Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/29—Laminated material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
  • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
  • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C09J123/0853—Vinylacetate
  • C09J123/0861—Saponified vinylacetate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
  • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C09J123/0869—Acids or derivatives thereof
  • C09J123/0876—Neutralised polymers, i.e. ionomers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/31—Heat sealable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2405/00—Adhesive articles, e.g. adhesive tapes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer

Definitions

• the provided adhesive articles and methods are directed to bonding articles to each other. More particularly, these adhesive articles are heat-bondable to at least one article.
• Foam tapes are commonly used in industrial sealing applications, such as sealing of automotive door jambs.
• a seal made from a thermoplastic rubber such as ethylene-propylene-diene-monomer (EPDM) is attached to one face of a double-sided foam tape either by priming the seal with an adhesion promoter, or more preferably, thermally fusing the seal to a heat bondable film adhesive that is pre-applied to one face of the foam tape.
• Historically high performance foam tapes were often based on acrylic pressure sensitive adhesive (PSA) and foam technologies; because of their relatively high polarity, these materials displayed at least moderate resistance to permeation by plasticizers.
• PSA acrylic pressure sensitive adhesive
• Typical block copolymer-based PSAs contain one or more of thermoplastic elastomers, tackifiers, plasticizers, and minor additives, combined with appropriate crosslinking agents. These compositions have been found empirically to give good performance in most industrial bonding applications and are well accepted. Summary
• the migrating plasticizer can permeate completely through even a thick foam core and compromise any adhesive that may be disposed on the opposite side of the tape from the bonded rubber seal.
• Symptoms of plasticizer migration can include abnormally high release values for removing liners from the adhesive after heat-aging the tape-seal construction, easy debonding of the block copolymer based adhesive layers from the acrylic core due to plasticizer buildup at the skin-core interface, cohesive failure of the pressure sensitive adhesive skin layer in peel or shear, and loss of shear resistance and reduced peel adhesion of the pressure sensitive adhesive to the target substrate.
• Described herein is a solution that uses a foam tape with a heat bondable layer comprised of a multilayer film having an internal barrier to plasticizers.
• the heat bondable layer can be fused to a thermoplastic elastomer seal for industrial applications, such as automotive applications.
• the internal barrier layer prevents migration of plasticizer from the bonded rubber seal into the tape, thereby limiting deterioration of tape performance on heat aging.
• Prevention of plasticizer migration from the rubber seals is an important need in the emerging business of tape-applied, body- and door-mounted seals.
• an adhesive article comprising: a barrier layer having opposed first and second major surfaces, the barrier layer being substantially impermeable to oxygen gas at ambient temperature and pressure; a heat- bondable layer extending across and coupled to the first major surface of the barrier layer; a backing extending across and coupled to the second major surface of the barrier layer; and an adhesive layer extending across and coupled to the backing opposite the barrier layer.
• an adhesive article comprising: a barrier layer having opposed first and second major surfaces, wherein the barrier layer is heat-bondable and substantially impermeable to oxygen gas at ambient temperature and pressure; a backing extending across and coupled to the second major surface of the barrier layer; and an adhesive layer extending across and coupled to the backing opposite the barrier layer.
• a method of making an adhesive article comprising: embedding a barrier layer between a pair of heat-bondable polymeric layers by coextrusion, wherein the barrier film is substantially impermeable to oxygen gas at ambient temperature and pressure; coupling one of the heat-bondable layers to a first major surface of a backing; and coupling an adhesive layer to a second major surface of the backing opposite the first major surface.
• FIG. 1 is an exploded, elevational cross-sectional view of a multi-layered adhesive article according to a first exemplary embodiment
• FIG. 2 is an elevational cross-sectional view of the adhesive article of FIG. 1 with its layers collapsed;
• FIG. 3 is an elevational cross-sectional view of an adhesive article according to a second exemplary embodiment.
• FIG. 4 is an elevational cross-sectional view of an adhesive article according to a third exemplary embodiment.
• FIG. 5 is an elevational cross-sectional view of an adhesive article according to a fourth exemplary embodiment.
• Ambient temperature means 25 degrees Celsius.
• Ambient pressure means at 1 atmosphere pressure.
• FIG. 1 presents an adhesive article according to one exemplary embodiment, designated herein by the numeral 100 and shown in exploded view for clarity.
• the adhesive article 100 has a composite configuration that includes a plurality of discrete layers serving various functions.
• the layers are, in order, a heat-bondable layer 108, a barrier layer 102, a backing 110, and an adhesive layer 112.
• a heat-bondable layer 108 a heat-bondable layer 108
• barrier layer 102 a barrier layer 102
• backing 110 a backing 110
• a functional element of the adhesive article 100 is the barrier layer 102.
• the barrier layer 102 is comprised of a polymer substantially impermeable to oxygen at an ambient temperature and pressure.
• the polymer preferably exhibits a transmission of oxygen gas (O2) of less than 100 cc/m 2 /day- atmosphere (hereinafter expressed as "cc/m 2 /d-atm"), less than 60 cc/m 2 /d-atm, less than 30 cc/m 2 /d-atm, less than 15 cc/m 2 /d-atm, or less than 5 cc-25 m/m 2 /d-atm, where the transmission measurements are taken at 25°C and zero percent relative humidity.
• Experimentally measured values of oxygen transmission can be found, for example, in Polymer Handbook, 4 th Edition, John Wiley & Sons, Inc. (1999).
• Permeability measurements are defined based on a multilayered barrier structure having a standardized barrier layer thickness of 25 micrometers. If O2 permeability is determined at other thicknesses, an appropriate linear adjustment of the permeability values can be made based on the thickness of the barrier layer and/or number of barrier layers used. In either case, the values should be normalized to a total barrier layer thickness of 25 micrometers. Values were normalized to standard barrier layer thickness of 25 micrometers by multiplying the oxygen transmission rate value by the ratio of barrier layer thickness to 25 micrometers.
• the barrier layer 102 can also exhibit barrier properties with respect to CO2, N2 and H2S gases, as well as to small molecules that are capable of migrating through polymeric films, particularly including plasticizers.
• oxygen transmission rate (or more broadly, permeability to small molecules) can be an effective proxy for the permeability of a given material to plasticizers commonly found in polymeric substrates, such as automotive bonded rubber seals.
• the barrier layer 102 be comprised of a material that is substantially impermeable to a given plasticizer while nonetheless substantially permeable to oxygen (or some other small molecule).
• the adhesive article 100 is bonded to a substrate containing significant amounts of a given plasticizer, where the barrier layer 102 is substantially impermeable to the given plasticizer.
• the materials that can be used in the barrier layer 102 there are no particular restrictions on the materials that can be used in the barrier layer 102.
• Non-limiting examples of such materials include vinyl alcohol containing polymers, such as ethylene vinyl alcohol copolymer (EVOH) and polyvinyl alcohol (PVOH), polyacrylonitrile, polystyrene, polyester, and nylon, either alone, or blended with each other, or another polymer.
• the barrier layer 102 comprises a vinyl alcohol containing polymer such as EVOH or PVOH, with EVOH being particularly preferred.
• the barrier layer 102 may preferably be comprised of substantially pure EVOH, most preferably comprising 99% or more EVOH.
• EVOH could be effectively blended with other polymers, such as ethylene vinyl acetate copolymer, while preserving its barrier properties.
• Suitable polymers may also include polar-group-containing polymers that have effective barrier properties, such as ionomers.
• Ionomers are polymers that have repeat units of both electrically neutral repeating units and a fraction of ionized units, typically less than 15 mole percent, that are covalently bonded to the polymer backbone as pendant moieties. This means that most ionomers are copolymers of the neutral segments and the ionized units. Examples of such materials include polystyrene sulfonate and sulfonated tetrafluoroethylene based fluoropolymer-copolymer (i.e., Nafion).
• the barrier layer 102 may optionally be comprised of a polymeric material having increased density to provide enhanced barrier properties.
• the polymeric material has a density of at least 1 g/cm , at least 1.10 g/cm , at least 1.15 g/cm 3 , or at least 1.2 g/cm 3 .
• barrier layer 102 that incorporates a filler that assists in blocking transmission of small molecules.
• the barrier layer 102 could be comprised of a polymer composite that includes a flake filler preferentially oriented parallel to its major surfaces.
• the barrier layer 102 has a first major surface 104 and a second major surface 106 opposed to the first major surface 104. Extending across and contacting the first major surface 104 of the barrier layer 102 is a heat-bondable layer 108.
• the barrier layer 102 and heat-bondable layer 108 are laminated to each other. As will be described later, however, these layers could also be adhesively or mechanically coupled to each other while retaining their respective functions.
• the heat-bondable layer 108 has an exposed surface for bonding to a suitable substrate and can include any of a number of suitable heat-bondable materials.
• heat-bondable means that the material layer forms a bond to one or more surfaces when heated and that the bond formed can be released upon subsequent heating.
• heat-bondable materials have insufficient tack at room temperature to bond to substrates.
• the bond formed by a heat-bondable material is generally reversible.
• Heat-bondable materials are known to those skilled in the art and include any of a number of thermoplastic materials. Suitable heat-bondable materials include fabric bonding films such as those available from 3M Company in St. Paul, MN, Bemis Associates in Shirley, MA, Framis Italia in Gaggiano, Italy, and Sealon in Seoul, Korea. Exemplary materials suitable for use as a heat-bondable layer include polyurethanes, polyamides, polyesters, vinyls, ethylene vinyl acetates, and polyolefins such as polyethylene, polypropylene, and blends/copolymers thereof.
• the heat-bondable layer 108 includes blends and copolymers of linear low density polyethylene (LLDPE) and octene, such as available from Bemis Corporation from Neenah, WI.
• LLDPE linear low density polyethylene
• octene such as available from Bemis Corporation from Neenah, WI.
• the heat-bondable layer is capable of being melted such that it can flow into substrates such as textiles, non-wovens, and foams while bonding.
• the heat-bondable layer can comprise multiple heat- bondable layers.
• the multiple heat-bondable layers can each comprise the same or different heat-bondable compositions.
• the heat-bondable layer can comprise an additional non-adhesive layer depending upon the needs of the intended application.
• the additional non-adhesive layer can comprise, for example, an elastic layer or a structural layer (e.g., a polymeric film, a foil, or scrim).
• the barrier layer 102 and the heat- bondable layer 108 could be merged into a single unitary layer. This could simplify the layer configuration of the adhesive article 100 significantly by reducing the 4-layered construction shown in FIGS. 1-2 to a 3 -layered construction.
• the barrier layer could be made from a heat-bondable polymer (such as a polyolefin) that is highly loaded with a filler that imparts barrier properties to the layer.
• the backing 110 extends across and contacts the second major surface 106 of the barrier layer 102.
• the backing 110 and barrier layer 102 are secured to each other by a heat lamination process.
• either or both opposing surfaces of the backing 110 and barrier layer 102 could be at least partially melted and the two layers pressed against each other. In this case, sufficient entanglement of polymer chains at the bonding interface can enable a strong bond.
• composition or shape of the backing 110 preferred materials for the backing 110 include polymeric foams and polymeric film layers.
• materials suitable for either a polymeric foam or solid polymeric film layer in the backing of the tape of this invention include polyolefins, such as polyethylene, including high density polyethylene, low density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylene, and polybutylenes; vinyl copolymers, such as polyvinyl chlorides, both plasticized and unplasticized, and polyvinyl acetates; olefinic copolymers, such as ethyl ene/methacry late copolymers, ethylene/vinyl acetate copolymers, acrylonitrile- butadiene-styrene copolymers, and ethylene/propylene copolymers; acrylic polymers and copolymers; polyurethanes; and combinations of the foregoing.
• a particularly preferred backing material is a crosslinked copolymer comprised of a 95:5 weight ratio of 2-ethylhexyl acrylate:acrylic acid.
• Polymeric foam layers for use in the backing of the tapes of the invention generally will have a density of about 2 to about 30 pounds per cubic foot (about 32 to about 481 kg/m3), particularly in tape constructions where the foam can be stretched to facilitate debonding.
• Preferred polymeric foam layers in the backing of the provided adhesive articles are comprised of a compressible foam.
• Such compressible foams may include open-celled or closed-cell foams, although the latter are often preferred for sealing applications.
• the compressible foam is a polyolefin foam or an acrylic foam.
• Suitable polyolefin foams are available under the trade designations VOLEXTRA and VOLARA from Voltek, a division of Sekisui America Corporation of Lawrence, MA. Foams may be prepared from expandable microspheres that expand with heat during a manufacturing step, or glass bubbles.
• Solid polymeric film backings are preferably selected from polyethylene and polypropylene films, with the most preferred materials being linear low density and ultra low density polyethylene films.
• a preferred polyethylene film is available under the trade designation MAXILE E 200 from Consolidated Thermoplastics Company of Schaumburg, IL.
• the backing may vary in overall thickness so long as it possesses sufficient integrity to be processed and handled, while providing the desired performance with respect to stretching properties for debonding the backing or tape from a given substrate.
• the specific overall thickness selected for a backing will depend upon the physical properties of the polymeric foam layer or layers and any solid polymeric film layer forming the backing. Where only one polymeric film or foam layer of a multi-layer backing is intended to be stretched to facilitate debonding, that layer should exhibit sufficient physical properties and be of a sufficient thickness to achieve that objective.
• the final layer shown in FIG. 1 is the adhesive layer 112, which extends across, and is adhesively coupled to, the adjacent backing 110.
• the adhesive layer 112 is a pressure sensitive adhesive layer.
• the pressure sensitive layer can be derived from a suitable polymer, including for example, acrylates such as those disclosed in U.S. Patent Nos. RE 24,906 (Ulrich), 3,389,827 (Abere et al.), 4, 1 12,213 (Waldman), 4,310,509 (Berglund et al.), 4,732,808 (Krampe et al.), 4,737,410 (Kantner), 5,876,855 (Wong et al.), and 7,097,853 (Garbe et al.); polyisobutylenes; polyisoprenes; styrene block copolymers (e.g., SEBS copolymers, SBS copolymers); and silicones as disclosed in U.S. Patent No. 5,232,702 (Pfister), and International Patent Application Nos. WO 2010/056541 (Liu et al.) and WO 2010
• Acrylic pressure sensitive adhesives generally have glass transition temperatures of about -20°C or less. Such adhesives may comprise from 80 to 100 weight percent of a C3- C12 alkyl ester component such as, for example, isooctyl acrylate, 2-ethylhexyl acrylate and n-butyl acrylate and from 0 to 20 weight percent of a polar component such as, for example, acrylic acid, methacrylic acid, acrylamide, ethylene vinyl acetate, N- vinylpyrrolidone and styrene macromer.
• the acrylic pressure sensitive adhesives comprise from 0 to 20 weight percent of acrylic acid and from 100 to 80 weight percent of isooctyl acrylate.
• Certain active agents e.g., CHG
• CHG may react with acrylic acid
• pressure sensitive adhesives containing acrylamide or N-vinylpyrollidone instead of acrylic acid may be desirable in such instances.
• Useful pressure sensitive adhesives may include an elastomeric material.
• suitable elastomeric materials include linear, radial, star and tapered styrene-isoprene block copolymers available under the trade designation KRATON from Shell Chemical Co. of Houston, TX and EUROPRENE from EniChem Elastomers Americas, Inc. of Houston, TX; linear styrene-(ethylene-butylene) block copolymers, linear styrene- (ethylene- propylene) block copolymers, and linear, radial, and star styrene-butadiene block copolymers, each available under the trade designation KRATON from Shell Chemical Co.
• polyetheresters such as HYTREL, available from E. I. du Pont de Nemours and Company of Wilmington, DE
• polyolefin-based thermoplastic elastomeric materials such as those represented by the formula— (CH2-CHR), where R is an alkyl group containing 2 to 10 carbon atoms and poly olefins based on metallocene catalysis available under the trade designation ENGAGE, an ethylene/polyolefin copolymer available from Dow Plastics Co.
• Pressure sensitive adhesives can optionally include one or more tackifiers.
• Useful tackifiers for acrylic polymers include rosin esters such as FORAL 85 from Hercules, Inc. of Wilmington, DE, aromatic resins such as PICCOTEX LC-55WK from Hercules, Inc. of Wilmington, DE, and aliphatic resins such as ESCOREZ 13 from Exxon Chemical Co. of Houston, TX.
• Tackifiers if present, typically comprise from about 5 to 75 percent by weight of the pressure sensitive adhesive.
• the pressure sensitive adhesive may be crosslinked or non-crosslinked.
• FIG. 2 shows the adhesive article 100 as assembled.
• the heat-bondable layer 108, barrier layer 102, backing 110, and adhesive layer 112 represent a stacked configuration where each layer continuously extends across and directly contacts the layer next to it.
• the adhesive layer 112 could be modified to be a patterned layer where the adhesive layer 112 extends over and contacts only a portion of the adjacent backing 110.
• the coupling between adjacent layers of the adhesive article 100 may be mechanically or chemically enhanced. This could include, for example, roughening the mating surfaces, incorporating interlocking features, and/or using surface modification techniques such as corona, flame plasma, or electron beam treatment to improve wetting at the interface.
• One or more additional layers may be coated or laminated to either exposed surface of the adhesive article 100.
• one or more intermediate layers may be interposed between any two adjacent layers present in the adhesive article 100.
• Such layer or layers may be similar to those described above or may be structurally or chemically distinct. Distinct layers could include, for example, extruded sheets of a different polymer, metal vapor coatings, printed graphics, particles, and primers.
• These additional layers may be continuous or discontinuous.
• a tie layer may be disposed between the backing 110 and the adhesive layer 112 to improve adhesion between the two layers.
• the adhesive article 100 can be advantageously used in a wide variety of bonding applications where a bonding surface may come into contact with a plasticizer. These include, for example, taped seal applications for permanently attaching rubber seals to the exterior surfaces of vehicles. This can provide a significant weight reduction compared with mechanical crimp-on seals known in the art. These seals, which can be made from EPDM or other plasticized polymers, are exposed to harsh outdoor environments, such as intense sun exposure and temperatures exceeding 90°C. Under these conditions, plasticizer contained within in the rubber seal tends to migrate or diffuse out of the rubber and into conventional adhesive articles that bond them to the vehicle. The adhesive article 100 overcomes this problem by blocking the plasticizer immediately adjacent to the bonding interface to avoid weakening the rubber seal and plasticizing the tape backing and adhesive layers.
• FIG. 3 shows an adhesive article 200 according to another exemplary embodiment.
• adhesive article 200 includes layers that are analogous, in structure and composition, to those of adhesive article 100—particularly, the heat-bondable layer 208, barrier layer 202, backing 210, and adhesive layer 212.
• the adhesive article 200 includes a second adhesive layer 214 disposed between the barrier layer 202 and backing 210 that adhesively couples these layers to each other.
• the second adhesive layer 214 is a pressure sensitive layer having any of the compositional and structural characteristics described previously with respect to the adhesive layer 112.
• the second adhesive layer 214 is similar or identical to the adhesive layer 212.
• the second adhesive layer 214 is not a pressure sensitive adhesive.
• the second adhesive layer 214 can be a hot melt adhesive or a polymer resin that functions as an adhesive when it is cured or otherwise hardened by heat, moisture, or radiation.
• the inclusion of the second adhesive layer 214 can be beneficial where the nature of the barrier layer 202 and/or the backing 210 prevents, or unduly complicates, heat laminating these layers to each other.
• FIG. 4 shows an adhesive article 300 according to yet another embodiment.
• the adhesive article 300 has a layered configuration analogous to that of adhesive article 200 (having a heat-bondable layer 308, barrier layer 302, backing 310, and first and second adhesive layers 312, 314), but further includes a support layer 316 extending across and releasably coupled to the first adhesive layer 312, as illustrated.
• the support layer 316 is a disposable liner that is manually stripped off and discarded before the adhesive article 300 is used.
• the support layer 316 protects the exposed surface of the first adhesive layer 312 for packaging purposes, but may also provide a benefit by adding strength to the overall adhesive article 300.
• FIG. 5 shows a fourth embodiment of the adhesive article 400 that employs a symmetric five-layer melt blown composite film 418 as a heat-sealable barrier.
• the composite film 418 includes a core barrier layer 402, a pair of tie layers 420, 420' extending across, and contacting, each major surface of the barrier layer 402. Disposed onto and contacting the outward-facing surfaces of the tie layers 420, 420' are a pair of heat-bondable layers 408, 408' . Characteristics of the remaining layers of the adhesive article 400 are similar to those described with respect to the adhesive articles 100, 200, 300 and shall not be repeated here.
• the tie layers 420, 420' improve adhesion between a polar-group- containing barrier layer 402 (e.g. EVOH) and respective heat-bondable layers 408, 408'. This may be especially beneficial, for example, where the heat-bondable layers 408, 408' are olefinic.
• the composite film 418 may further include slip adds on the peripheral surfaces of the heat-bondable layers 408 to facilitate smooth extrusion of the composite film 418 components through the die in a coextrusion process, such as a blown film process.
• Each of tie layers 420 functions as an adhesive which binds the heat-bondable layers 408 to the barrier layer 402.
• the tie layer may be formed by grafting at least one polymerizable ethylenically unsaturated monomer to a material which is chemically similar to the adjacent heat-bondable layer 408 to form a graft copolymer. This can enables improved compatibility and wetting of the tie layer 420 to the heat bondable layer 408.
• the heat bondable layer 408 is polyethylene
• the tie layer 420 could be made from a graft copolymer of polyethylene and a polymerizable ethylenically unsaturated monomer.
• Exemplary polymerizable ethylenically unsatured monomers include maleic acid, maleic anhydride, acrylic acid, alkyl acrylate esters, methacrylic acid, alkyl methacrylate esters, itaconic acid, citraconic acid, mesaconic acid, 4-methyl cyclohexene-l,2-dicarboxylic acid anhydride.
• Commercially available materials that may be used in the tie layers 420 include, for example, graft copolymers derived from polyolefin and maleic anhydride and sold under the trade designation ADMER, from Mitsui Chemicals of Tokyo, Japan.
• the major surface of the heat-bondable layer 408' facing away from the barrier layer 402 may be chemically modified to improve its adhesion to adhesive layer 414 in the finished product.
• Such surface modification may be achieved, for example, by air corona discharge treatment.
• nitrogen corona, plasma treatment, or even use of chemical primers may be employed for the same purpose.
• the multi-layered configuration of FIG. 5 can be advantageous when using hygroscopic materials such as EVOH as a barrier layer because it prevents moisture in humid environments from impinging on the major surfaces of the barrier layer. Absorbed moisture is often detrimental because it can significantly degrade the barrier properties of EVOH and similar polymers.
• the symmetric layer construction shown is also well suited to existing industrial blown film manufacturing methods.
• the provided adhesive articles preferably display high strength and robustness under high static loads. Further, these properties should be preserved even when these articles are used to bond plasticized rubber seals to various substrates. In automotive original equipment manufacturer (OEM) testing, these bonds should be capable of withstanding many years of service. Such performance can be measured on an accelerated time scale through heat aging. For example, adhesive articles can be exposed to a temperature of 90 degrees Celsius for 10 days or more. This can be carried out either on liners to simulate parts in storage or after bonding to a test panel to simulate actual use. In these tests, the provided adhesive articles were observed to show bond performance that was superior compared with conventional taped seals.
• OEM original equipment manufacturer
• Adhesive articles provided herein are preferably capable of being significantly stretched along their plane while retaining the plasticizer-blocking properties of the barrier layer.
• the adhesive article is capable of being uniaxially stretched to an overall elongation of at least 10 percent, at least 20 percent, at least 30 percent, at least 40 percent, at least 50 percent, at least 60 percent, at least 70 percent, at least 80 percent, at least 90 percent, or at least 100 percent, with the barrier layer continuing to be substantially impermeable to oxygen gas at ambient temperature and pressure.
• the use of a blown film extrusion process to embed EVOH within a pair of symmetrically disposed, heat-bondable, polyolefin layers provides a barrier layer that can significantly stretch and deform without compromising its barrier properties.
• An adhesive article comprising: a barrier layer having opposed first and second major surfaces, the barrier layer being substantially impermeable to oxygen gas at ambient temperature and pressure; a heat-bondable layer extending across and coupled to the first major surface of the barrier layer; a backing extending across and coupled to the second major surface of the barrier layer; and an adhesive layer extending across and coupled to the backing opposite the barrier layer.
• An adhesive article comprising: a barrier layer having opposed first and second major surfaces, wherein the barrier layer is heat-bondable and substantially impermeable to oxygen gas at ambient temperature and pressure; a backing extending across and coupled to the second major surface of the barrier layer; and an adhesive layer extending across and coupled to the backing opposite the barrier layer. 3.
• the adhesive article of embodiment 1 or 2 further comprising a liner extending across and contacting a major surface of the adhesive layer opposite the backing.
• each adhesive layer is a pressure sensitive adhesive layer.
• At least one tie layer comprises a graft copolymer of a polyolefin and an ethylenically unsaturated monomer.
• the barrier layer comprises a crosslinked polymer network.
• the barrier layer comprises a polymer composite that includes a flake filler preferentially oriented parallel to the first and second major surfaces.
• the heat-bondable layer comprises a polyolefin.
• thermoplastic layer comprises a copolymer of linear low density polyethylene and octene.
• the adhesive article of embodiment 20, wherein the compressible backing comprises a foam.
• the foam is a closed-cell foam.
• a bondable seal comprising:
• a method of making an adhesive article comprising:
• barrier layer embedding a barrier layer between a pair of heat-bondable polymeric layers by coextrusion, wherein the barrier film is substantially impermeable to oxygen gas at ambient temperature and pressure;
• each of the heat-bondable polymeric layers comprise linear low density polyethylene.
• Example 1 and Comparative CI were laminated to a flat EPDM rubber stock (3.2 cm width by 3.2 mm thickness), available from Lauren Manufacturing, Philadelphia, OH, as Lauren Part Number 102997-00, to simulate an EPDM weatherstrip using a laboratory Straub WL-30 continuous hot air laminator obtained from Straub Design Company of Minneapolis, MN.
• the rubber stock was first cleaned off-line by a heptane solvent wipe. The rubber was then placed on the conveyor track of the laminator. The heat-bond film side of the test tape, which was slit to a width of 12.5 mm, was then brought into contact with the approximate center of the cleaned side of the rubber.
• the rubber/tape laminates were then bonded to 10.2 cm width by 30.5 cm length clear-coated paint panels (obtained from ACT of Detroit, MI).
• Two clear-coats were used for the testing; a carbamate based composition (R10CG060X, made by BASF, Detroit, MI) and a 2-component urethane based clear-coat (RK8211, made by Axalta Coating Systems, Philadelphia, PA).
• Teflon tape 2.54 cm wide
• the liner was left intact on this overhanging strip of rubber.
• This strip, plus the 2.54 cm wide Teflon tape allowed about 5 cm of the taped rubber specimen to be gripped in the jaws of a tensile testing machine set up in a 90 degree peel configuration.
• the rubber stock was peeled from each end of the paint panel.
• peel test Under the programmed test condition, a portion of the peel test was conducted at 13 mm/minute for 3.8 cm, the test was paused, and then peeling restarted at 305 mm/minute for 12.7 cm. Two replicates were run for each sample. Aging conditions for samples were 240 hours at 70°C or 240 hours at 90°C. The results are reported in newtons per cm and shown in Table 1 (peel speed: 13 mm/min) and Table 2 (peel speed: 305 mm/min) below for initial and aged conditions.
• Adhesive articles were prepared using the following components and techniques provided below.
• a seven layer coextruded blown film consisting of the following layers; LLDPE (octene-based with slip and anti -block additives)/LLDPE (octene-based)/tie layer/EVOH/tie layer/LLDPE (octene-based)/ LLDPE (octene-based with slip and anti- block additives) having a thickness of 0.06 mm, was obtained from Bemis Company of Neenah, WI, having a thickness of 0.06 mm. The film was air corona treated on one side. The EVOH (ethylene-vinyl-alcohol polymer) in the middle layer of the film served as the barrier layer.
• LLDPE octene-based with slip and anti -block additives
• LLDPE octene-based
• a pressure sensitive adhesive coated foam obtained from 3M Company of St. Paul, MN under the designation Acrylic Plus Weatherstrip Tape WT4112 having an olefin- based heat bondable layer laminated thereon.
• WT4112 made without the standard heat-bondable layer was used as a backing to which the barrier film was laminated to the non-liner side.
• the foam tape composition of WT4112 was used as received, except with the air- corona-treated side of the multi-layer heat-bondable barrier film laminated to the non-liner side.
• the lamination was carried out manually using a rubber roller and hand pressure.
• the laminated construction was allowed to dwell for a minimum of 72 hours to allow adhesion to build between the barrier film and the backing.
• WT4112 was used as manufactured with the heat bondable layer in place.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Adhesive Tapes (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 2015
  • 2015-12-14 EP EP15834776.5A patent/EP3234055B1/en active Active
  • 2015-12-14 KR KR1020177018459A patent/KR20170095917A/ko not_active Withdrawn
  • 2015-12-14 JP JP2017532123A patent/JP6917302B2/ja active Active
  • 2015-12-14 US US15/529,310 patent/US11028289B2/en active Active
  • 2015-12-14 WO PCT/US2015/065437 patent/WO2016100153A2/en not_active Ceased
  • 2015-12-14 BR BR112017012824A patent/BR112017012824A2/pt not_active Application Discontinuation
  • 2015-12-14 CN CN201580066150.5A patent/CN107001873B/zh not_active Expired - Fee Related
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