgery, Inc. | Surgical stapling instrument with cutting member arrangement |
US8561870B2 (en) | 2008-02-13 | 2013-10-22 | Ethicon Endo-Surgery, Inc. | Surgical stapling instrument |
US8584919B2 (en) | 2008-02-14 | 2013-11-19 | Ethicon Endo-Sugery, Inc. | Surgical stapling apparatus with load-sensitive firing mechanism |
US7793812B2 (en) | 2008-02-14 | 2010-09-14 | Ethicon Endo-Surgery, Inc. | Disposable motor-driven loading unit for use with a surgical cutting and stapling apparatus |
US8752749B2 (en) | 2008-02-14 | 2014-06-17 | Ethicon Endo-Surgery, Inc. | Robotically-controlled disposable motor-driven loading unit |
BRPI0901282A2 (en) | 2008-02-14 | 2009-11-17 | Ethicon Endo Surgery Inc | surgical cutting and fixation instrument with rf electrodes |
US8636736B2 (en) | 2008-02-14 | 2014-01-28 | Ethicon Endo-Surgery, Inc. | Motorized surgical cutting and fastening instrument |
US7819298B2 (en) | 2008-02-14 | 2010-10-26 | Ethicon Endo-Surgery, Inc. | Surgical stapling apparatus with control features operable with one hand |
US8622274B2 (en) | 2008-02-14 | 2014-01-07 | Ethicon Endo-Surgery, Inc. | Motorized cutting and fastening instrument having control circuit for optimizing battery usage |
US8459525B2 (en) | 2008-02-14 | 2013-06-11 | Ethicon Endo-Sugery, Inc. | Motorized surgical cutting and fastening instrument having a magnetic drive train torque limiting device |
US8573465B2 (en) | 2008-02-14 | 2013-11-05 | Ethicon Endo-Surgery, Inc. | Robotically-controlled surgical end effector system with rotary actuated closure systems |
US7866527B2 (en) | 2008-02-14 | 2011-01-11 | Ethicon Endo-Surgery, Inc. | Surgical stapling apparatus with interlockable firing system |
US8758391B2 (en) | 2008-02-14 | 2014-06-24 | Ethicon Endo-Surgery, Inc. | Interchangeable tools for surgical instruments |
US9179912B2 (en) | 2008-02-14 | 2015-11-10 | Ethicon Endo-Surgery, Inc. | Robotically-controlled motorized surgical cutting and fastening instrument |
US8657174B2 (en) | 2008-02-14 | 2014-02-25 | Ethicon Endo-Surgery, Inc. | Motorized surgical cutting and fastening instrument having handle based power source |
US11272927B2 (en) | 2008-02-15 | 2022-03-15 | Cilag Gmbh International | Layer arrangements for surgical staple cartridges |
US10390823B2 (en) | 2008-02-15 | 2019-08-27 | Ethicon Llc | End effector comprising an adjunct |
PL3476312T3 (en) | 2008-09-19 | 2024-03-11 | Ethicon Llc | Surgical stapler with apparatus for adjusting staple height |
US9050083B2 (en) | 2008-09-23 | 2015-06-09 | Ethicon Endo-Surgery, Inc. | Motorized surgical instrument |
US9005230B2 (en) | 2008-09-23 | 2015-04-14 | Ethicon Endo-Surgery, Inc. | Motorized surgical instrument |
US8210411B2 (en) | 2008-09-23 | 2012-07-03 | Ethicon Endo-Surgery, Inc. | Motor-driven surgical cutting instrument |
US11648005B2 (en) | 2008-09-23 | 2023-05-16 | Cilag Gmbh International | Robotically-controlled motorized surgical instrument with an end effector |
US9386983B2 (en) | 2008-09-23 | 2016-07-12 | Ethicon Endo-Surgery, Llc | Robotically-controlled motorized surgical instrument |
US8608045B2 (en) | 2008-10-10 | 2013-12-17 | Ethicon Endo-Sugery, Inc. | Powered surgical cutting and stapling apparatus with manually retractable firing system |
KR101755723B1 (en) * | 2008-12-15 | 2017-07-07 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Composite article including viscoelastic layer with barrier layer |
US10525667B2 (en) * | 2008-12-15 | 2020-01-07 | 3M Innovative Properties Company | Surfacing film for composites with barrier layer |
US8517239B2 (en) | 2009-02-05 | 2013-08-27 | Ethicon Endo-Surgery, Inc. | Surgical stapling instrument comprising a magnetic element driver |
US8397971B2 (en) | 2009-02-05 | 2013-03-19 | Ethicon Endo-Surgery, Inc. | Sterilizable surgical instrument |
US8414577B2 (en) | 2009-02-05 | 2013-04-09 | Ethicon Endo-Surgery, Inc. | Surgical instruments and components for use in sterile environments |
US8444036B2 (en) | 2009-02-06 | 2013-05-21 | Ethicon Endo-Surgery, Inc. | Motor driven surgical fastener device with mechanisms for adjusting a tissue gap within the end effector |
BRPI1008667A2 (en) | 2009-02-06 | 2016-03-08 | Ethicom Endo Surgery Inc | improvement of the operated surgical stapler |
US8453907B2 (en) | 2009-02-06 | 2013-06-04 | Ethicon Endo-Surgery, Inc. | Motor driven surgical fastener device with cutting member reversing mechanism |
US8397446B2 (en) * | 2009-02-10 | 2013-03-19 | Certainteed Corporation | Composite roofing or other surfacing board, method of making and using and roof made thereby |
US20110017278A1 (en) | 2009-06-25 | 2011-01-27 | Kalkanoglu Husnu M | Roofing products, photovoltaic roofing elements and systems using them |
JP2013514439A (en) | 2009-12-15 | 2013-04-25 | スリーエム イノベイティブ プロパティズ カンパニー | Fluoropolymer film with epoxy adhesive |
US8220688B2 (en) | 2009-12-24 | 2012-07-17 | Ethicon Endo-Surgery, Inc. | Motor-driven surgical cutting instrument with electric actuator directional control assembly |
US8851354B2 (en) | 2009-12-24 | 2014-10-07 | Ethicon Endo-Surgery, Inc. | Surgical cutting instrument that analyzes tissue thickness |
US10632740B2 (en) | 2010-04-23 | 2020-04-28 | Landa Corporation Ltd. | Digital printing process |
US8211265B2 (en) * | 2010-06-07 | 2012-07-03 | E. I. Du Pont De Nemours And Company | Method for preparing multilayer structures containing a perfluorinated copolymer resin layer |
WO2011153681A1 (en) * | 2010-06-07 | 2011-12-15 | E.I. Du Pont De Nemours And Company | Transparent film containing tetrafluoroethylene-hexafluoropropylene copolymer and having an organosilane coupling agent treated surface |
US8783543B2 (en) | 2010-07-30 | 2014-07-22 | Ethicon Endo-Surgery, Inc. | Tissue acquisition arrangements and methods for surgical stapling devices |
US20120078244A1 (en) | 2010-09-24 | 2012-03-29 | Worrell Barry C | Control features for articulating surgical device |
US8733613B2 (en) | 2010-09-29 | 2014-05-27 | Ethicon Endo-Surgery, Inc. | Staple cartridge |
US9232941B2 (en) | 2010-09-30 | 2016-01-12 | Ethicon Endo-Surgery, Inc. | Tissue thickness compensator comprising a reservoir |
US9861361B2 (en) | 2010-09-30 | 2018-01-09 | Ethicon Llc | Releasable tissue thickness compensator and fastener cartridge having the same |
US9332974B2 (en) | 2010-09-30 | 2016-05-10 | Ethicon Endo-Surgery, Llc | Layered tissue thickness compensator |
US9204880B2 (en) | 2012-03-28 | 2015-12-08 | Ethicon Endo-Surgery, Inc. | Tissue thickness compensator comprising capsules defining a low pressure environment |
US8840003B2 (en) | 2010-09-30 | 2014-09-23 | Ethicon Endo-Surgery, Inc. | Surgical stapling instrument with compact articulation control arrangement |
US9220501B2 (en) | 2010-09-30 | 2015-12-29 | Ethicon Endo-Surgery, Inc. | Tissue thickness compensators |
US8893949B2 (en) | 2010-09-30 | 2014-11-25 | Ethicon Endo-Surgery, Inc. | Surgical stapler with floating anvil |
US9386988B2 (en) | 2010-09-30 | 2016-07-12 | Ethicon End-Surgery, LLC | Retainer assembly including a tissue thickness compensator |
US10945731B2 (en) | 2010-09-30 | 2021-03-16 | Ethicon Llc | Tissue thickness compensator comprising controlled release and expansion |
US9364233B2 (en) | 2010-09-30 | 2016-06-14 | Ethicon Endo-Surgery, Llc | Tissue thickness compensators for circular surgical staplers |
US11812965B2 (en) | 2010-09-30 | 2023-11-14 | Cilag Gmbh International | Layer of material for a surgical end effector |
US20120080498A1 (en) | 2010-09-30 | 2012-04-05 | Ethicon Endo-Surgery, Inc. | Curved end effector for a stapling instrument |
CN103140178B (en) | 2010-09-30 | 2015-09-23 | 伊西康内外科公司 | Comprise the closure system keeping matrix and alignment matrix |
US9307989B2 (en) | 2012-03-28 | 2016-04-12 | Ethicon Endo-Surgery, Llc | Tissue stapler having a thickness compensator incorportating a hydrophobic agent |
US10123798B2 (en) | 2010-09-30 | 2018-11-13 | Ethicon Llc | Tissue thickness compensator comprising controlled release and expansion |
US9414838B2 (en) | 2012-03-28 | 2016-08-16 | Ethicon Endo-Surgery, Llc | Tissue thickness compensator comprised of a plurality of materials |
US8864009B2 (en) | 2010-09-30 | 2014-10-21 | Ethicon Endo-Surgery, Inc. | Tissue thickness compensator for a surgical stapler comprising an adjustable anvil |
US9839420B2 (en) | 2010-09-30 | 2017-12-12 | Ethicon Llc | Tissue thickness compensator comprising at least one medicament |
US11298125B2 (en) | 2010-09-30 | 2022-04-12 | Cilag Gmbh International | Tissue stapler having a thickness compensator |
US9314246B2 (en) | 2010-09-30 | 2016-04-19 | Ethicon Endo-Surgery, Llc | Tissue stapler having a thickness compensator incorporating an anti-inflammatory agent |
US9629814B2 (en) | 2010-09-30 | 2017-04-25 | Ethicon Endo-Surgery, Llc | Tissue thickness compensator configured to redistribute compressive forces |
US11849952B2 (en) | 2010-09-30 | 2023-12-26 | Cilag Gmbh International | Staple cartridge comprising staples positioned within a compressible portion thereof |
US8695866B2 (en) | 2010-10-01 | 2014-04-15 | Ethicon Endo-Surgery, Inc. | Surgical instrument having a power control circuit |
JP6026509B2 (en) | 2011-04-29 | 2016-11-16 | エシコン・エンド−サージェリィ・インコーポレイテッドEthicon Endo−Surgery,Inc. | Staple cartridge including staples disposed within a compressible portion of the staple cartridge itself |
US11207064B2 (en) | 2011-05-27 | 2021-12-28 | Cilag Gmbh International | Automated end effector component reloading system for use with a robotic system |
US9072535B2 (en) | 2011-05-27 | 2015-07-07 | Ethicon Endo-Surgery, Inc. | Surgical stapling instruments with rotatable staple deployment arrangements |
GB201108963D0 (en) * | 2011-05-27 | 2011-07-13 | 3M Innovative Properties Co | Composite materials comprising polyamides and fluoroelastomers |
US9050084B2 (en) | 2011-09-23 | 2015-06-09 | Ethicon Endo-Surgery, Inc. | Staple cartridge including collapsible deck arrangement |
WO2013101822A2 (en) * | 2011-12-29 | 2013-07-04 | 3M Innovative Properties Company | Metallization of fluoroelastomer films |
US9044230B2 (en) | 2012-02-13 | 2015-06-02 | Ethicon Endo-Surgery, Inc. | Surgical cutting and fastening instrument with apparatus for determining cartridge and firing motion status |
US10569534B2 (en) | 2012-03-05 | 2020-02-25 | Landa Corporation Ltd. | Digital printing system |
US20150024648A1 (en) | 2012-03-05 | 2015-01-22 | Landa Corporation Ltd. | Intermediate transfer members for use with indirect printing systems |
EP2822779B1 (en) | 2012-03-05 | 2018-07-18 | Landa Corporation Ltd. | Protonatable intermediate transfer members for use with indirect printing systems |
US9902147B2 (en) | 2012-03-05 | 2018-02-27 | Landa Corporation Ltd. | Digital printing system |
US10190012B2 (en) | 2012-03-05 | 2019-01-29 | Landa Corporation Ltd. | Treatment of release layer and inkjet ink formulations |
EP4019596A1 (en) | 2012-03-05 | 2022-06-29 | Landa Corporation Ltd. | Method for manufacturing an ink film construction |
US9643403B2 (en) | 2012-03-05 | 2017-05-09 | Landa Corporation Ltd. | Printing system |
CN104271356B (en) | 2012-03-05 | 2016-10-19 | 兰达公司 | Digital printing process |
US10434761B2 (en) | 2012-03-05 | 2019-10-08 | Landa Corporation Ltd. | Digital printing process |
EP2822776B1 (en) | 2012-03-05 | 2018-08-01 | Landa Corporation Ltd. | Transfer printing method |
US10642198B2 (en) | 2012-03-05 | 2020-05-05 | Landa Corporation Ltd. | Intermediate transfer members for use with indirect printing systems and protonatable intermediate transfer members for use with indirect printing systems |
US9498946B2 (en) | 2012-03-05 | 2016-11-22 | Landa Corporation Ltd. | Apparatus and method for control or monitoring of a printing system |
US9327496B2 (en) | 2012-03-05 | 2016-05-03 | Landa Corporation Ltd. | Ink film constructions |
JP6393190B2 (en) | 2012-03-15 | 2018-09-19 | ランダ コーポレイション リミテッド | Endless flexible belt for printing system |
BR112014024098B1 (en) | 2012-03-28 | 2021-05-25 | Ethicon Endo-Surgery, Inc. | staple cartridge |
MX353040B (en) | 2012-03-28 | 2017-12-18 | Ethicon Endo Surgery Inc | Retainer assembly including a tissue thickness compensator. |
JP6305979B2 (en) | 2012-03-28 | 2018-04-04 | エシコン・エンド−サージェリィ・インコーポレイテッドEthicon Endo−Surgery,Inc. | Tissue thickness compensator with multiple layers |
US9198662B2 (en) | 2012-03-28 | 2015-12-01 | Ethicon Endo-Surgery, Inc. | Tissue thickness compensator having improved visibility |
US9101358B2 (en) | 2012-06-15 | 2015-08-11 | Ethicon Endo-Surgery, Inc. | Articulatable surgical instrument comprising a firing drive |
US20140001231A1 (en) | 2012-06-28 | 2014-01-02 | Ethicon Endo-Surgery, Inc. | Firing system lockout arrangements for surgical instruments |
US9649111B2 (en) | 2012-06-28 | 2017-05-16 | Ethicon Endo-Surgery, Llc | Replaceable clip cartridge for a clip applier |
US9204879B2 (en) | 2012-06-28 | 2015-12-08 | Ethicon Endo-Surgery, Inc. | Flexible drive member |
US9072536B2 (en) | 2012-06-28 | 2015-07-07 | Ethicon Endo-Surgery, Inc. | Differential locking arrangements for rotary powered surgical instruments |
BR112014032776B1 (en) | 2012-06-28 | 2021-09-08 | Ethicon Endo-Surgery, Inc | SURGICAL INSTRUMENT SYSTEM AND SURGICAL KIT FOR USE WITH A SURGICAL INSTRUMENT SYSTEM |
US9101385B2 (en) | 2012-06-28 | 2015-08-11 | Ethicon Endo-Surgery, Inc. | Electrode connections for rotary driven surgical tools |
US20140001234A1 (en) | 2012-06-28 | 2014-01-02 | Ethicon Endo-Surgery, Inc. | Coupling arrangements for attaching surgical end effectors to drive systems therefor |
US9289256B2 (en) | 2012-06-28 | 2016-03-22 | Ethicon Endo-Surgery, Llc | Surgical end effectors having angled tissue-contacting surfaces |
US8747238B2 (en) | 2012-06-28 | 2014-06-10 | Ethicon Endo-Surgery, Inc. | Rotary drive shaft assemblies for surgical instruments with articulatable end effectors |
US11202631B2 (en) | 2012-06-28 | 2021-12-21 | Cilag Gmbh International | Stapling assembly comprising a firing lockout |
EP2866686A1 (en) | 2012-06-28 | 2015-05-06 | Ethicon Endo-Surgery, Inc. | Empty clip cartridge lockout |
US9119657B2 (en) | 2012-06-28 | 2015-09-01 | Ethicon Endo-Surgery, Inc. | Rotary actuatable closure arrangement for surgical end effector |
US9028494B2 (en) | 2012-06-28 | 2015-05-12 | Ethicon Endo-Surgery, Inc. | Interchangeable end effector coupling arrangement |
US9561038B2 (en) | 2012-06-28 | 2017-02-07 | Ethicon Endo-Surgery, Llc | Interchangeable clip applier |
US9125662B2 (en) | 2012-06-28 | 2015-09-08 | Ethicon Endo-Surgery, Inc. | Multi-axis articulating and rotating surgical tools |
EP2888297B1 (en) | 2012-08-21 | 2019-12-11 | 3M Innovative Properties Company | Semi-fluorinated thermoplastic resins with low gel content |
US9386984B2 (en) | 2013-02-08 | 2016-07-12 | Ethicon Endo-Surgery, Llc | Staple cartridge comprising a releasable cover |
US10092292B2 (en) | 2013-02-28 | 2018-10-09 | Ethicon Llc | Staple forming features for surgical stapling instrument |
US20140249557A1 (en) | 2013-03-01 | 2014-09-04 | Ethicon Endo-Surgery, Inc. | Thumbwheel switch arrangements for surgical instruments |
BR112015021098B1 (en) | 2013-03-01 | 2022-02-15 | Ethicon Endo-Surgery, Inc | COVERAGE FOR A JOINT JOINT AND SURGICAL INSTRUMENT |
JP6345707B2 (en) | 2013-03-01 | 2018-06-20 | エシコン・エンド−サージェリィ・インコーポレイテッドEthicon Endo−Surgery,Inc. | Surgical instrument with soft stop |
US20140263552A1 (en) | 2013-03-13 | 2014-09-18 | Ethicon Endo-Surgery, Inc. | Staple cartridge tissue thickness sensor system |
US9629629B2 (en) | 2013-03-14 | 2017-04-25 | Ethicon Endo-Surgey, LLC | Control systems for surgical instruments |
US9808244B2 (en) | 2013-03-14 | 2017-11-07 | Ethicon Llc | Sensor arrangements for absolute positioning system for surgical instruments |
US9332984B2 (en) | 2013-03-27 | 2016-05-10 | Ethicon Endo-Surgery, Llc | Fastener cartridge assemblies |
US9795384B2 (en) | 2013-03-27 | 2017-10-24 | Ethicon Llc | Fastener cartridge comprising a tissue thickness compensator and a gap setting element |
US9572577B2 (en) | 2013-03-27 | 2017-02-21 | Ethicon Endo-Surgery, Llc | Fastener cartridge comprising a tissue thickness compensator including openings therein |
US9867612B2 (en) | 2013-04-16 | 2018-01-16 | Ethicon Llc | Powered surgical stapler |
BR112015026109B1 (en) | 2013-04-16 | 2022-02-22 | Ethicon Endo-Surgery, Inc | surgical instrument |
JP2016524520A (en) | 2013-04-18 | 2016-08-18 | スリーエム イノベイティブ プロパティズ カンパニー | Buried clay / nanosilica static dissipative coating |
US9574644B2 (en) | 2013-05-30 | 2017-02-21 | Ethicon Endo-Surgery, Llc | Power module for use with a surgical instrument |
CN105339166B (en) * | 2013-05-31 | 2018-06-22 | 住友电气工业株式会社 | The manufacturing method of metal-resin complex, wiring material and metal-resin complex |
JP6416260B2 (en) | 2013-08-23 | 2018-10-31 | エシコン エルエルシー | Firing member retractor for a powered surgical instrument |
US9775609B2 (en) | 2013-08-23 | 2017-10-03 | Ethicon Llc | Tamper proof circuit for surgical instrument battery pack |
US9243170B2 (en) * | 2013-08-26 | 2016-01-26 | Tyco Electronics Corporation | Adhesive manufacturing process, adhesive, and article |
GB201401173D0 (en) | 2013-09-11 | 2014-03-12 | Landa Corp Ltd | Ink formulations and film constructions thereof |
EP3044010B1 (en) | 2013-09-11 | 2019-11-06 | Landa Corporation Ltd. | Release layer treatment formulations |
US9724092B2 (en) | 2013-12-23 | 2017-08-08 | Ethicon Llc | Modular surgical instruments |
US9839428B2 (en) | 2013-12-23 | 2017-12-12 | Ethicon Llc | Surgical cutting and stapling instruments with independent jaw control features |
US9687232B2 (en) | 2013-12-23 | 2017-06-27 | Ethicon Llc | Surgical staples |
US20150173756A1 (en) | 2013-12-23 | 2015-06-25 | Ethicon Endo-Surgery, Inc. | Surgical cutting and stapling methods |
US9962161B2 (en) | 2014-02-12 | 2018-05-08 | Ethicon Llc | Deliverable surgical instrument |
CN106232029B (en) | 2014-02-24 | 2019-04-12 | 伊西康内外科有限责任公司 | Fastening system including firing member locking piece |
US9839422B2 (en) | 2014-02-24 | 2017-12-12 | Ethicon Llc | Implantable layers and methods for altering implantable layers for use with surgical fastening instruments |
US9820738B2 (en) | 2014-03-26 | 2017-11-21 | Ethicon Llc | Surgical instrument comprising interactive systems |
US9750499B2 (en) | 2014-03-26 | 2017-09-05 | Ethicon Llc | Surgical stapling instrument system |
US9826977B2 (en) | 2014-03-26 | 2017-11-28 | Ethicon Llc | Sterilization verification circuit |
BR112016021943B1 (en) | 2014-03-26 | 2022-06-14 | Ethicon Endo-Surgery, Llc | SURGICAL INSTRUMENT FOR USE BY AN OPERATOR IN A SURGICAL PROCEDURE |
US9913642B2 (en) | 2014-03-26 | 2018-03-13 | Ethicon Llc | Surgical instrument comprising a sensor system |
US9801628B2 (en) | 2014-09-26 | 2017-10-31 | Ethicon Llc | Surgical staple and driver arrangements for staple cartridges |
US10299792B2 (en) | 2014-04-16 | 2019-05-28 | Ethicon Llc | Fastener cartridge comprising non-uniform fasteners |
US20150297223A1 (en) | 2014-04-16 | 2015-10-22 | Ethicon Endo-Surgery, Inc. | Fastener cartridges including extensions having different configurations |
BR112016023807B1 (en) | 2014-04-16 | 2022-07-12 | Ethicon Endo-Surgery, Llc | CARTRIDGE SET OF FASTENERS FOR USE WITH A SURGICAL INSTRUMENT |
CN106456158B (en) | 2014-04-16 | 2019-02-05 | 伊西康内外科有限责任公司 | Fastener cartridge including non-uniform fastener |
JP6636452B2 (en) | 2014-04-16 | 2020-01-29 | エシコン エルエルシーEthicon LLC | Fastener cartridge including extension having different configurations |
US10045781B2 (en) | 2014-06-13 | 2018-08-14 | Ethicon Llc | Closure lockout systems for surgical instruments |
BR112017004361B1 (en) | 2014-09-05 | 2023-04-11 | Ethicon Llc | ELECTRONIC SYSTEM FOR A SURGICAL INSTRUMENT |
US10016199B2 (en) | 2014-09-05 | 2018-07-10 | Ethicon Llc | Polarity of hall magnet to identify cartridge type |
US11311294B2 (en) | 2014-09-05 | 2022-04-26 | Cilag Gmbh International | Powered medical device including measurement of closure state of jaws |
US10105142B2 (en) | 2014-09-18 | 2018-10-23 | Ethicon Llc | Surgical stapler with plurality of cutting elements |
BR112017005981B1 (en) | 2014-09-26 | 2022-09-06 | Ethicon, Llc | ANCHOR MATERIAL FOR USE WITH A SURGICAL STAPLE CARTRIDGE AND SURGICAL STAPLE CARTRIDGE FOR USE WITH A SURGICAL INSTRUMENT |
US11523821B2 (en) | 2014-09-26 | 2022-12-13 | Cilag Gmbh International | Method for creating a flexible staple line |
US10076325B2 (en) | 2014-10-13 | 2018-09-18 | Ethicon Llc | Surgical stapling apparatus comprising a tissue stop |
US9924944B2 (en) | 2014-10-16 | 2018-03-27 | Ethicon Llc | Staple cartridge comprising an adjunct material |
US10517594B2 (en) | 2014-10-29 | 2019-12-31 | Ethicon Llc | Cartridge assemblies for surgical staplers |
US11141153B2 (en) | 2014-10-29 | 2021-10-12 | Cilag Gmbh International | Staple cartridges comprising driver arrangements |
US9844376B2 (en) | 2014-11-06 | 2017-12-19 | Ethicon Llc | Staple cartridge comprising a releasable adjunct material |
US10736636B2 (en) | 2014-12-10 | 2020-08-11 | Ethicon Llc | Articulatable surgical instrument system |
US10188385B2 (en) | 2014-12-18 | 2019-01-29 | Ethicon Llc | Surgical instrument system comprising lockable systems |
US10117649B2 (en) | 2014-12-18 | 2018-11-06 | Ethicon Llc | Surgical instrument assembly comprising a lockable articulation system |
US9844375B2 (en) | 2014-12-18 | 2017-12-19 | Ethicon Llc | Drive arrangements for articulatable surgical instruments |
US9844374B2 (en) | 2014-12-18 | 2017-12-19 | Ethicon Llc | Surgical instrument systems comprising an articulatable end effector and means for adjusting the firing stroke of a firing member |
BR112017012996B1 (en) | 2014-12-18 | 2022-11-08 | Ethicon Llc | SURGICAL INSTRUMENT WITH AN ANvil WHICH IS SELECTIVELY MOVABLE ABOUT AN IMMOVABLE GEOMETRIC AXIS DIFFERENT FROM A STAPLE CARTRIDGE |
US10085748B2 (en) | 2014-12-18 | 2018-10-02 | Ethicon Llc | Locking arrangements for detachable shaft assemblies with articulatable surgical end effectors |
US9943309B2 (en) | 2014-12-18 | 2018-04-17 | Ethicon Llc | Surgical instruments with articulatable end effectors and movable firing beam support arrangements |
US9987000B2 (en) | 2014-12-18 | 2018-06-05 | Ethicon Llc | Surgical instrument assembly comprising a flexible articulation system |
US10226250B2 (en) | 2015-02-27 | 2019-03-12 | Ethicon Llc | Modular stapling assembly |
US10180463B2 (en) | 2015-02-27 | 2019-01-15 | Ethicon Llc | Surgical apparatus configured to assess whether a performance parameter of the surgical apparatus is within an acceptable performance band |
US11154301B2 (en) | 2015-02-27 | 2021-10-26 | Cilag Gmbh International | Modular stapling assembly |
US9931118B2 (en) | 2015-02-27 | 2018-04-03 | Ethicon Endo-Surgery, Llc | Reinforced battery for a surgical instrument |
US9993248B2 (en) | 2015-03-06 | 2018-06-12 | Ethicon Endo-Surgery, Llc | Smart sensors with local signal processing |
US9924961B2 (en) | 2015-03-06 | 2018-03-27 | Ethicon Endo-Surgery, Llc | Interactive feedback system for powered surgical instruments |
US10245033B2 (en) | 2015-03-06 | 2019-04-02 | Ethicon Llc | Surgical instrument comprising a lockable battery housing |
US9901342B2 (en) | 2015-03-06 | 2018-02-27 | Ethicon Endo-Surgery, Llc | Signal and power communication system positioned on a rotatable shaft |
JP2020121162A (en) | 2015-03-06 | 2020-08-13 | エシコン エルエルシーEthicon LLC | Time dependent evaluation of sensor data to determine stability element, creep element and viscoelastic element of measurement |
US10617412B2 (en) | 2015-03-06 | 2020-04-14 | Ethicon Llc | System for detecting the mis-insertion of a staple cartridge into a surgical stapler |
US10052044B2 (en) | 2015-03-06 | 2018-08-21 | Ethicon Llc | Time dependent evaluation of sensor data to determine stability, creep, and viscoelastic elements of measures |
US10441279B2 (en) | 2015-03-06 | 2019-10-15 | Ethicon Llc | Multiple level thresholds to modify operation of powered surgical instruments |
US10045776B2 (en) | 2015-03-06 | 2018-08-14 | Ethicon Llc | Control techniques and sub-processor contained within modular shaft with select control processing from handle |
US9895148B2 (en) | 2015-03-06 | 2018-02-20 | Ethicon Endo-Surgery, Llc | Monitoring speed control and precision incrementing of motor for powered surgical instruments |
US9808246B2 (en) | 2015-03-06 | 2017-11-07 | Ethicon Endo-Surgery, Llc | Method of operating a powered surgical instrument |
US10687806B2 (en) | 2015-03-06 | 2020-06-23 | Ethicon Llc | Adaptive tissue compression techniques to adjust closure rates for multiple tissue types |
GB2536489B (en) | 2015-03-20 | 2018-08-29 | Landa Corporation Ltd | Indirect printing system |
US10213201B2 (en) | 2015-03-31 | 2019-02-26 | Ethicon Llc | Stapling end effector configured to compensate for an uneven gap between a first jaw and a second jaw |
GB2537813A (en) | 2015-04-14 | 2016-11-02 | Landa Corp Ltd | Apparatus for threading an intermediate transfer member of a printing system |
US10703093B2 (en) | 2015-07-10 | 2020-07-07 | Landa Corporation Ltd. | Indirect inkjet printing system |
US10368861B2 (en) | 2015-06-18 | 2019-08-06 | Ethicon Llc | Dual articulation drive system arrangements for articulatable surgical instruments |
US11058425B2 (en) | 2015-08-17 | 2021-07-13 | Ethicon Llc | Implantable layers for a surgical instrument |
US10160829B2 (en) | 2015-08-20 | 2018-12-25 | 3M Innovative Properties Company | Functionalized polyester polymers and film articles |
MX2022009705A (en) | 2015-08-26 | 2022-11-07 | Ethicon Llc | Surgical staples comprising hardness variations for improved fastening of tissue. |
JP6828018B2 (en) | 2015-08-26 | 2021-02-10 | エシコン エルエルシーEthicon LLC | Surgical staple strips that allow you to change the characteristics of staples and facilitate filling into cartridges |
US10166026B2 (en) | 2015-08-26 | 2019-01-01 | Ethicon Llc | Staple cartridge assembly including features for controlling the rotation of staples when being ejected therefrom |
US10357252B2 (en) | 2015-09-02 | 2019-07-23 | Ethicon Llc | Surgical staple configurations with camming surfaces located between portions supporting surgical staples |
MX2022006192A (en) | 2015-09-02 | 2022-06-16 | Ethicon Llc | Surgical staple configurations with camming surfaces located between portions supporting surgical staples. |
US10105139B2 (en) | 2015-09-23 | 2018-10-23 | Ethicon Llc | Surgical stapler having downstream current-based motor control |
US10076326B2 (en) | 2015-09-23 | 2018-09-18 | Ethicon Llc | Surgical stapler having current mirror-based motor control |
US10085751B2 (en) | 2015-09-23 | 2018-10-02 | Ethicon Llc | Surgical stapler having temperature-based motor control |
US10327769B2 (en) | 2015-09-23 | 2019-06-25 | Ethicon Llc | Surgical stapler having motor control based on a drive system component |
US10363036B2 (en) | 2015-09-23 | 2019-07-30 | Ethicon Llc | Surgical stapler having force-based motor control |
US10238386B2 (en) | 2015-09-23 | 2019-03-26 | Ethicon Llc | Surgical stapler having motor control based on an electrical parameter related to a motor current |
US10299878B2 (en) | 2015-09-25 | 2019-05-28 | Ethicon Llc | Implantable adjunct systems for determining adjunct skew |
US10478188B2 (en) | 2015-09-30 | 2019-11-19 | Ethicon Llc | Implantable layer comprising a constricted configuration |
US10980539B2 (en) | 2015-09-30 | 2021-04-20 | Ethicon Llc | Implantable adjunct comprising bonded layers |
US11890015B2 (en) | 2015-09-30 | 2024-02-06 | Cilag Gmbh International | Compressible adjunct with crossing spacer fibers |
US10736633B2 (en) | 2015-09-30 | 2020-08-11 | Ethicon Llc | Compressible adjunct with looping members |
US10265068B2 (en) | 2015-12-30 | 2019-04-23 | Ethicon Llc | Surgical instruments with separable motors and motor control circuits |
US10368865B2 (en) | 2015-12-30 | 2019-08-06 | Ethicon Llc | Mechanisms for compensating for drivetrain failure in powered surgical instruments |
US10292704B2 (en) | 2015-12-30 | 2019-05-21 | Ethicon Llc | Mechanisms for compensating for battery pack failure in powered surgical instruments |
US11213293B2 (en) | 2016-02-09 | 2022-01-04 | Cilag Gmbh International | Articulatable surgical instruments with single articulation link arrangements |
US10245029B2 (en) | 2016-02-09 | 2019-04-02 | Ethicon Llc | Surgical instrument with articulating and axially translatable end effector |
BR112018016098B1 (en) | 2016-02-09 | 2023-02-23 | Ethicon Llc | SURGICAL INSTRUMENT |
US11224426B2 (en) | 2016-02-12 | 2022-01-18 | Cilag Gmbh International | Mechanisms for compensating for drivetrain failure in powered surgical instruments |
US10448948B2 (en) | 2016-02-12 | 2019-10-22 | Ethicon Llc | Mechanisms for compensating for drivetrain failure in powered surgical instruments |
US10258331B2 (en) | 2016-02-12 | 2019-04-16 | Ethicon Llc | Mechanisms for compensating for drivetrain failure in powered surgical instruments |
US10485542B2 (en) | 2016-04-01 | 2019-11-26 | Ethicon Llc | Surgical stapling instrument comprising multiple lockouts |
US10617413B2 (en) | 2016-04-01 | 2020-04-14 | Ethicon Llc | Closure system arrangements for surgical cutting and stapling devices with separate and distinct firing shafts |
US10405859B2 (en) | 2016-04-15 | 2019-09-10 | Ethicon Llc | Surgical instrument with adjustable stop/start control during a firing motion |
US10492783B2 (en) | 2016-04-15 | 2019-12-03 | Ethicon, Llc | Surgical instrument with improved stop/start control during a firing motion |
US11607239B2 (en) | 2016-04-15 | 2023-03-21 | Cilag Gmbh International | Systems and methods for controlling a surgical stapling and cutting instrument |
US10426467B2 (en) | 2016-04-15 | 2019-10-01 | Ethicon Llc | Surgical instrument with detection sensors |
US10335145B2 (en) | 2016-04-15 | 2019-07-02 | Ethicon Llc | Modular surgical instrument with configurable operating mode |
US11179150B2 (en) | 2016-04-15 | 2021-11-23 | Cilag Gmbh International | Systems and methods for controlling a surgical stapling and cutting instrument |
US10828028B2 (en) | 2016-04-15 | 2020-11-10 | Ethicon Llc | Surgical instrument with multiple program responses during a firing motion |
US10456137B2 (en) | 2016-04-15 | 2019-10-29 | Ethicon Llc | Staple formation detection mechanisms |
US10357247B2 (en) | 2016-04-15 | 2019-07-23 | Ethicon Llc | Surgical instrument with multiple program responses during a firing motion |
US20170296173A1 (en) | 2016-04-18 | 2017-10-19 | Ethicon Endo-Surgery, Llc | Method for operating a surgical instrument |
US10426469B2 (en) | 2016-04-18 | 2019-10-01 | Ethicon Llc | Surgical instrument comprising a primary firing lockout and a secondary firing lockout |
US11317917B2 (en) | 2016-04-18 | 2022-05-03 | Cilag Gmbh International | Surgical stapling system comprising a lockable firing assembly |
GB201609463D0 (en) | 2016-05-30 | 2016-07-13 | Landa Labs 2012 Ltd | Method of manufacturing a multi-layer article |
US10933661B2 (en) | 2016-05-30 | 2021-03-02 | Landa Corporation Ltd. | Digital printing process |
WO2017222812A1 (en) | 2016-06-20 | 2017-12-28 | 3M Innovative Properties Company | Self-priming adhesive |
USD826405S1 (en) | 2016-06-24 | 2018-08-21 | Ethicon Llc | Surgical fastener |
USD850617S1 (en) | 2016-06-24 | 2019-06-04 | Ethicon Llc | Surgical fastener cartridge |
USD847989S1 (en) | 2016-06-24 | 2019-05-07 | Ethicon Llc | Surgical fastener cartridge |
US10702270B2 (en) | 2016-06-24 | 2020-07-07 | Ethicon Llc | Stapling system for use with wire staples and stamped staples |
CN109310431B (en) | 2016-06-24 | 2022-03-04 | 伊西康有限责任公司 | Staple cartridge comprising wire staples and punch staples |
US10667809B2 (en) | 2016-12-21 | 2020-06-02 | Ethicon Llc | Staple cartridge and staple cartridge channel comprising windows defined therein |
US10893864B2 (en) | 2016-12-21 | 2021-01-19 | Ethicon | Staple cartridges and arrangements of staples and staple cavities therein |
US20180168619A1 (en) | 2016-12-21 | 2018-06-21 | Ethicon Endo-Surgery, Llc | Surgical stapling systems |
US10568626B2 (en) | 2016-12-21 | 2020-02-25 | Ethicon Llc | Surgical instruments with jaw opening features for increasing a jaw opening distance |
CN110087565A (en) | 2016-12-21 | 2019-08-02 | 爱惜康有限责任公司 | Surgical stapling system |
US10835245B2 (en) | 2016-12-21 | 2020-11-17 | Ethicon Llc | Method for attaching a shaft assembly to a surgical instrument and, alternatively, to a surgical robot |
US20180168615A1 (en) | 2016-12-21 | 2018-06-21 | Ethicon Endo-Surgery, Llc | Method of deforming staples from two different types of staple cartridges with the same surgical stapling instrument |
JP7010956B2 (en) | 2016-12-21 | 2022-01-26 | エシコン エルエルシー | How to staple tissue |
US10993715B2 (en) | 2016-12-21 | 2021-05-04 | Ethicon Llc | Staple cartridge comprising staples with different clamping breadths |
CN110099619B (en) | 2016-12-21 | 2022-07-15 | 爱惜康有限责任公司 | Lockout device for surgical end effector and replaceable tool assembly |
US10758230B2 (en) | 2016-12-21 | 2020-09-01 | Ethicon Llc | Surgical instrument with primary and safety processors |
US11684367B2 (en) | 2016-12-21 | 2023-06-27 | Cilag Gmbh International | Stepped assembly having and end-of-life indicator |
US10675026B2 (en) | 2016-12-21 | 2020-06-09 | Ethicon Llc | Methods of stapling tissue |
US11160551B2 (en) | 2016-12-21 | 2021-11-02 | Cilag Gmbh International | Articulatable surgical stapling instruments |
US11419606B2 (en) | 2016-12-21 | 2022-08-23 | Cilag Gmbh International | Shaft assembly comprising a clutch configured to adapt the output of a rotary firing member to two different systems |
US11134942B2 (en) | 2016-12-21 | 2021-10-05 | Cilag Gmbh International | Surgical stapling instruments and staple-forming anvils |
US10426471B2 (en) | 2016-12-21 | 2019-10-01 | Ethicon Llc | Surgical instrument with multiple failure response modes |
US10945727B2 (en) | 2016-12-21 | 2021-03-16 | Ethicon Llc | Staple cartridge with deformable driver retention features |
US10898186B2 (en) | 2016-12-21 | 2021-01-26 | Ethicon Llc | Staple forming pocket arrangements comprising primary sidewalls and pocket sidewalls |
US10537324B2 (en) | 2016-12-21 | 2020-01-21 | Ethicon Llc | Stepped staple cartridge with asymmetrical staples |
US10856868B2 (en) | 2016-12-21 | 2020-12-08 | Ethicon Llc | Firing member pin configurations |
US10758229B2 (en) | 2016-12-21 | 2020-09-01 | Ethicon Llc | Surgical instrument comprising improved jaw control |
US10687810B2 (en) | 2016-12-21 | 2020-06-23 | Ethicon Llc | Stepped staple cartridge with tissue retention and gap setting features |
US10568624B2 (en) | 2016-12-21 | 2020-02-25 | Ethicon Llc | Surgical instruments with jaws that are pivotable about a fixed axis and include separate and distinct closure and firing systems |
US11517325B2 (en) | 2017-06-20 | 2022-12-06 | Cilag Gmbh International | Closed loop feedback control of motor velocity of a surgical stapling and cutting instrument based on measured displacement distance traveled over a specified time interval |
US10779820B2 (en) | 2017-06-20 | 2020-09-22 | Ethicon Llc | Systems and methods for controlling motor speed according to user input for a surgical instrument |
US10813639B2 (en) | 2017-06-20 | 2020-10-27 | Ethicon Llc | Closed loop feedback control of motor velocity of a surgical stapling and cutting instrument based on system conditions |
USD890784S1 (en) | 2017-06-20 | 2020-07-21 | Ethicon Llc | Display panel with changeable graphical user interface |
US11653914B2 (en) | 2017-06-20 | 2023-05-23 | Cilag Gmbh International | Systems and methods for controlling motor velocity of a surgical stapling and cutting instrument according to articulation angle of end effector |
US10646220B2 (en) | 2017-06-20 | 2020-05-12 | Ethicon Llc | Systems and methods for controlling displacement member velocity for a surgical instrument |
US10327767B2 (en) | 2017-06-20 | 2019-06-25 | Ethicon Llc | Control of motor velocity of a surgical stapling and cutting instrument based on angle of articulation |
US11071554B2 (en) | 2017-06-20 | 2021-07-27 | Cilag Gmbh International | Closed loop feedback control of motor velocity of a surgical stapling and cutting instrument based on magnitude of velocity error measurements |
US10390841B2 (en) | 2017-06-20 | 2019-08-27 | Ethicon Llc | Control of motor velocity of a surgical stapling and cutting instrument based on angle of articulation |
US10881396B2 (en) | 2017-06-20 | 2021-01-05 | Ethicon Llc | Surgical instrument with variable duration trigger arrangement |
USD879808S1 (en) | 2017-06-20 | 2020-03-31 | Ethicon Llc | Display panel with graphical user interface |
US11382638B2 (en) | 2017-06-20 | 2022-07-12 | Cilag Gmbh International | Closed loop feedback control of motor velocity of a surgical stapling and cutting instrument based on measured time over a specified displacement distance |
US11090046B2 (en) | 2017-06-20 | 2021-08-17 | Cilag Gmbh International | Systems and methods for controlling displacement member motion of a surgical stapling and cutting instrument |
US10624633B2 (en) | 2017-06-20 | 2020-04-21 | Ethicon Llc | Systems and methods for controlling motor velocity of a surgical stapling and cutting instrument |
US10368864B2 (en) | 2017-06-20 | 2019-08-06 | Ethicon Llc | Systems and methods for controlling displaying motor velocity for a surgical instrument |
US10881399B2 (en) | 2017-06-20 | 2021-01-05 | Ethicon Llc | Techniques for adaptive control of motor velocity of a surgical stapling and cutting instrument |
USD879809S1 (en) | 2017-06-20 | 2020-03-31 | Ethicon Llc | Display panel with changeable graphical user interface |
US10307170B2 (en) | 2017-06-20 | 2019-06-04 | Ethicon Llc | Method for closed loop control of motor velocity of a surgical stapling and cutting instrument |
US10980537B2 (en) | 2017-06-20 | 2021-04-20 | Ethicon Llc | Closed loop feedback control of motor velocity of a surgical stapling and cutting instrument based on measured time over a specified number of shaft rotations |
US10888321B2 (en) | 2017-06-20 | 2021-01-12 | Ethicon Llc | Systems and methods for controlling velocity of a displacement member of a surgical stapling and cutting instrument |
US10856869B2 (en) | 2017-06-27 | 2020-12-08 | Ethicon Llc | Surgical anvil arrangements |
US11266405B2 (en) | 2017-06-27 | 2022-03-08 | Cilag Gmbh International | Surgical anvil manufacturing methods |
US10772629B2 (en) | 2017-06-27 | 2020-09-15 | Ethicon Llc | Surgical anvil arrangements |
US10993716B2 (en) | 2017-06-27 | 2021-05-04 | Ethicon Llc | Surgical anvil arrangements |
US11324503B2 (en) | 2017-06-27 | 2022-05-10 | Cilag Gmbh International | Surgical firing member arrangements |
US11141154B2 (en) | 2017-06-27 | 2021-10-12 | Cilag Gmbh International | Surgical end effectors and anvils |
US11058424B2 (en) | 2017-06-28 | 2021-07-13 | Cilag Gmbh International | Surgical instrument comprising an offset articulation joint |
US11246592B2 (en) | 2017-06-28 | 2022-02-15 | Cilag Gmbh International | Surgical instrument comprising an articulation system lockable to a frame |
US10716614B2 (en) | 2017-06-28 | 2020-07-21 | Ethicon Llc | Surgical shaft assemblies with slip ring assemblies with increased contact pressure |
USD869655S1 (en) | 2017-06-28 | 2019-12-10 | Ethicon Llc | Surgical fastener cartridge |
EP4070740A1 (en) | 2017-06-28 | 2022-10-12 | Cilag GmbH International | Surgical instrument comprising selectively actuatable rotatable couplers |
US11564686B2 (en) | 2017-06-28 | 2023-01-31 | Cilag Gmbh International | Surgical shaft assemblies with flexible interfaces |
US11259805B2 (en) | 2017-06-28 | 2022-03-01 | Cilag Gmbh International | Surgical instrument comprising firing member supports |
US10588633B2 (en) | 2017-06-28 | 2020-03-17 | Ethicon Llc | Surgical instruments with open and closable jaws and axially movable firing member that is initially parked in close proximity to the jaws prior to firing |
USD851762S1 (en) | 2017-06-28 | 2019-06-18 | Ethicon Llc | Anvil |
US10765427B2 (en) | 2017-06-28 | 2020-09-08 | Ethicon Llc | Method for articulating a surgical instrument |
US10211586B2 (en) | 2017-06-28 | 2019-02-19 | Ethicon Llc | Surgical shaft assemblies with watertight housings |
USD854151S1 (en) | 2017-06-28 | 2019-07-16 | Ethicon Llc | Surgical instrument shaft |
USD906355S1 (en) | 2017-06-28 | 2020-12-29 | Ethicon Llc | Display screen or portion thereof with a graphical user interface for a surgical instrument |
US10903685B2 (en) | 2017-06-28 | 2021-01-26 | Ethicon Llc | Surgical shaft assemblies with slip ring assemblies forming capacitive channels |
US10398434B2 (en) | 2017-06-29 | 2019-09-03 | Ethicon Llc | Closed loop velocity control of closure member for robotic surgical instrument |
US10932772B2 (en) | 2017-06-29 | 2021-03-02 | Ethicon Llc | Methods for closed loop velocity control for robotic surgical instrument |
US11007022B2 (en) | 2017-06-29 | 2021-05-18 | Ethicon Llc | Closed loop velocity control techniques based on sensed tissue parameters for robotic surgical instrument |
US10898183B2 (en) | 2017-06-29 | 2021-01-26 | Ethicon Llc | Robotic surgical instrument with closed loop feedback techniques for advancement of closure member during firing |
US10258418B2 (en) | 2017-06-29 | 2019-04-16 | Ethicon Llc | System for controlling articulation forces |
US11944300B2 (en) | 2017-08-03 | 2024-04-02 | Cilag Gmbh International | Method for operating a surgical system bailout |
US11304695B2 (en) | 2017-08-03 | 2022-04-19 | Cilag Gmbh International | Surgical system shaft interconnection |
US11471155B2 (en) | 2017-08-03 | 2022-10-18 | Cilag Gmbh International | Surgical system bailout |
US10434764B1 (en) | 2017-09-06 | 2019-10-08 | Landa Corporation Ltd. | YAW measurement by spectral analysis |
USD907648S1 (en) | 2017-09-29 | 2021-01-12 | Ethicon Llc | Display screen or portion thereof with animated graphical user interface |
USD907647S1 (en) | 2017-09-29 | 2021-01-12 | Ethicon Llc | Display screen or portion thereof with animated graphical user interface |
US10765429B2 (en) | 2017-09-29 | 2020-09-08 | Ethicon Llc | Systems and methods for providing alerts according to the operational state of a surgical instrument |
US10743872B2 (en) | 2017-09-29 | 2020-08-18 | Ethicon Llc | System and methods for controlling a display of a surgical instrument |
US11399829B2 (en) | 2017-09-29 | 2022-08-02 | Cilag Gmbh International | Systems and methods of initiating a power shutdown mode for a surgical instrument |
USD917500S1 (en) | 2017-09-29 | 2021-04-27 | Ethicon Llc | Display screen or portion thereof with graphical user interface |
US10729501B2 (en) | 2017-09-29 | 2020-08-04 | Ethicon Llc | Systems and methods for language selection of a surgical instrument |
US10796471B2 (en) | 2017-09-29 | 2020-10-06 | Ethicon Llc | Systems and methods of displaying a knife position for a surgical instrument |
CN111212736B (en) | 2017-10-19 | 2021-11-23 | 兰达公司 | Endless flexible belt for a printing system |
US11090075B2 (en) | 2017-10-30 | 2021-08-17 | Cilag Gmbh International | Articulation features for surgical end effector |
US11134944B2 (en) | 2017-10-30 | 2021-10-05 | Cilag Gmbh International | Surgical stapler knife motion controls |
US10842490B2 (en) | 2017-10-31 | 2020-11-24 | Ethicon Llc | Cartridge body design with force reduction based on firing completion |
US10779903B2 (en) | 2017-10-31 | 2020-09-22 | Ethicon Llc | Positive shaft rotation lock activated by jaw closure |
US10410100B1 (en) | 2017-11-14 | 2019-09-10 | Landa Corporation Ltd. | AM Screening |
WO2019097464A1 (en) | 2017-11-19 | 2019-05-23 | Landa Corporation Ltd. | Digital printing system |
US11511536B2 (en) | 2017-11-27 | 2022-11-29 | Landa Corporation Ltd. | Calibration of runout error in a digital printing system |
US11707943B2 (en) | 2017-12-06 | 2023-07-25 | Landa Corporation Ltd. | Method and apparatus for digital printing |
WO2019111223A1 (en) | 2017-12-07 | 2019-06-13 | Landa Corporation Ltd. | Digital printing process and method |
US10779826B2 (en) | 2017-12-15 | 2020-09-22 | Ethicon Llc | Methods of operating surgical end effectors |
US10743875B2 (en) | 2017-12-15 | 2020-08-18 | Ethicon Llc | Surgical end effectors with jaw stiffener arrangements configured to permit monitoring of firing member |
US10687813B2 (en) | 2017-12-15 | 2020-06-23 | Ethicon Llc | Adapters with firing stroke sensing arrangements for use in connection with electromechanical surgical instruments |
US10966718B2 (en) | 2017-12-15 | 2021-04-06 | Ethicon Llc | Dynamic clamping assemblies with improved wear characteristics for use in connection with electromechanical surgical instruments |
US10869666B2 (en) | 2017-12-15 | 2020-12-22 | Ethicon Llc | Adapters with control systems for controlling multiple motors of an electromechanical surgical instrument |
US11033267B2 (en) | 2017-12-15 | 2021-06-15 | Ethicon Llc | Systems and methods of controlling a clamping member firing rate of a surgical instrument |
US10743874B2 (en) | 2017-12-15 | 2020-08-18 | Ethicon Llc | Sealed adapters for use with electromechanical surgical instruments |
US10828033B2 (en) | 2017-12-15 | 2020-11-10 | Ethicon Llc | Handheld electromechanical surgical instruments with improved motor control arrangements for positioning components of an adapter coupled thereto |
US10779825B2 (en) | 2017-12-15 | 2020-09-22 | Ethicon Llc | Adapters with end effector position sensing and control arrangements for use in connection with electromechanical surgical instruments |
US11197670B2 (en) | 2017-12-15 | 2021-12-14 | Cilag Gmbh International | Surgical end effectors with pivotal jaws configured to touch at their respective distal ends when fully closed |
US11071543B2 (en) | 2017-12-15 | 2021-07-27 | Cilag Gmbh International | Surgical end effectors with clamping assemblies configured to increase jaw aperture ranges |
US11006955B2 (en) | 2017-12-15 | 2021-05-18 | Ethicon Llc | End effectors with positive jaw opening features for use with adapters for electromechanical surgical instruments |
CN111601858B (en) * | 2017-12-18 | 2022-06-21 | 3M创新有限公司 | Fluorinated elastomers cured by actinic radiation and methods thereof |
US10716565B2 (en) | 2017-12-19 | 2020-07-21 | Ethicon Llc | Surgical instruments with dual articulation drivers |
US10729509B2 (en) | 2017-12-19 | 2020-08-04 | Ethicon Llc | Surgical instrument comprising closure and firing locking mechanism |
US11020112B2 (en) | 2017-12-19 | 2021-06-01 | Ethicon Llc | Surgical tools configured for interchangeable use with different controller interfaces |
US11045270B2 (en) | 2017-12-19 | 2021-06-29 | Cilag Gmbh International | Robotic attachment comprising exterior drive actuator |
USD910847S1 (en) | 2017-12-19 | 2021-02-16 | Ethicon Llc | Surgical instrument assembly |
US10835330B2 (en) | 2017-12-19 | 2020-11-17 | Ethicon Llc | Method for determining the position of a rotatable jaw of a surgical instrument attachment assembly |
US11129680B2 (en) | 2017-12-21 | 2021-09-28 | Cilag Gmbh International | Surgical instrument comprising a projector |
US11583274B2 (en) | 2017-12-21 | 2023-02-21 | Cilag Gmbh International | Self-guiding stapling instrument |
US11076853B2 (en) | 2017-12-21 | 2021-08-03 | Cilag Gmbh International | Systems and methods of displaying a knife position during transection for a surgical instrument |
US11311290B2 (en) | 2017-12-21 | 2022-04-26 | Cilag Gmbh International | Surgical instrument comprising an end effector dampener |
WO2019239320A1 (en) | 2018-06-12 | 2019-12-19 | 3M Innovative Properties Company | Fluoropolymer compositions comprising fluorinated additives, coated substrates and methods |
CN112399918B (en) | 2018-06-26 | 2023-01-31 | 兰达公司 | Intermediate transmission member of digital printing system |
US10994528B1 (en) | 2018-08-02 | 2021-05-04 | Landa Corporation Ltd. | Digital printing system with flexible intermediate transfer member |
US11324501B2 (en) | 2018-08-20 | 2022-05-10 | Cilag Gmbh International | Surgical stapling devices with improved closure members |
USD914878S1 (en) | 2018-08-20 | 2021-03-30 | Ethicon Llc | Surgical instrument anvil |
US10779821B2 (en) | 2018-08-20 | 2020-09-22 | Ethicon Llc | Surgical stapler anvils with tissue stop features configured to avoid tissue pinch |
US11083458B2 (en) | 2018-08-20 | 2021-08-10 | Cilag Gmbh International | Powered surgical instruments with clutching arrangements to convert linear drive motions to rotary drive motions |
US11207065B2 (en) | 2018-08-20 | 2021-12-28 | Cilag Gmbh International | Method for fabricating surgical stapler anvils |
US10856870B2 (en) | 2018-08-20 | 2020-12-08 | Ethicon Llc | Switching arrangements for motor powered articulatable surgical instruments |
US11291440B2 (en) | 2018-08-20 | 2022-04-05 | Cilag Gmbh International | Method for operating a powered articulatable surgical instrument |
US10842492B2 (en) | 2018-08-20 | 2020-11-24 | Ethicon Llc | Powered articulatable surgical instruments with clutching and locking arrangements for linking an articulation drive system to a firing drive system |
US10912559B2 (en) | 2018-08-20 | 2021-02-09 | Ethicon Llc | Reinforced deformable anvil tip for surgical stapler anvil |
US11039834B2 (en) | 2018-08-20 | 2021-06-22 | Cilag Gmbh International | Surgical stapler anvils with staple directing protrusions and tissue stability features |
US11045192B2 (en) | 2018-08-20 | 2021-06-29 | Cilag Gmbh International | Fabricating techniques for surgical stapler anvils |
US11253256B2 (en) | 2018-08-20 | 2022-02-22 | Cilag Gmbh International | Articulatable motor powered surgical instruments with dedicated articulation motor arrangements |
US11318734B2 (en) | 2018-10-08 | 2022-05-03 | Landa Corporation Ltd. | Friction reduction means for printing systems and method |
WO2020099945A1 (en) | 2018-11-15 | 2020-05-22 | Landa Corporation Ltd. | Pulse waveforms for ink jet printing |
US20220112319A1 (en) * | 2018-11-29 | 2022-04-14 | 3M Innovative Properties Company | Composite film, method of making the same, and article including the same |
EP3902680A4 (en) | 2018-12-24 | 2022-08-31 | Landa Corporation Ltd. | A digital printing system |
EP3902684A4 (en) | 2018-12-27 | 2022-09-14 | Saint-Gobain Performance Plastics Corporation | Printer assembly low friction roller liner |
WO2020139640A1 (en) | 2018-12-27 | 2020-07-02 | Saint-Gobain Performance Plastics Corporation | Solenoid low friction bearing liner |
US11172929B2 (en) | 2019-03-25 | 2021-11-16 | Cilag Gmbh International | Articulation drive arrangements for surgical systems |
US11696761B2 (en) | 2019-03-25 | 2023-07-11 | Cilag Gmbh International | Firing drive arrangements for surgical systems |
US11147551B2 (en) | 2019-03-25 | 2021-10-19 | Cilag Gmbh International | Firing drive arrangements for surgical systems |
US11147553B2 (en) | 2019-03-25 | 2021-10-19 | Cilag Gmbh International | Firing drive arrangements for surgical systems |
US11452528B2 (en) | 2019-04-30 | 2022-09-27 | Cilag Gmbh International | Articulation actuators for a surgical instrument |
US11648009B2 (en) | 2019-04-30 | 2023-05-16 | Cilag Gmbh International | Rotatable jaw tip for a surgical instrument |
US11432816B2 (en) | 2019-04-30 | 2022-09-06 | Cilag Gmbh International | Articulation pin for a surgical instrument |
US11426251B2 (en) | 2019-04-30 | 2022-08-30 | Cilag Gmbh International | Articulation directional lights on a surgical instrument |
US11903581B2 (en) | 2019-04-30 | 2024-02-20 | Cilag Gmbh International | Methods for stapling tissue using a surgical instrument |
US11253254B2 (en) | 2019-04-30 | 2022-02-22 | Cilag Gmbh International | Shaft rotation actuator on a surgical instrument |
US11471157B2 (en) | 2019-04-30 | 2022-10-18 | Cilag Gmbh International | Articulation control mapping for a surgical instrument |
US11298132B2 (en) | 2019-06-28 | 2022-04-12 | Cilag GmbH Inlernational | Staple cartridge including a honeycomb extension |
US11627959B2 (en) | 2019-06-28 | 2023-04-18 | Cilag Gmbh International | Surgical instruments including manual and powered system lockouts |
US11051807B2 (en) | 2019-06-28 | 2021-07-06 | Cilag Gmbh International | Packaging assembly including a particulate trap |
US11259803B2 (en) | 2019-06-28 | 2022-03-01 | Cilag Gmbh International | Surgical stapling system having an information encryption protocol |
US11298127B2 (en) | 2019-06-28 | 2022-04-12 | Cilag GmbH Interational | Surgical stapling system having a lockout mechanism for an incompatible cartridge |
US11399837B2 (en) | 2019-06-28 | 2022-08-02 | Cilag Gmbh International | Mechanisms for motor control adjustments of a motorized surgical instrument |
US11376098B2 (en) | 2019-06-28 | 2022-07-05 | Cilag Gmbh International | Surgical instrument system comprising an RFID system |
US11660163B2 (en) | 2019-06-28 | 2023-05-30 | Cilag Gmbh International | Surgical system with RFID tags for updating motor assembly parameters |
US11291451B2 (en) | 2019-06-28 | 2022-04-05 | Cilag Gmbh International | Surgical instrument with battery compatibility verification functionality |
US11478241B2 (en) | 2019-06-28 | 2022-10-25 | Cilag Gmbh International | Staple cartridge including projections |
US11241235B2 (en) | 2019-06-28 | 2022-02-08 | Cilag Gmbh International | Method of using multiple RFID chips with a surgical assembly |
US11224497B2 (en) | 2019-06-28 | 2022-01-18 | Cilag Gmbh International | Surgical systems with multiple RFID tags |
US11426167B2 (en) | 2019-06-28 | 2022-08-30 | Cilag Gmbh International | Mechanisms for proper anvil attachment surgical stapling head assembly |
US11464601B2 (en) | 2019-06-28 | 2022-10-11 | Cilag Gmbh International | Surgical instrument comprising an RFID system for tracking a movable component |
US11638587B2 (en) | 2019-06-28 | 2023-05-02 | Cilag Gmbh International | RFID identification systems for surgical instruments |
US11497492B2 (en) | 2019-06-28 | 2022-11-15 | Cilag Gmbh International | Surgical instrument including an articulation lock |
US11771419B2 (en) | 2019-06-28 | 2023-10-03 | Cilag Gmbh International | Packaging for a replaceable component of a surgical stapling system |
US11523822B2 (en) | 2019-06-28 | 2022-12-13 | Cilag Gmbh International | Battery pack including a circuit interrupter |
US11684434B2 (en) | 2019-06-28 | 2023-06-27 | Cilag Gmbh International | Surgical RFID assemblies for instrument operational setting control |
US11246678B2 (en) | 2019-06-28 | 2022-02-15 | Cilag Gmbh International | Surgical stapling system having a frangible RFID tag |
US11219455B2 (en) | 2019-06-28 | 2022-01-11 | Cilag Gmbh International | Surgical instrument including a lockout key |
US11553971B2 (en) | 2019-06-28 | 2023-01-17 | Cilag Gmbh International | Surgical RFID assemblies for display and communication |
WO2021088198A1 (en) | 2019-11-04 | 2021-05-14 | 3M Innovative Properties Company | Electronic telecommunications articles comprising crosslinked fluoropolymers and methods |
WO2021090147A1 (en) | 2019-11-07 | 2021-05-14 | 3M Innovative Properties Company | Bonding highly-fluorinated plastics to elastomers using silane-based primers |
EP4066064A4 (en) | 2019-11-25 | 2024-01-10 | Landa Corp Ltd | Drying ink in digital printing using infrared radiation absorbed by particles embedded inside itm |
US11321028B2 (en) | 2019-12-11 | 2022-05-03 | Landa Corporation Ltd. | Correcting registration errors in digital printing |
US11464512B2 (en) | 2019-12-19 | 2022-10-11 | Cilag Gmbh International | Staple cartridge comprising a curved deck surface |
US11446029B2 (en) | 2019-12-19 | 2022-09-20 | Cilag Gmbh International | Staple cartridge comprising projections extending from a curved deck surface |
US11234698B2 (en) | 2019-12-19 | 2022-02-01 | Cilag Gmbh International | Stapling system comprising a clamp lockout and a firing lockout |
US11911032B2 (en) | 2019-12-19 | 2024-02-27 | Cilag Gmbh International | Staple cartridge comprising a seating cam |
US11304696B2 (en) | 2019-12-19 | 2022-04-19 | Cilag Gmbh International | Surgical instrument comprising a powered articulation system |
US11931033B2 (en) | 2019-12-19 | 2024-03-19 | Cilag Gmbh International | Staple cartridge comprising a latch lockout |
US11607219B2 (en) | 2019-12-19 | 2023-03-21 | Cilag Gmbh International | Staple cartridge comprising a detachable tissue cutting knife |
US11576672B2 (en) | 2019-12-19 | 2023-02-14 | Cilag Gmbh International | Surgical instrument comprising a closure system including a closure member and an opening member driven by a drive screw |
US11701111B2 (en) | 2019-12-19 | 2023-07-18 | Cilag Gmbh International | Method for operating a surgical stapling instrument |
US11529139B2 (en) | 2019-12-19 | 2022-12-20 | Cilag Gmbh International | Motor driven surgical instrument |
US11844520B2 (en) | 2019-12-19 | 2023-12-19 | Cilag Gmbh International | Staple cartridge comprising driver retention members |
US11529137B2 (en) | 2019-12-19 | 2022-12-20 | Cilag Gmbh International | Staple cartridge comprising driver retention members |
US11291447B2 (en) | 2019-12-19 | 2022-04-05 | Cilag Gmbh International | Stapling instrument comprising independent jaw closing and staple firing systems |
US11504122B2 (en) | 2019-12-19 | 2022-11-22 | Cilag Gmbh International | Surgical instrument comprising a nested firing member |
US11559304B2 (en) | 2019-12-19 | 2023-01-24 | Cilag Gmbh International | Surgical instrument comprising a rapid closure mechanism |
USD975851S1 (en) | 2020-06-02 | 2023-01-17 | Cilag Gmbh International | Staple cartridge |
USD975850S1 (en) | 2020-06-02 | 2023-01-17 | Cilag Gmbh International | Staple cartridge |
USD966512S1 (en) | 2020-06-02 | 2022-10-11 | Cilag Gmbh International | Staple cartridge |
USD967421S1 (en) | 2020-06-02 | 2022-10-18 | Cilag Gmbh International | Staple cartridge |
USD976401S1 (en) | 2020-06-02 | 2023-01-24 | Cilag Gmbh International | Staple cartridge |
USD975278S1 (en) | 2020-06-02 | 2023-01-10 | Cilag Gmbh International | Staple cartridge |
USD974560S1 (en) | 2020-06-02 | 2023-01-03 | Cilag Gmbh International | Staple cartridge |
US20220031320A1 (en) | 2020-07-28 | 2022-02-03 | Cilag Gmbh International | Surgical instruments with flexible firing member actuator constraint arrangements |
US11931025B2 (en) | 2020-10-29 | 2024-03-19 | Cilag Gmbh International | Surgical instrument comprising a releasable closure drive lock |
US11517390B2 (en) | 2020-10-29 | 2022-12-06 | Cilag Gmbh International | Surgical instrument comprising a limited travel switch |
US11896217B2 (en) | 2020-10-29 | 2024-02-13 | Cilag Gmbh International | Surgical instrument comprising an articulation lock |
USD980425S1 (en) | 2020-10-29 | 2023-03-07 | Cilag Gmbh International | Surgical instrument assembly |
US11617577B2 (en) | 2020-10-29 | 2023-04-04 | Cilag Gmbh International | Surgical instrument comprising a sensor configured to sense whether an articulation drive of the surgical instrument is actuatable |
US11534259B2 (en) | 2020-10-29 | 2022-12-27 | Cilag Gmbh International | Surgical instrument comprising an articulation indicator |
US11717289B2 (en) | 2020-10-29 | 2023-08-08 | Cilag Gmbh International | Surgical instrument comprising an indicator which indicates that an articulation drive is actuatable |
US11452526B2 (en) | 2020-10-29 | 2022-09-27 | Cilag Gmbh International | Surgical instrument comprising a staged voltage regulation start-up system |
USD1013170S1 (en) | 2020-10-29 | 2024-01-30 | Cilag Gmbh International | Surgical instrument assembly |
US11779330B2 (en) | 2020-10-29 | 2023-10-10 | Cilag Gmbh International | Surgical instrument comprising a jaw alignment system |
US11844518B2 (en) | 2020-10-29 | 2023-12-19 | Cilag Gmbh International | Method for operating a surgical instrument |
US11890010B2 (en) | 2020-12-02 | 2024-02-06 | Cllag GmbH International | Dual-sided reinforced reload for surgical instruments |
US11944296B2 (en) | 2020-12-02 | 2024-04-02 | Cilag Gmbh International | Powered surgical instruments with external connectors |
US11678882B2 (en) | 2020-12-02 | 2023-06-20 | Cilag Gmbh International | Surgical instruments with interactive features to remedy incidental sled movements |
US11849943B2 (en) | 2020-12-02 | 2023-12-26 | Cilag Gmbh International | Surgical instrument with cartridge release mechanisms |
US11737751B2 (en) | 2020-12-02 | 2023-08-29 | Cilag Gmbh International | Devices and methods of managing energy dissipated within sterile barriers of surgical instrument housings |
US11744581B2 (en) | 2020-12-02 | 2023-09-05 | Cilag Gmbh International | Powered surgical instruments with multi-phase tissue treatment |
US11653920B2 (en) | 2020-12-02 | 2023-05-23 | Cilag Gmbh International | Powered surgical instruments with communication interfaces through sterile barrier |
US11653915B2 (en) | 2020-12-02 | 2023-05-23 | Cilag Gmbh International | Surgical instruments with sled location detection and adjustment features |
US11627960B2 (en) | 2020-12-02 | 2023-04-18 | Cilag Gmbh International | Powered surgical instruments with smart reload with separately attachable exteriorly mounted wiring connections |
US11730473B2 (en) | 2021-02-26 | 2023-08-22 | Cilag Gmbh International | Monitoring of manufacturing life-cycle |
US11744583B2 (en) | 2021-02-26 | 2023-09-05 | Cilag Gmbh International | Distal communication array to tune frequency of RF systems |
US11925349B2 (en) | 2021-02-26 | 2024-03-12 | Cilag Gmbh International | Adjustment to transfer parameters to improve available power |
US11793514B2 (en) | 2021-02-26 | 2023-10-24 | Cilag Gmbh International | Staple cartridge comprising sensor array which may be embedded in cartridge body |
US11701113B2 (en) | 2021-02-26 | 2023-07-18 | Cilag Gmbh International | Stapling instrument comprising a separate power antenna and a data transfer antenna |
US11950777B2 (en) | 2021-02-26 | 2024-04-09 | Cilag Gmbh International | Staple cartridge comprising an information access control system |
US11812964B2 (en) | 2021-02-26 | 2023-11-14 | Cilag Gmbh International | Staple cartridge comprising a power management circuit |
US11696757B2 (en) | 2021-02-26 | 2023-07-11 | Cilag Gmbh International | Monitoring of internal systems to detect and track cartridge motion status |
US11723657B2 (en) | 2021-02-26 | 2023-08-15 | Cilag Gmbh International | Adjustable communication based on available bandwidth and power capacity |
US11749877B2 (en) | 2021-02-26 | 2023-09-05 | Cilag Gmbh International | Stapling instrument comprising a signal antenna |
US11751869B2 (en) | 2021-02-26 | 2023-09-12 | Cilag Gmbh International | Monitoring of multiple sensors over time to detect moving characteristics of tissue |
US11950779B2 (en) | 2021-02-26 | 2024-04-09 | Cilag Gmbh International | Method of powering and communicating with a staple cartridge |
US11717291B2 (en) | 2021-03-22 | 2023-08-08 | Cilag Gmbh International | Staple cartridge comprising staples configured to apply different tissue compression |
US11826042B2 (en) | 2021-03-22 | 2023-11-28 | Cilag Gmbh International | Surgical instrument comprising a firing drive including a selectable leverage mechanism |
US11759202B2 (en) | 2021-03-22 | 2023-09-19 | Cilag Gmbh International | Staple cartridge comprising an implantable layer |
US11723658B2 (en) | 2021-03-22 | 2023-08-15 | Cilag Gmbh International | Staple cartridge comprising a firing lockout |
US11806011B2 (en) | 2021-03-22 | 2023-11-07 | Cilag Gmbh International | Stapling instrument comprising tissue compression systems |
US11826012B2 (en) | 2021-03-22 | 2023-11-28 | Cilag Gmbh International | Stapling instrument comprising a pulsed motor-driven firing rack |
US11737749B2 (en) | 2021-03-22 | 2023-08-29 | Cilag Gmbh International | Surgical stapling instrument comprising a retraction system |
US11793516B2 (en) | 2021-03-24 | 2023-10-24 | Cilag Gmbh International | Surgical staple cartridge comprising longitudinal support beam |
US11857183B2 (en) | 2021-03-24 | 2024-01-02 | Cilag Gmbh International | Stapling assembly components having metal substrates and plastic bodies |
US11896218B2 (en) | 2021-03-24 | 2024-02-13 | Cilag Gmbh International | Method of using a powered stapling device |
US11849945B2 (en) | 2021-03-24 | 2023-12-26 | Cilag Gmbh International | Rotary-driven surgical stapling assembly comprising eccentrically driven firing member |
US11896219B2 (en) | 2021-03-24 | 2024-02-13 | Cilag Gmbh International | Mating features between drivers and underside of a cartridge deck |
US11849944B2 (en) | 2021-03-24 | 2023-12-26 | Cilag Gmbh International | Drivers for fastener cartridge assemblies having rotary drive screws |
US11786239B2 (en) | 2021-03-24 | 2023-10-17 | Cilag Gmbh International | Surgical instrument articulation joint arrangements comprising multiple moving linkage features |
US11786243B2 (en) | 2021-03-24 | 2023-10-17 | Cilag Gmbh International | Firing members having flexible portions for adapting to a load during a surgical firing stroke |
US11744603B2 (en) | 2021-03-24 | 2023-09-05 | Cilag Gmbh International | Multi-axis pivot joints for surgical instruments and methods for manufacturing same |
US11903582B2 (en) | 2021-03-24 | 2024-02-20 | Cilag Gmbh International | Leveraging surfaces for cartridge installation |
US11832816B2 (en) | 2021-03-24 | 2023-12-05 | Cilag Gmbh International | Surgical stapling assembly comprising nonplanar staples and planar staples |
US11944336B2 (en) | 2021-03-24 | 2024-04-02 | Cilag Gmbh International | Joint arrangements for multi-planar alignment and support of operational drive shafts in articulatable surgical instruments |
US11826047B2 (en) | 2021-05-28 | 2023-11-28 | Cilag Gmbh International | Stapling instrument comprising jaw mounts |
US11877745B2 (en) | 2021-10-18 | 2024-01-23 | Cilag Gmbh International | Surgical stapling assembly having longitudinally-repeating staple leg clusters |
US11957337B2 (en) | 2021-10-18 | 2024-04-16 | Cilag Gmbh International | Surgical stapling assembly with offset ramped drive surfaces |
US11937816B2 (en) | 2021-10-28 | 2024-03-26 | Cilag Gmbh International | Electrical lead arrangements for surgical instruments |
Family Cites Families (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2789063A (en) | 1954-03-26 | 1957-04-16 | Minnesota Mining & Mfg | Method of activating the surface of perfluorocarbon polymers and resultant article |
US3309425A (en) * | 1963-07-30 | 1967-03-14 | American Cyanamid Co | Thermoplastic resins containing phosphonium salts as flame-retardant agents |
US3563871A (en) | 1969-11-14 | 1971-02-16 | Ford Motor Co | Process for reducing the surface friction of an elastomer using radiation and an oxygen free atmosphere |
CA1053994A (en) | 1974-07-03 | 1979-05-08 | Amp Incorporated | Sensitization of polyimide polymer for electroless metal deposition |
US4186084A (en) | 1975-05-20 | 1980-01-29 | E. I. Du Pont De Nemours And Company | Hydrophilic fluoropolymers |
US4164463A (en) | 1975-05-20 | 1979-08-14 | E. I. Du Pont De Nemours And Company | Hydrophilic fluoropolymers |
US4151154A (en) * | 1976-09-29 | 1979-04-24 | Union Carbide Corporation | Silicon treated surfaces |
US4261800A (en) | 1977-08-15 | 1981-04-14 | Western Electric Co., Inc. | Method of selectively depositing a metal on a surface of a substrate |
US4233421A (en) | 1979-02-26 | 1980-11-11 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition containing sulfonium curing agents |
DE3024450A1 (en) | 1980-06-28 | 1982-01-28 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING AQUEOUS, COLLOIDAL DISPERSIONS OF TYPE TETRAFLUORETHYLENE ETHYLENE COPOLYMERS |
US4495247A (en) * | 1983-06-30 | 1985-01-22 | E. I. Du Pont De Nemours And Company | Primer coating composition of a fluorocarbon polymer and an amino alkyl alkoxy silane |
US5086123A (en) | 1984-02-27 | 1992-02-04 | Minnesota Mining And Manufacturing Company | Fluoroelastomer compositions containing fluoroaliphatic sulfonamides as curing agents |
US4613653A (en) | 1984-06-11 | 1986-09-23 | The Dow Chemical Company | Modification of polymers |
JPS6272775A (en) * | 1985-09-25 | 1987-04-03 | Nok Corp | Adhesive composition |
US4775449A (en) | 1986-12-29 | 1988-10-04 | General Electric Company | Treatment of a polyimide surface to improve the adhesion of metal deposited thereon |
US4824692A (en) | 1987-07-27 | 1989-04-25 | The Goodyear Tire & Rubber Company | Process for the surface treatment of unsaturated rubber by photochemical modification with alkyl halides |
JPH01225675A (en) | 1988-03-07 | 1989-09-08 | Dainippon Ink & Chem Inc | Finishing by coating |
JPH01225674A (en) | 1988-03-07 | 1989-09-08 | Sumitomo Metal Ind Ltd | Surface modification of steel sheet coated with fluorocarbon resin |
US4912171A (en) | 1988-04-01 | 1990-03-27 | Minnesota Mining And Manufacturing Company | Fluoroelastomer curing process with phosphonium compound |
US5141969A (en) * | 1988-11-21 | 1992-08-25 | Eastman Kodak Company | Onium salts and the use thereof as photoinitiators |
US5284611A (en) | 1989-06-22 | 1994-02-08 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition with improved bonding properties |
US5478652A (en) | 1989-06-22 | 1995-12-26 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition with improved bonding properties |
US5051312A (en) | 1990-03-29 | 1991-09-24 | E. I. Du Pont De Nemours And Company | Modification of polymer surfaces |
US5320789A (en) | 1991-11-06 | 1994-06-14 | Japan Atomic Energy Research Institute | Surface modification of fluorine resin with laser light |
JPH05339536A (en) | 1992-06-11 | 1993-12-21 | Minnesota Mining & Mfg Co <3M> | Fluorinated rubber composition for coating |
US5262490A (en) | 1992-08-24 | 1993-11-16 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition with organo-onium compounds |
JPH075773B2 (en) | 1992-12-22 | 1995-01-25 | 工業技術院長 | Surface modification method of fluoropolymer moldings using ultraviolet laser |
US5419968A (en) | 1993-02-16 | 1995-05-30 | Gunze Limited | Surface-hydrophilized fluororesin moldings and method of producing same |
EP0644227B1 (en) | 1993-03-23 | 2003-07-23 | Tokai University | Solid surface modifying method and apparatus |
US5285002A (en) | 1993-03-23 | 1994-02-08 | Minnesota Mining And Manufacturing Company | Fluorine-containing polymers and preparation and use thereof |
JP2612404B2 (en) | 1993-03-29 | 1997-05-21 | 浜松ホトニクス株式会社 | Method and apparatus for surface modification of fluororesin |
MY120404A (en) | 1993-10-15 | 2005-10-31 | Kuraishiki Boseki Kabushiki Kaisha | Process for modifying the surfaces of the molded materials made of fluorine resins |
JP3211532B2 (en) | 1993-12-21 | 2001-09-25 | ウシオ電機株式会社 | Plastics surface modification method |
JP3390763B2 (en) | 1993-12-24 | 2003-03-31 | オリンパス光学工業株式会社 | Surface modification method for resin tube |
JP3206310B2 (en) | 1994-07-01 | 2001-09-10 | ダイキン工業株式会社 | Surface-modified fluororesin molded product |
JP3814664B2 (en) | 1994-08-19 | 2006-08-30 | スリーエム カンパニー | Multilayer structure having a fluoropolymer layer |
US5656121A (en) | 1994-08-19 | 1997-08-12 | Minnesota Mining And Manufacturing Company | Method of making multi-layer composites having a fluoropolymer layer |
US5562991A (en) * | 1994-10-31 | 1996-10-08 | E. I. Du Pont De Nemours And Company | Universal Primer for non-stick finish |
US6057014A (en) | 1995-07-26 | 2000-05-02 | E. I. Du Pont De Nemours And Company | Laminates of composition for improving adhesion of elastomers to polymer compositions |
DE19537003A1 (en) * | 1995-10-04 | 1997-04-10 | Inventa Ag | Adhesion promoter based on polyamide |
US5955556A (en) | 1995-11-06 | 1999-09-21 | Alliedsignal Inc. | Method of manufacturing fluoropolymers |
US5734085A (en) | 1995-12-21 | 1998-03-31 | Minnesota Mining And Manufacturing Company | Fluorinated phosphonium salts |
JP3437361B2 (en) | 1996-01-24 | 2003-08-18 | 独立行政法人産業技術総合研究所 | Mold for resin molding |
US5859086A (en) | 1996-08-07 | 1999-01-12 | Competitive Technologies Of Pa, Inc. | Light directed modification fluoropolymers |
JPH10168419A (en) * | 1996-12-13 | 1998-06-23 | Asahi Glass Co Ltd | Adhesive composition |
US5908704A (en) * | 1997-06-30 | 1999-06-01 | Norton Performance Plastics Corporation | Interlayer film for protective glazing laminates |
DE60007850T2 (en) * | 1999-03-02 | 2004-11-04 | 3M Innovative Properties Co., St. Paul | COMPOSITIONS FOR JOINING FLUORINE POLYMERS WITH NON-FLUORINE POLYMERS |
JP4357024B2 (en) | 1999-03-09 | 2009-11-04 | 静岡県 | Surface treatment method for fluororesin linear body |
JP4010721B2 (en) | 1999-04-08 | 2007-11-21 | 沖電気工業株式会社 | Polymer material for optical communication, synthesis method thereof, and optical waveguide using the material |
US6488921B1 (en) * | 2000-07-14 | 2002-12-03 | General Electric Company | Silicone compositions for personal care products and method for making |
US6753087B2 (en) | 2001-05-21 | 2004-06-22 | 3M Innovative Properties Company | Fluoropolymer bonding |
US6685793B2 (en) * | 2001-05-21 | 2004-02-03 | 3M Innovative Properties Company | Fluoropolymer bonding composition and method |
US6630047B2 (en) * | 2001-05-21 | 2003-10-07 | 3M Innovative Properties Company | Fluoropolymer bonding composition and method |
US6752894B2 (en) * | 2001-12-14 | 2004-06-22 | 3M Innovative Properties Company | Process for modifying a polymeric surface |
-
2001
- 2001-05-21 US US09/862,022 patent/US6630047B2/en not_active Expired - Lifetime
-
2002
- 2002-03-13 AT AT02719247T patent/ATE335782T1/en not_active IP Right Cessation
- 2002-03-13 DE DE2002613811 patent/DE60213811T2/en not_active Expired - Lifetime
- 2002-03-13 WO PCT/US2002/007951 patent/WO2002094912A1/en active IP Right Grant
- 2002-03-13 CA CA 2446142 patent/CA2446142A1/en not_active Abandoned
- 2002-03-13 EP EP20020719247 patent/EP1401926B1/en not_active Expired - Lifetime
- 2002-03-13 CN CNB028102452A patent/CN1250616C/en not_active Expired - Fee Related
- 2002-03-13 JP JP2002592382A patent/JP4711603B2/en not_active Expired - Fee Related
-
2003
- 2003-08-25 US US10/647,523 patent/US7235302B2/en not_active Expired - Fee Related
- 2003-09-19 US US10/665,761 patent/US7175733B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US7175733B2 (en) | 2007-02-13 |
DE60213811D1 (en) | 2006-09-21 |
EP1401926B1 (en) | 2006-08-09 |
JP2004533514A (en) | 2004-11-04 |
ATE335782T1 (en) | 2006-09-15 |
US20040069403A1 (en) | 2004-04-15 |
US20030049455A1 (en) | 2003-03-13 |
US20040058161A1 (en) | 2004-03-25 |
CN1537132A (en) | 2004-10-13 |
WO2002094912A1 (en) | 2002-11-28 |
CN1250616C (en) | 2006-04-12 |
JP4711603B2 (en) | 2011-06-29 |
US6630047B2 (en) | 2003-10-07 |
US7235302B2 (en) | 2007-06-26 |
DE60213811T2 (en) | 2007-03-29 |
EP1401926A1 (en) | 2004-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6630047B2 (en) | Fluoropolymer bonding composition and method | |
US6685793B2 (en) | Fluoropolymer bonding composition and method | |
EP1401927B1 (en) | Fluoropolymer bonding | |
US6080487A (en) | Method of improving adhesion between a fluoropolymer and a substrate | |
US6759129B2 (en) | Adhesion and bonding of multi-layer articles including a fluoropolymer layer | |
JP4146534B2 (en) | Polytetrafluoroethylene articles adhered to a substrate | |
EP1080140B1 (en) | Multi-layer compositions comprising a fluoropolymer | |
KR20010033090A (en) | Elastomer compositions for bonding to fluoropolymers | |
EP1453896B1 (en) | Process for modifying a polymeric surface | |
EP1461376A1 (en) | Improved process for modifying a polymeric surface | |
WO1999000460A1 (en) | Method of adhering a fluoropolymer layer to a second layer of an adhesive article and articles produced by same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |