WO2010080567A2 - Method of manufacturing adhesive articles - Google Patents

Method of manufacturing adhesive articles Download PDF

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Publication number
WO2010080567A2
WO2010080567A2 PCT/US2009/068632 US2009068632W WO2010080567A2 WO 2010080567 A2 WO2010080567 A2 WO 2010080567A2 US 2009068632 W US2009068632 W US 2009068632W WO 2010080567 A2 WO2010080567 A2 WO 2010080567A2
Authority
WO
WIPO (PCT)
Prior art keywords
pressure sensitive
sensitive adhesive
layer
extrudable feedstock
adhesive
Prior art date
Application number
PCT/US2009/068632
Other languages
French (fr)
Other versions
WO2010080567A3 (en
Inventor
Jeffrey O. Emslander
Danny L. Fleming
George J. Clements
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to EP09837959.7A priority Critical patent/EP2370538B1/en
Priority to US13/140,043 priority patent/US9486982B2/en
Priority to JP2011542461A priority patent/JP2012512952A/en
Priority to CN200980156279.XA priority patent/CN102307962B/en
Publication of WO2010080567A2 publication Critical patent/WO2010080567A2/en
Publication of WO2010080567A3 publication Critical patent/WO2010080567A3/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/22Articles comprising two or more components, e.g. co-extruded layers the components being layers with means connecting the layers, e.g. tie layers or undercuts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04Layered 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
    • B32B25/08Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/12Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/18Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/16Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241Polyolefin, e.g.rubber
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • B29C48/9135Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514Oriented
    • B32B2307/518Oriented bi-axially
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/71Resistive to light or to UV
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/72Density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/748Releasability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00Adhesive articles, e.g. adhesive tapes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/005Presence of polyolefin in the release coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00Presence of block copolymer
    • C09J2453/005Presence of block copolymer in the release coating

Definitions

  • the present application is directed to a method for manufacturing adhesive articles.
  • Adhesive articles including pressure sensitive adhesive articles, have many uses.
  • the article Generally it is known to manufacture adhesive articles with a layer of adhesive, and generally with a backing. In some adhesive articles, the article also comprises a liner on the adhesive, opposite the backing.
  • the backing and/or the liner generally comprise a release agent.
  • Release agents are well known in the pressure sensitive adhesive tape industry to provide a release surface so that a tape can be unwound from a roll without the adhesive sticking to the backside of the tape or the surface of the liner.
  • the present application is directed to a method of manufacturing an adhesive article.
  • the method comprises providing a first extrudable feedstock comprising a pressure sensitive adhesive and providing a second extrudable feedstock comprising a polyolefm polymer having a density of no greater than 0.91 g/cc.
  • the first extrudable feedstock and the second extrudable feedstock are coextruded in contact with each other to form a coextruded film.
  • the method also comprises cooling the coextruded film.
  • the coextruded film comprises an adhesive layer comprising the pressure sensitive adhesive and a release layer comprising the polyolefm polymer having a density of no greater than 0.91 g/cc.
  • the method further comprises removing the first layer from the second layer.
  • the polyolefm is a block copolymer.
  • the polyolefin is made using a metallocene catalyst.
  • the present application is directed to a method of manufacturing an adhesive article.
  • the adhesive article is manufactured using extrusion technology, by coextruding a first extrudable feedstock in contact with a second extrudable feedstock to form a coextruded film.
  • the first extrudable feedstock comprises a pressure sensitive adhesive.
  • the second extrudable feedstock comprises a polyolefm polymer having a density of no greater than 0.91 g/cc.
  • the coextruded film then comprises an adhesive layer comprising the pressure sensitive adhesive and a release layer comprising the polyolefm polymer having a density of no greater than 0.91 g/cc.
  • additional feedstocks are added on one or both sides of the first or second feedstock.
  • a third extrudable feedstock may be used to make a film on the adhesive layer opposite the release layer.
  • a layer may be, for example, a graphic film such as polyvinyl chloride or an olefinic graphic film substrate like that described in U.S. 6,589,636 - Emslander, etal) or a tape backing such as ethylene acrylic acid copolymer or another layer comprising a release agent.
  • Additional layers could include films used as labelstock, graphic protection films and antigraffiti films.
  • Coextrusion is a known method of manufacturing films.
  • Coextrusion means, for the present application, the simultaneous melt processing of multiple molten streams and the combination of such molten streams into a single unified structure, or coextruded film, for example from a single extrusion die, for example cast extrusion and blown film extrusion.
  • Adhesive articles have been manufactured with extrusion technology as shown, for example, in U.S. Patent 5,660,922 (coextruding double sided adhesive tapes) and U.S. Patent Number 6,777,053. It is also known to extrude release material blends to form a release film. See, for example, U.S. Patent Application 2004-0127121. Blown film processes generally result in a tube that is later collapsed.
  • the tube may then be separated into two films (for example by slitting) or may result in a single film (for example if the inner most layer self bonds).
  • the process is run generally by processing the feedstocks at or above their melt temperature through the die, resulting in the coextruded film.
  • a coextruded film is generally a composite of all the molten feedstocks placed within the co-extrusion process.
  • the resulting co-extruded films are generally multilayer.
  • the layers are in contact with one another in the molten state. In certain embodiments, the layers are in contact throughout the extrusion, for example they are in contact as soon as they are molten.
  • the coextruded film may further be processed, for example by orientation.
  • orientation of a film is biaxial orientation.
  • Biaxial orientation involves stretching the film in two directions perpendicular to each other, generally in the down- web direction and cross-web direction.
  • the freshly extruded molten film is fed onto a chill roll to produce a quenched amorphous film which is briefly heated and stretched in the down- web direction, and then conducted through a tenter frame where it is stretched transversely with moderate heating.
  • Down-web direction stretching may be accomplished by passing between two sets of nip rolls, the second set rotating at a higher speed than the first.
  • any adhesive that is extrudable is appropriate for the present application.
  • the adhesive is a pressure sensitive adhesive after cooling.
  • the pressure sensitive adhesive may be, for example, an acrylic adhesive.
  • the pressure sensitive adhesive may be tackified.
  • the pressure sensitive adhesive is substantially free of silicones.
  • substantially free means the pressure sensitive adhesive has less than 10% by weight of silicones, for example less than 5% by weight if silicones.
  • the pressure sensitive adhesive is an acid containing acrylic pressure sensitive adhesive, for example 10% acid such as acrylic acid or less in the adhesive.
  • the pressure sensitive adhesive is a base containing acrylic pressure sensitive adhesive.
  • the pressure sensitive adhesive may also be a conventional, or natural rubber pressure sensitive adhesive or a block-copolymer synthetic rubber pressure sensitive adhesive.
  • the pressure sensitive adhesive component can be a single pressure sensitive adhesive or the pressure sensitive adhesive can be a combination of two or more pressure sensitive adhesives.
  • Pressure sensitive adhesives useful in the present application include, for example, those based on natural rubbers, synthetic rubbers, styrene block copolymers, polyvinyl ethers, poly (meth)acrylates (including both acrylates and methacrylates), polyolefms, and silicones.
  • the pressure sensitive adhesive may be inherently tacky.
  • tackifiers may be added to a base material to form the pressure sensitive adhesive.
  • Useful tackifiers include, for example, rosin ester resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and terpene resins.
  • Other materials can be added for special purposes, including, for example, oils, plasticizers, antioxidants, ultraviolet (“UV”) stabilizers, hydrogenated butyl rubber, pigments, and curing agents.
  • suitable adhesive include acrylic acid containing pressure sensitive adhesives, such as those disclosed in WO 2002/081586 and U.S. Patent No. 6,294,249.
  • the release layer comprises a release agent.
  • the release layer may also comprise other polymers, blended with the release agent.
  • the release agent comprises copolymers of ethylene and alpha-olefins having from 3 to about 10 carbon atoms and density no greater than 0.91 g/cc.
  • Suitable alpha-olefins include 1-butene, 1-hexene, 1-octene, and combinations thereof.
  • Copolymers of ethylene and octene-1 are preferred for use with acrylate-based pressure sensitive adhesives.
  • the copolymers may be either block copolymers or non- block copolymers.
  • the copolymer has a density of no greater than 0.91 g/cc, for examples no greater than 0.89 g/cc.
  • Suitable copolymers are commercially available from Dow Chemical Company, Midland, Michigan, under the INFUSE tradenames and from ExxonMobil Chemical Company, Houston, TX, under the EXACT tradenames.
  • the copolymer is polyolefm polymer made using a metallocene catalyst.
  • the release agent may additionally be blended with other polymers to form the release layer.
  • the polymers useful for blending with the release agent include other polyolefm polymers having a density of no greater than 0.91 g/cc; polyethylene (including low density polyethylene), polydiorganosiloxane polyoxamide copolymers, polypropylene and those polymers sold under the trade names Nucrel, Basell HL 456 J , Vistamax, Bynel, and combinations thereof.
  • at least the adhesive is subject to post extrusion processing, either in the coextruded film or after separation from the release liner.
  • the adhesive may be crosslinked.
  • Crosslinking sometimes also known as post curing, usually comprises exposing the coated material to some form of radiant energy, such as electron beam, or ultraviolet light with the use of a chemical crosslinking agent.
  • radiant energy such as electron beam, or ultraviolet light
  • useful crosslinkers include copolymerizable photoinitiators disclosed, for example, in US Patent Nos. 6,369,123 (Stark et al), 5,407,971 (Everaerts et al), and 4,737,559 (Kellen et al.).
  • the copolymerizable photocrosslinking agents either generate free radicals directly or use hydrogen abstraction atoms to generate free radicals.
  • Examples of hydrogen abstraction type photocrosslinkers include, for example, those based on benzophenones, acetophenones, anthraquinones, and the like.
  • suitable copolymerizable hydrogen abstraction crosslinking compounds include mono-ethylenically unsaturated aromatic ketone monomers free of orthoaromatic hydroxyl groups.
  • suitable free-radical generating copolymerizable crosslinking agents include but are not limited to those selected from the group consisting of 4-acryloxybenzophenone (ABP), para- acryloxyethoxybenzophenone, and para-N-(methacryloxyethyl)- carbamoylethoxybenzophenone.
  • Copolymerizable initiators when used, are typically included in the amount of about 0% to about 2%, or in the amount of about 0.025% to about 0.5%, based on the total monomer content.
  • Coextruded film The coextruded film is cooled after the extrusion, resulting in a multilayer film.
  • the multilayer film is then capable of being separated along the release layer/adhesive layer interface.
  • the release force for such an embodiment, where the release layer acts as a release liner is generally less than 190 g-force/inch (7 N/dm), for example 50 g-force/inch (1.9 N/dm), and in specific examples less than 40 g-force/inch (1.5 N/dm) .
  • the release layer acts as a tape backing with a low adhesion backsize ("LAB").
  • the adhesive is rolled on to the release layer.
  • the release for such an embodiment, where the release layer is a low adhesion backsize, is generally less than 1100 g-force/inch (42 N/dm), for example less than 750 g-force/inch (29 N/dm) and in specific embodiments, less than 500 g-force/inch (19 N/dm).
  • PSA 1 Acrylic Acid Containing Acrylate PSA
  • a PSA composition was made by mixing 93 parts by weight IOA, 7 parts by weight AA, 0.15 parts by weight Irgacure 651 , 0.10 parts by weight ABP, 0.05 parts by weight IOTG, and 0.4 parts by weight Irganox 1076.
  • the PSA composition was placed into packages made of a VA-24 film measuring approximately 10 centimeters by 5 centimeters and heat sealed. The composition was polymerized as described in U. S. Patent No. 5,804,610.
  • PSA 2 Tackified Acrylic Acid Containing Acrylate
  • a PSA composition was made by mixing 93 parts by weight IOA, 7 parts by weight AA, 0.15 parts by weight Irgacure 651, 0.10 parts by weight ABP, 0.05 parts by weight IOTG, and 0.4 parts by weight Irganox 1076.
  • the PSA composition was placed into packages made of a VA-24 film measuring approximately 10 centimeters by 5 centimeters and heat sealed.
  • the composition was polymerized as described in U. S. Patent No. 5,804,610.
  • the polymerized PSA was melt blended by conventional means with 14 parts by weight
  • PSA 3 Acrylamide based Acrylic PSA
  • a pressure sensitive adhesive composition having a composition of 96 wt-% 2- methylbutyl acrylate and 4 wt-% acrylamide was provided by heating a ca. 50% solids solvent solution of the monomers and a thermal initiator. Next, 0.6 wt-% benzophenone was added to the resulting polymer solution. This polymer solution had an intrinsic viscosity of ca. 0.57 dL/g in ethyl acetate at 27°C. Next, the polymer solution was stripped of solvent to provide a solid mass that was employed in the extrusion process.
  • PSA 4 Acrylic Acid Containing Acrylate PSA
  • a PSA composition was made by mixing 96.3 parts by weight 2-EHA, 3.5 parts by weight AA, 0.19 parts by weight Irgacure 184, 0.075 parts by weight ABP, and 0.05 parts by weight IOTG.
  • the PSA composition was placed into packages made of a VA-24 film measuring approximately 10 centimeters by 5 centimeters and heat sealed. The composition was polymerized as described in U. S. Patent No. 5,804,610.
  • Coated Tape 851, 3M Company, St. Paul, MN was placed over the exposed release layer and rolled down as described above.
  • the protective liner of the double coated tape was then removed and the exposed adhesive surface placed on the working platen of a SHIMADZU Autograph Model AG-X (100N) followed by rolling the rubber roller back and forth two times over the resulting laminate construction.
  • the single coated tape- reinforced outer release layer of the laminate construction was then peeled back at an angle of 180° at a peel rate of 30 cm/minute, and data was collected for about 15 seconds. Results were obtained in Newtons (N) / 2 cm and converted to N/cm. Two samples were evaluated and their average reported. All tests were run at 23°C and 65% Relative Humidity, unless otherwise noted.
  • Shear strength was evaluated at 70 0 C using a stainless steel panel and a 500 gram (gm) weight as follows.
  • the release layer reinforced with silicone treated polyester film was removed from a sample of a linered tape construction having a width of about 2 cm and a nominal length of about 10 cm.
  • a 25 micrometer thick polyester film (“EMBLET", available from Unitika Limited, Osaka, Japan) was laminated onto the exposed adhesive layer to form a linered single side pressure sensitive adhesive (PSA) tape. This tape was then cut into strips having a width of 1.2 cm and a nominal length of 10 cm, and the remaining release layer removed.
  • the resulting test strip was adhered in lengthwise contact to a stainless steel substrate (SUS panel, available from Nihon Tact Company, Limited, Tokyo, Japan) such that the tape sample covered an area measuring 2.5 cm by 1.2 cm and there was sufficient excess tape extending beyond the edge of the substrate to form a loop. Then a 2 kg rubber roller was rolled back and forth once over the resulting test panel to ensure intimate and consistent contact. The excess tape extending beyond the edge of the substrate was wrapped around a metal hook and then onto itself, adhesive to adhesive, and secured by stapling to secure the hook and provide the test sample.
  • a stainless steel substrate SUS panel, available from Nihon Tact Company, Limited, Tokyo, Japan
  • test sample was then transferred to a fixture, in a oven at 70 C, and positioned such that panel was disposed at an angle of 2 degrees to the vertical with the free end of the tape extended downward at an angle of 178 degrees to the test panel. After conditioning for 15 minutes a 500 g weight was hung on the hook and the time until the weight dropped was measured. Two samples were evaluated and the average shear time in minutes was reported.
  • Examples 11 and 12 The difference between Examples 11 and 12 was the thickness of the individual layers, as shown in the table below.
  • a blown film process employing a 3 layer, 2 inch diameter annular die was used to generate a 3 layered tubular coextruded film with an inside backing layer, a middle PSA layer, and an outside release layer. Each layer was fed through a 3 A inch diameter Brabender extruder.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Middle layer extruder barrel zone temperature profile 150 0 C, 170 0 C, 175°C.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 140 0 C, 150 0 C, 165°C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Middle layer extruder barrel zone temperature profile 155°C, 170 0 C, 180 0 C.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 130 0 C, 160 0 C, 180 0 C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 140 0 C, 150 0 C, 160 0 C.
  • outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 140 0 C, 150 0 C, 160 0 C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 155°C, 170 0 C, 180 0 C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 18°C.
  • Middle layer extruder barrel zone temperature profile 140 0 C, 150 0 C, 160 0 C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 140 0 C, 150 0 C, 160 0 C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • the resulting tubular coextruded blown films were collapsed to form a flat tube approximately 6 inches (15.2 cm) wide.
  • the collapsed tube was then rolled up on a 3 inch (7.6 cm) paper core.
  • the 3 coextruded layers formed a linered tape construction where the inside layer of the collapsed blown film tube was the tape backing, the middle layer was the PSA that bonded to the inside tape backing layer, and the outside layer was a release film that released from the PSA layer.
  • the inside and outside layers were approximately 2 mils (50 micrometers) thick and the core adhesive layer was approximately 1 mil (25 micrometers) thick.
  • a section of the collapsed coextruded film of approximately 2 feet (61 cm) in length was irradiated through the outside layer by passing it twice under a medium pressure Hg lamp for a total dose of 100 mJ/cm 2 UVC as measured by an EIT Power PUCK radiometer (EIT Incorporated, Sterling, VA).
  • a blown film was provided as described for the examples above using the temperature profiles given below.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 130 0 C, 160 0 C, 180 0 C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • the resulting tubular coextruded blown film was collapsed and crosslinked as described in the examples above to form a double linered adhesive transfer tape construction.
  • the resulting PSA/release layer article was then applied to a substrate with the PSA and substrate in contact with each other, and rubbed down using hand pressure.
  • the release layer still attached to the PSA was then removed resulting in an exposed PSA layer on a substrate.
  • the inside and outside layers were approximately 2 mils (50 micrometers) thick and the middle adhesive layer was approximately 1 mil (25 micrometers) thick.
  • a blown film was provided as described for the examples above using the temperature profiles given below.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C.
  • Middle layer extruder barrel zone temperature profile 155°C, 170 0 C, 180 0 C.
  • Inside layer extruder barrel zone temperature profile Not used - extruder shut off. Die temperature 182°C.
  • the inside extruder was shut off resulting in a 2 layer bubble of adhesive (inside) and Exact 8201 on the outside.
  • the bubble was collapsed at the nip to form a flat tube approximately 6 inches (15.2 cm) wide.
  • the inside adhesive layer of was contacted to itself, forming a continuous adhesive film that could not be separated with a release liner on each side of the adhesive layer.
  • the resulting construction was a double linered adhesive transfer tape.
  • the collapsed tube was then rolled up on a 3 (7.6 cm) inch paper core.
  • a section of the collapsed coextruded film of approximately 2 feet (61 cm) in length was crosslinked as described in the examples above.
  • the resulting PSA/release layer article was then applied to a substrate with the PSA and substrate in contact with each other, and rubbed down using hand pressure.
  • the release layer still attached to the PSA was then removed resulting in an exposed PSA layer on a substrate.
  • the release layers were approximately 2 mils (50 micrometers) thick and the adhesive layer was approximately 1 mil (25 micrometers) thick.
  • a blown film was provided as described for the examples above using the temperature profiles given below.
  • Outside layer extruder barrel zone temperature profile 160 0 C, 175°C, 185°C.
  • Middle layer extruder barrel zone temperature profile 130 0 C, 160 0 C, 180 0 C.
  • Inside layer extruder barrel zone temperature profile 160 0 C, 170 0 C, 180 0 C. Die temperature 182°C.
  • the resulting tubular coextruded blown film was collapsed and crosslinked to provide a double linered adhesive transfer tape construction which was applied to a substrate, all as described in Example 5 above.
  • EXAMPLES 11 AND 12 A blown film process employing a 3 layer, 2 inch diameter annular die was used to generate a 3 layered tubular coextruded film with an inside backing layer, a middle PSA layer, and an outside release layer.
  • the backing and release layers were fed through a 20 mm diameter single screw extruders.
  • the PSA layer was fed through a 20 mm diameter twin screw extruder.
  • the backing feed material was prepared by dry mixing the backing resin components and a red pigmented olefin blend (45 wt. % red pigment) in a plastic bag in a weight ratio of 95:5:1 / Vector 4111 : Elastollan ET-590: pigmented olefin blend.
  • the release layer feed material was prepared by dry mixing the release resin component and a blue pigmented olefin blend (20 wt. % blue pigment) in a plastic bag in a weight ratio of 100: 1.
  • the difference between Examples 11 and 12 was the extruder screw speed for the inner (backing) layer, as shown below.
  • Outside layer extruder barrel zone temperature profile 175°C, 230 0 C, 230 0 C.
  • Middle layer extruder barrel zone temperature profile 120 0 C, 120 0 C, 120 0 C.
  • Outside layer extruder barrel zone temperature profile 175°C, 230 0 C, 230 0 C.
  • Middle layer extruder barrel zone temperature profile 120 0 C, 120 0 C, 120 0 C.
  • Inside layer extruder barrel zone temperature profile 175°C, 200 0 C, 210 0 C.
  • the resulting tubular coextruded blown films were collapsed to form a flat tube approximately 30 cm (ca. 12 inches) wide.
  • the collapsed tube was then laminated to the silicone treated side of a reinforcing polyester release film and rolled up on a 7.6 cm (3 inch) diameter paper core.
  • the three coextruded layers formed a linered double coated tape construction where the inner self-bonded layers formed the tape backing, the middle layer was the PSA layer that bonded to the inside tape backing layer, and the outer layer was a release film that released from the PSA layer.
  • the combined thickness of the collapsed backing and PSA layers was measured since they could not be readily separated, and the individual thickness of the collapsed backing layer and each adhesive layer was estimated based on the extruder screw speeds for these two materials.

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Abstract

The present application is directed to a method of manufacturing an adhesive article. The method comprises providing a first extrudable feedstock comprising a pressure sensitive adhesive and providing a second extrudable feedstock comprising a polyolefin polymer having a density of no greater than 0.91 g/cc. The first extrudable feedstock and the second extrudable feedstock are coextruded in contact with each other to form a coextruded film. The method also comprises cooling the coextruded film.

Description

METHOD OF MANUFACTURING ADHESIVE ARTICLES
Field
The present application is directed to a method for manufacturing adhesive articles.
Background
Adhesive articles, including pressure sensitive adhesive articles, have many uses.
Generally it is known to manufacture adhesive articles with a layer of adhesive, and generally with a backing. In some adhesive articles, the article also comprises a liner on the adhesive, opposite the backing.
The backing and/or the liner generally comprise a release agent. Release agents are well known in the pressure sensitive adhesive tape industry to provide a release surface so that a tape can be unwound from a roll without the adhesive sticking to the backside of the tape or the surface of the liner.
Summary
Generally, co-extrusion of an adhesive layer with a layer comprising release agents has not been done because the adhesive and the release layer fail to actually effectively release from one another. The present application is directed to a method of manufacturing an adhesive article.
The method comprises providing a first extrudable feedstock comprising a pressure sensitive adhesive and providing a second extrudable feedstock comprising a polyolefm polymer having a density of no greater than 0.91 g/cc. The first extrudable feedstock and the second extrudable feedstock are coextruded in contact with each other to form a coextruded film. The method also comprises cooling the coextruded film.
The coextruded film comprises an adhesive layer comprising the pressure sensitive adhesive and a release layer comprising the polyolefm polymer having a density of no greater than 0.91 g/cc. In specific embodiments, the method further comprises removing the first layer from the second layer. In some embodiments, the polyolefm is a block copolymer. In other embodiments, the polyolefin is made using a metallocene catalyst. Detailed Description
The present application is directed to a method of manufacturing an adhesive article. The adhesive article is manufactured using extrusion technology, by coextruding a first extrudable feedstock in contact with a second extrudable feedstock to form a coextruded film. The first extrudable feedstock comprises a pressure sensitive adhesive. The second extrudable feedstock comprises a polyolefm polymer having a density of no greater than 0.91 g/cc. The coextruded film then comprises an adhesive layer comprising the pressure sensitive adhesive and a release layer comprising the polyolefm polymer having a density of no greater than 0.91 g/cc.
In some embodiments, additional feedstocks are added on one or both sides of the first or second feedstock. For example, a third extrudable feedstock may be used to make a film on the adhesive layer opposite the release layer. Such a layer may be, for example, a graphic film such as polyvinyl chloride or an olefinic graphic film substrate like that described in U.S. 6,589,636 - Emslander, etal) or a tape backing such as ethylene acrylic acid copolymer or another layer comprising a release agent. Additional layers could include films used as labelstock, graphic protection films and antigraffiti films.
Extrusion Technology
Coextrusion is a known method of manufacturing films. Coextrusion means, for the present application, the simultaneous melt processing of multiple molten streams and the combination of such molten streams into a single unified structure, or coextruded film, for example from a single extrusion die, for example cast extrusion and blown film extrusion. Adhesive articles have been manufactured with extrusion technology as shown, for example, in U.S. Patent 5,660,922 (coextruding double sided adhesive tapes) and U.S. Patent Number 6,777,053. It is also known to extrude release material blends to form a release film. See, for example, U.S. Patent Application 2004-0127121. Blown film processes generally result in a tube that is later collapsed. The tube may then be separated into two films (for example by slitting) or may result in a single film (for example if the inner most layer self bonds). The process is run generally by processing the feedstocks at or above their melt temperature through the die, resulting in the coextruded film. A coextruded film is generally a composite of all the molten feedstocks placed within the co-extrusion process. The resulting co-extruded films are generally multilayer. The layers are in contact with one another in the molten state. In certain embodiments, the layers are in contact throughout the extrusion, for example they are in contact as soon as they are molten.
The coextruded film may further be processed, for example by orientation. One example of orientation of a film is biaxial orientation. Biaxial orientation involves stretching the film in two directions perpendicular to each other, generally in the down- web direction and cross-web direction. In a typical operation, the freshly extruded molten film is fed onto a chill roll to produce a quenched amorphous film which is briefly heated and stretched in the down- web direction, and then conducted through a tenter frame where it is stretched transversely with moderate heating. Down-web direction stretching may be accomplished by passing between two sets of nip rolls, the second set rotating at a higher speed than the first.
Adhesive Technology
Any adhesive that is extrudable is appropriate for the present application. Generally the adhesive is a pressure sensitive adhesive after cooling. The pressure sensitive adhesive may be, for example, an acrylic adhesive. The pressure sensitive adhesive may be tackified.
In some embodiments, the pressure sensitive adhesive is substantially free of silicones. For the purpose of the present application, "substantially free" means the pressure sensitive adhesive has less than 10% by weight of silicones, for example less than 5% by weight if silicones.
In some embodiments, the pressure sensitive adhesive is an acid containing acrylic pressure sensitive adhesive, for example 10% acid such as acrylic acid or less in the adhesive. In other embodiments, the pressure sensitive adhesive is a base containing acrylic pressure sensitive adhesive. The pressure sensitive adhesive may also be a conventional, or natural rubber pressure sensitive adhesive or a block-copolymer synthetic rubber pressure sensitive adhesive. Furthermore, the pressure sensitive adhesive component can be a single pressure sensitive adhesive or the pressure sensitive adhesive can be a combination of two or more pressure sensitive adhesives.
Pressure sensitive adhesives useful in the present application include, for example, those based on natural rubbers, synthetic rubbers, styrene block copolymers, polyvinyl ethers, poly (meth)acrylates (including both acrylates and methacrylates), polyolefms, and silicones.
The pressure sensitive adhesive may be inherently tacky. If desired, tackifiers may be added to a base material to form the pressure sensitive adhesive. Useful tackifiers include, for example, rosin ester resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and terpene resins. Other materials can be added for special purposes, including, for example, oils, plasticizers, antioxidants, ultraviolet ("UV") stabilizers, hydrogenated butyl rubber, pigments, and curing agents.
Specific examples of suitable adhesive include acrylic acid containing pressure sensitive adhesives, such as those disclosed in WO 2002/081586 and U.S. Patent No. 6,294,249.
Release Technology
The release layer comprises a release agent. The release layer may also comprise other polymers, blended with the release agent.
In the present application, the release agent comprises copolymers of ethylene and alpha-olefins having from 3 to about 10 carbon atoms and density no greater than 0.91 g/cc. Suitable alpha-olefins include 1-butene, 1-hexene, 1-octene, and combinations thereof. Copolymers of ethylene and octene-1 are preferred for use with acrylate-based pressure sensitive adhesives. The copolymers may be either block copolymers or non- block copolymers. In some embodiments, the copolymer has a density of no greater than 0.91 g/cc, for examples no greater than 0.89 g/cc. Suitable copolymers are commercially available from Dow Chemical Company, Midland, Michigan, under the INFUSE tradenames and from ExxonMobil Chemical Company, Houston, TX, under the EXACT tradenames. In some embodiments, the copolymer is polyolefm polymer made using a metallocene catalyst.
As stated above, the release agent may additionally be blended with other polymers to form the release layer. Examples of the polymers useful for blending with the release agent include other polyolefm polymers having a density of no greater than 0.91 g/cc; polyethylene (including low density polyethylene), polydiorganosiloxane polyoxamide copolymers, polypropylene and those polymers sold under the trade names Nucrel, Basell HL 456 J , Vistamax, Bynel, and combinations thereof. In some embodiments, at least the adhesive is subject to post extrusion processing, either in the coextruded film or after separation from the release liner. For example, the adhesive may be crosslinked. Crosslinking, sometimes also known as post curing, usually comprises exposing the coated material to some form of radiant energy, such as electron beam, or ultraviolet light with the use of a chemical crosslinking agent. Examples of useful crosslinkers include copolymerizable photoinitiators disclosed, for example, in US Patent Nos. 6,369,123 (Stark et al), 5,407,971 (Everaerts et al), and 4,737,559 (Kellen et al.). The copolymerizable photocrosslinking agents either generate free radicals directly or use hydrogen abstraction atoms to generate free radicals. Examples of hydrogen abstraction type photocrosslinkers include, for example, those based on benzophenones, acetophenones, anthraquinones, and the like. Examples of suitable copolymerizable hydrogen abstraction crosslinking compounds include mono-ethylenically unsaturated aromatic ketone monomers free of orthoaromatic hydroxyl groups. Examples of suitable free-radical generating copolymerizable crosslinking agents include but are not limited to those selected from the group consisting of 4-acryloxybenzophenone (ABP), para- acryloxyethoxybenzophenone, and para-N-(methacryloxyethyl)- carbamoylethoxybenzophenone. Copolymerizable initiators, when used, are typically included in the amount of about 0% to about 2%, or in the amount of about 0.025% to about 0.5%, based on the total monomer content.
Coextruded film The coextruded film is cooled after the extrusion, resulting in a multilayer film. In some embodiments, the multilayer film is then capable of being separated along the release layer/adhesive layer interface. The release force for such an embodiment, where the release layer acts as a release liner, is generally less than 190 g-force/inch (7 N/dm), for example 50 g-force/inch (1.9 N/dm), and in specific examples less than 40 g-force/inch (1.5 N/dm) . In other embodiments, after cooling, the release layer acts as a tape backing with a low adhesion backsize ("LAB"). In such an embodiment, the adhesive is rolled on to the release layer. The release for such an embodiment, where the release layer is a low adhesion backsize, is generally less than 1100 g-force/inch (42 N/dm), for example less than 750 g-force/inch (29 N/dm) and in specific embodiments, less than 500 g-force/inch (19 N/dm).
EXAMPLES
These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, unless noted otherwise.
Figure imgf000007_0001
Figure imgf000008_0001
EXTRUDABLE PSA DESCRIPTIONS
PSA 1 : Acrylic Acid Containing Acrylate PSA
A PSA composition was made by mixing 93 parts by weight IOA, 7 parts by weight AA, 0.15 parts by weight Irgacure 651 , 0.10 parts by weight ABP, 0.05 parts by weight IOTG, and 0.4 parts by weight Irganox 1076. The PSA composition was placed into packages made of a VA-24 film measuring approximately 10 centimeters by 5 centimeters and heat sealed. The composition was polymerized as described in U. S. Patent No. 5,804,610.
PSA 2: Tackified Acrylic Acid Containing Acrylate PSA
A PSA composition was made by mixing 93 parts by weight IOA, 7 parts by weight AA, 0.15 parts by weight Irgacure 651, 0.10 parts by weight ABP, 0.05 parts by weight IOTG, and 0.4 parts by weight Irganox 1076. The PSA composition was placed into packages made of a VA-24 film measuring approximately 10 centimeters by 5 centimeters and heat sealed. The composition was polymerized as described in U. S. Patent No. 5,804,610. The polymerized PSA was melt blended by conventional means with 14 parts by weight
Foral 85 to form a ribbon of tackified PSA of approximately 5 centimeters in width and Vi centimeter thick. The ribbon was formed for ease of handling and feeding to the feed throat of the extruders used to generate the examples.
PSA 3 : Acrylamide based Acrylic PSA A pressure sensitive adhesive composition having a composition of 96 wt-% 2- methylbutyl acrylate and 4 wt-% acrylamide was provided by heating a ca. 50% solids solvent solution of the monomers and a thermal initiator. Next, 0.6 wt-% benzophenone was added to the resulting polymer solution. This polymer solution had an intrinsic viscosity of ca. 0.57 dL/g in ethyl acetate at 27°C. Next, the polymer solution was stripped of solvent to provide a solid mass that was employed in the extrusion process.
PSA 4: Acrylic Acid Containing Acrylate PSA
A PSA composition was made by mixing 96.3 parts by weight 2-EHA, 3.5 parts by weight AA, 0.19 parts by weight Irgacure 184, 0.075 parts by weight ABP, and 0.05 parts by weight IOTG. The PSA composition was placed into packages made of a VA-24 film measuring approximately 10 centimeters by 5 centimeters and heat sealed. The composition was polymerized as described in U. S. Patent No. 5,804,610.
RELEASE TEST 1
The working platen of an INSTRUMENTORS, Inc. Slip/Peel tester Model 3M90A was covered with 3M Brand double coated adhesive tape. A test sample of a linered tape construction having a width of 2.54 cm and a nominal length of 25 cm was positioned on the surface of the working platen such that the release layer was in contact with the exposed surface of the double coated tape.
A 2.3-kg rubber roller was rolled back and forth two times over the test sample. The combined backing and pressure sensitive adhesive (PSA) layers were then peeled back from the release layer at a rate of 2.3 meters/minute (90 inches/minute) over a five second data collection time. Three samples were tested and the average of the three individual average release forces was reported. All tests were done in a facility at constant temperature (700C) and constant humidity (50% RH) unless noted. Measurements were obtained in g/inch and converted to N/dm.
RELEASE TEST 2 The lower release layer of a sample of a linered tape construction, having a width of 2 centimeters (cm) and a nominal length of 10 cm, was positioned such that it was in contact with one adhesive side of a double coated adhesive tape (3M™ Y-410 Double Coated Tape, Sumitomo 3M, Japan) and rolled down using a 2 kilogram (kg) rubber roller. Next, the reinforcing polyester release film was removed from the outer release layer of the linered tape construction and a piece of reinforcing single coated tape (3M™ Single
Coated Tape 851, 3M Company, St. Paul, MN) was placed over the exposed release layer and rolled down as described above. The protective liner of the double coated tape was then removed and the exposed adhesive surface placed on the working platen of a SHIMADZU Autograph Model AG-X (100N) followed by rolling the rubber roller back and forth two times over the resulting laminate construction. The single coated tape- reinforced outer release layer of the laminate construction was then peeled back at an angle of 180° at a peel rate of 30 cm/minute, and data was collected for about 15 seconds. Results were obtained in Newtons (N) / 2 cm and converted to N/cm. Two samples were evaluated and their average reported. All tests were run at 23°C and 65% Relative Humidity, unless otherwise noted.
SHEAR TEST
Shear strength was evaluated at 700C using a stainless steel panel and a 500 gram (gm) weight as follows. The release layer reinforced with silicone treated polyester film was removed from a sample of a linered tape construction having a width of about 2 cm and a nominal length of about 10 cm. A 25 micrometer thick polyester film ("EMBLET", available from Unitika Limited, Osaka, Japan) was laminated onto the exposed adhesive layer to form a linered single side pressure sensitive adhesive (PSA) tape. This tape was then cut into strips having a width of 1.2 cm and a nominal length of 10 cm, and the remaining release layer removed. The resulting test strip was adhered in lengthwise contact to a stainless steel substrate (SUS panel, available from Nihon Tact Company, Limited, Tokyo, Japan) such that the tape sample covered an area measuring 2.5 cm by 1.2 cm and there was sufficient excess tape extending beyond the edge of the substrate to form a loop. Then a 2 kg rubber roller was rolled back and forth once over the resulting test panel to ensure intimate and consistent contact. The excess tape extending beyond the edge of the substrate was wrapped around a metal hook and then onto itself, adhesive to adhesive, and secured by stapling to secure the hook and provide the test sample. The test sample was then transferred to a fixture, in a oven at 70 C, and positioned such that panel was disposed at an angle of 2 degrees to the vertical with the free end of the tape extended downward at an angle of 178 degrees to the test panel. After conditioning for 15 minutes a 500 g weight was hung on the hook and the time until the weight dropped was measured. Two samples were evaluated and the average shear time in minutes was reported.
Examples
Figure imgf000011_0001
Figure imgf000012_0001
* Examples 1-10 and Comparative Examples A and B were evaluated for release force using "Release Test 1". Examples 11 and 12 were evaluated for release force using "Release Test 2".
** Partial adhesive transfer was observed during separation of the release layer
The difference between Examples 11 and 12 was the thickness of the individual layers, as shown in the table below.
Figure imgf000012_0002
* Partial adhesive transfer was observed during separation of the release layer N.T. = not tested
EXAMPLES 1. 2. 3. 4. 8. 9. 10 AND COMP. EXAMPLES A AND B
A blown film process employing a 3 layer, 2 inch diameter annular die was used to generate a 3 layered tubular coextruded film with an inside backing layer, a middle PSA layer, and an outside release layer. Each layer was fed through a 3A inch diameter Brabender extruder.
Temperature profiles for each example are given below. A die temperature of 182C was used for all examples given below.
Comparative Example A
Outside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C. Middle layer extruder barrel zone temperature profile: 1500C, 1700C, 175°C.
Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
Comparative Example B
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 1400C, 1500C, 165°C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
Example 1
Outside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C. Middle layer extruder barrel zone temperature profile: 155°C, 1700C, 1800C.
Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
Example 2
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 1300C, 1600C, 1800C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
Example 3
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 1400C, 1500C, 1600C.
Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
Example 4
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 1400C, 1500C, 1600C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C. Example 8
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 155°C, 1700C, 1800C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
Example 9
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 18°C. Middle layer extruder barrel zone temperature profile: 1400C, 1500C, 1600C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
Example 10
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 1400C, 1500C, 1600C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C.
For the examples described above, the resulting tubular coextruded blown films were collapsed to form a flat tube approximately 6 inches (15.2 cm) wide. The collapsed tube was then rolled up on a 3 inch (7.6 cm) paper core. The 3 coextruded layers formed a linered tape construction where the inside layer of the collapsed blown film tube was the tape backing, the middle layer was the PSA that bonded to the inside tape backing layer, and the outside layer was a release film that released from the PSA layer. The inside and outside layers were approximately 2 mils (50 micrometers) thick and the core adhesive layer was approximately 1 mil (25 micrometers) thick.
A section of the collapsed coextruded film of approximately 2 feet (61 cm) in length was irradiated through the outside layer by passing it twice under a medium pressure Hg lamp for a total dose of 100 mJ/cm2 UVC as measured by an EIT Power PUCK radiometer (EIT Incorporated, Sterling, VA).
EXAMPLE 5
A blown film was provided as described for the examples above using the temperature profiles given below. Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 1300C, 1600C, 1800C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C. Die temperature 182C.
The resulting tubular coextruded blown film was collapsed and crosslinked as described in the examples above to form a double linered adhesive transfer tape construction. After removing one of the release layers from the PSA, the resulting PSA/release layer article was then applied to a substrate with the PSA and substrate in contact with each other, and rubbed down using hand pressure. The release layer still attached to the PSA was then removed resulting in an exposed PSA layer on a substrate. The inside and outside layers were approximately 2 mils (50 micrometers) thick and the middle adhesive layer was approximately 1 mil (25 micrometers) thick.
EXAMPLE 6
A blown film was provided as described for the examples above using the temperature profiles given below.
Outside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C. Middle layer extruder barrel zone temperature profile: 155°C, 1700C, 1800C. Inside layer extruder barrel zone temperature profile: Not used - extruder shut off. Die temperature 182°C. After producing a stable bubble, the inside extruder was shut off resulting in a 2 layer bubble of adhesive (inside) and Exact 8201 on the outside. The bubble was collapsed at the nip to form a flat tube approximately 6 inches (15.2 cm) wide. During the collapsing operation the inside adhesive layer of was contacted to itself, forming a continuous adhesive film that could not be separated with a release liner on each side of the adhesive layer. The resulting construction was a double linered adhesive transfer tape. The collapsed tube was then rolled up on a 3 (7.6 cm) inch paper core. A section of the collapsed coextruded film of approximately 2 feet (61 cm) in length was crosslinked as described in the examples above. After removing one of the release layers from the PSA, the resulting PSA/release layer article was then applied to a substrate with the PSA and substrate in contact with each other, and rubbed down using hand pressure. The release layer still attached to the PSA was then removed resulting in an exposed PSA layer on a substrate. The release layers were approximately 2 mils (50 micrometers) thick and the adhesive layer was approximately 1 mil (25 micrometers) thick.
EXAMPLE 7
A blown film was provided as described for the examples above using the temperature profiles given below.
Outside layer extruder barrel zone temperature profile: 1600C, 175°C, 185°C. Middle layer extruder barrel zone temperature profile: 1300C, 1600C, 1800C. Inside layer extruder barrel zone temperature profile: 1600C, 1700C, 1800C. Die temperature 182°C.
The resulting tubular coextruded blown film was collapsed and crosslinked to provide a double linered adhesive transfer tape construction which was applied to a substrate, all as described in Example 5 above.
EXAMPLES 11 AND 12 A blown film process employing a 3 layer, 2 inch diameter annular die was used to generate a 3 layered tubular coextruded film with an inside backing layer, a middle PSA layer, and an outside release layer. The backing and release layers were fed through a 20 mm diameter single screw extruders. The PSA layer was fed through a 20 mm diameter twin screw extruder. The backing feed material was prepared by dry mixing the backing resin components and a red pigmented olefin blend (45 wt. % red pigment) in a plastic bag in a weight ratio of 95:5:1 / Vector 4111 : Elastollan ET-590: pigmented olefin blend. The release layer feed material was prepared by dry mixing the release resin component and a blue pigmented olefin blend (20 wt. % blue pigment) in a plastic bag in a weight ratio of 100: 1. The difference between Examples 11 and 12 was the extruder screw speed for the inner (backing) layer, as shown below.
Temperature profiles for each example are given below. A die temperature of 2000C was used for the two examples given below.
Example 11
Outside layer extruder barrel zone temperature profile: 175°C, 2300C, 2300C. Middle layer extruder barrel zone temperature profile: 1200C, 1200C, 1200C.
Inside layer extruder barrel zone temperature profile: 175°C, 2000C, 2100C.
Extruder Screw Speed (rpm) Inner Middle Outer
Backing PSA Release 60 : 30 : 60
Example 12
Outside layer extruder barrel zone temperature profile: 175°C, 2300C, 2300C. Middle layer extruder barrel zone temperature profile: 1200C, 1200C, 1200C. Inside layer extruder barrel zone temperature profile: 175°C, 2000C, 2100C.
Extruder Screw Speed (rpm) Inner Middle Outer
Backing PSA Release
30 : 30 : 60
For examples 11 and 12 described above, the resulting tubular coextruded blown films were collapsed to form a flat tube approximately 30 cm (ca. 12 inches) wide. The collapsed tube was then laminated to the silicone treated side of a reinforcing polyester release film and rolled up on a 7.6 cm (3 inch) diameter paper core. The three coextruded layers formed a linered double coated tape construction where the inner self-bonded layers formed the tape backing, the middle layer was the PSA layer that bonded to the inside tape backing layer, and the outer layer was a release film that released from the PSA layer. The combined thickness of the collapsed backing and PSA layers was measured since they could not be readily separated, and the individual thickness of the collapsed backing layer and each adhesive layer was estimated based on the extruder screw speeds for these two materials.
These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, unless noted otherwise. Various modifications and alterations of the present invention will become apparent to those skilled in the art without departing from the spirit and scope of the invention.

Claims

What is Claimed is:
1. A method of manufacturing an adhesive article comprising: providing a first extrudable feedstock comprising a pressure sensitive adhesive; providing a second extrudable feedstock comprising a polyolefin polymer having a density of no greater than 0.91 g/cc; coextruding the first extrudable feedstock in contact with the second extrudable feedstock to form a coextruded film; and cooling the coextruded film.
2. The method of claim 1 wherein the coextruded film comprises an adhesive layer comprising the pressure sensitive adhesive and a release layer comprising the polyolefin polymer having a density of no greater than 0.91 g/cc,
the method further comprising removing the first layer from the second layer.
3. The method of claim 1 wherein the polyolefin is a block copolymer.
4. The method of claim 1 wherein the polyolefin is made using a metallocene catalyst.
5. The method of claim 1 wherein the polyolefin polymer comprises polyethylene.
6. The method of claim 1 wherein the polyolefin polymer comprises polypropylene.
7. The method of claim 1 wherein the first extrudable feedstock and the second extrudable feedstock are in continuous contact throughout the coextruding step.
8. The method of claim 2 wherein the pressure sensitive adhesive is an acrylic adhesive.
9. The method of claim 8 wherein the acrylic adhesive is tackified.
10. The method of claim 1 wherein the first extrudable feedstock comprises a crosslinker.
11. The method of claim 10 comprising exposing the coextruded film to ultraviolet light.
12. The method of claim 10 comprising exposing the coextruded film to electron beam radiation.
13. The method of claim 2 wherein the pressure sensitive adhesive is substantially free of silicones.
14. The method of claim 2 wherein the pressure sensitive adhesive is an acid containing pressure sensitive adhesive.
15. The method of claim 2 wherein the pressure sensitive adhesive is a base containing pressure sensitive adhesive.
16. The method of claim 2 wherein the pressure sensitive adhesive is a conventional rubber pressure sensitive adhesive.
17. The method of claim 2 wherein the pressure sensitive adhesive is a block-copolymer synthetic rubber pressure sensitive adhesive.
18. The method of claim 1 wherein the second extrudable feedstock further comprises a second polyolefin polymer having a density of no greater than 0.91 g/cc.
19. The method of claim 1 wherein the second extrudable feedstock further comprises polypropylene.
20. The method of claim 1 wherein the second extrudable feedstock further comprises polyester.
21. The method of claim 1 wherein the second extrudable feedstock further comprises polyurethane.
22. The method of claim 1 wherein the second extrudable feedstock further comprises polylactic acid.
23. The method of claim 1 wherein the second extrudable feedstock further comprises a polydiorganosiloxane polyoxamide copolymer.
24. The method of claim 1 wherein the co-extrusion step is a blown film step.
25. The method of claim 24 wherein a tube is formed in the blown film step, and the method comprising collapsing the tube after the extruding step.
26. The method of claim 1 wherein the co-extrusion step is a cast extrusion step.
27. The method of claim 1 comprising orienting the coextruded film.
28. The method of claim 1 comprising a third extrudable feedstock in contact with the first extrudable feedstock opposite the second extrudable feedstock.
29. The method of claim 28 wherein the co-extrusion step is a blown film step.
30. The method of claim 29 wherein a tube is formed in the blown film step, and the method comprising collapsing the tube after the extruding step.
31. The method of claim 30 wherein the third extrudable feedstock is the inner most layer in the tube, and the inner most layer self bonds to form a film.
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WO2024083887A1 (en) * 2022-10-21 2024-04-25 Follmann Gmbh & Co. Kg Free-radical polymerisation of uv-crosslinking silane acrylates in an isocyanate-containing polyurethane matrix

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US20110316203A1 (en) 2011-12-29
JP2012512952A (en) 2012-06-07
CN102307962A (en) 2012-01-04
JP2015044999A (en) 2015-03-12
WO2010080567A3 (en) 2010-10-07
EP2370538B1 (en) 2019-03-20
JP6353129B2 (en) 2018-07-04
US9486982B2 (en) 2016-11-08
JP2017201033A (en) 2017-11-09
CN102307962B (en) 2015-09-23
EP2370538A2 (en) 2011-10-05
KR20110104051A (en) 2011-09-21
EP2370538A4 (en) 2015-03-04

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