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WO2025083620A1 - Ruban comprenant un film adhésif durcissable, ainsi que système et procédé adhésifs associés - Google Patents

Ruban comprenant un film adhésif durcissable, ainsi que système et procédé adhésifs associés Download PDF

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Publication number
WO2025083620A1
WO2025083620A1 PCT/IB2024/060235 IB2024060235W WO2025083620A1 WO 2025083620 A1 WO2025083620 A1 WO 2025083620A1 IB 2024060235 W IB2024060235 W IB 2024060235W WO 2025083620 A1 WO2025083620 A1 WO 2025083620A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
tape
adhesive film
curable adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/IB2024/060235
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English (en)
Inventor
Nicholas W. LANG
Alexander J. KUGEL
Tzu-Yu LAI
Dean A. Miner
Matthew T. HOLBROOK
Andrew Satrijo
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3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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Publication date
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Publication of WO2025083620A1 publication Critical patent/WO2025083620A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • C09J2400/243—Presence of a foam in the substrate
    • 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
    • C09J2453/00—Presence of block copolymer

Definitions

  • Nos.2020/0362204, 2021/0102095, and 2021/0102097 each to Ranade et al., each describe an adhesive system including a curable adhesive free-standing film comprising a blend of a) a first film-forming polymer or oligomer, b) a first species comprising first unsaturated free-radically polymerizable groups, which may be a) or a species other than a), and c) a first transition metal cation.
  • the curable adhesive free-standing film may be a pressure sensitive adhesive.
  • the curable adhesive free- standing film may be used with a primer that is liquid at normal temperature and pressure and includes an oxidizing agent.
  • the curable adhesive free-standing film may also include d) a reducing agent and no oxidizing agent and may be used in combination with a second curable adhesive free-standing film comprising a blend of: e) a second film-forming polymer or oligomer; f) a second species comprising second unsaturated free-radically polymerizable groups, which may be e) or may be a species other than e); and g) an oxidizing agent.
  • Methods of bonding using such a curable adhesive free-standing film are also described.
  • WO 2023/111958 describes an adhesive system including a tape and an activator.
  • the tape includes a curable adhesive free-standing film adjacent to a curable foam support layer.
  • U.S. Pat. Appl. Pub. No.2020/0062998 (Schumann et al.) describes a reactive two-component adhesive system in film form having improved heat and humidity resistance.
  • the present disclosure provides a curable adhesive film including a polymer blend including a (meth)acrylate copolymer and a nitrogen-containing polymer, unsaturated free-radically polymerizable groups, which may be bonded to the (meth)acrylate copolymer or in a species other than the (meth)acrylate copolymer, and a transition metal cation.
  • the (meth)acrylate copolymer comprises acidic monomer units.
  • the tape has improved bulk creep and static shear performance than a tape having the same components except without the nitrogen-containing polymer.
  • the tape including the nitrogen-containing polymer can have greater dimensional stability before it is cured.
  • the bulk creep and static shear properties are unexpectedly better than those achieved with a non-functional or acid-functional block copolymer and unexpectedly better at a lower concentration than a poly(vinyl butyral) additive, which can be used to increase the modulus.
  • the cured overlap shear strength of the adhesive is not negatively impacted by the nitrogen-containing polymer.
  • the present disclosure provides an adhesive system that includes the tape and an activator composition comprising an oxidizing agent.
  • the adhesive system may be provided in a kit that includes the tape and the activator composition.
  • the present disclosure provides a method of bonding a first substrate.
  • the method includes applying an activator composition onto a surface of the first substrate and contacting the activator composition with a first surface of the tape.
  • the activator composition includes an oxidizing agent.
  • polymer refers to a molecule having a structure which includes the multiple repetition of units derived, actually or conceptually, from one or more monomers.
  • monomer refers to a molecule of low relative molecular mass that can combine with others to form a polymer.
  • the term “polymer” includes homopolymers and copolymers, as well as homopolymers or copolymers that may be formed in a miscible blend, e.g., by coextrusion or by reaction.
  • polymer includes random, block, graft, and star polymers.
  • polymer encompasses oligomers.
  • nitrogen-containing polymer as used herein means that the polymer includes at least one nitrogen atom in at least one repeating unit. Thus, this element may also be called a “nitrogen atom- containing polymer”.
  • curable refers to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure, the terms “cured” and “crosslinked” may be used interchangeably.
  • a cured or crosslinked polymer is generally characterized by insolubility but may be swellable in the presence of an appropriate solvent.
  • crosslinked includes partially crosslinked.
  • Oxygen permeable refers to having an oxygen permeability of a least 4000 centimeters cubed (cm 3 ) * micrometer ( ⁇ m)/meter squared (m 2 ) * day * atmosphere (atm) (4000 cm 3 * ⁇ m/m 2 *day*atm) at 23 ⁇ C to 25 ⁇ C without a specified relative humidity percentage.
  • the term adjacent refers to two superimposed layers within the tape or constructions including the tape, activator, and one or more substrates, which are arranged directly next to each other, i.e., which are abutting each other and are typically in direct contact with each other.
  • film-forming means capable of forming a continuous and coherent film, which in some embodiments may result from one or more of solidification, curing, drying, or solvent removal of a melt, solution, or suspension.
  • solid means materials that are substantially self-supporting at room temperature (i.e., 20°C to 25°C) such that if left at rest they will retain their shape without deforming or flowing.
  • free-standing film means a film that is solid at normal temperature and pressure and has mechanical integrity independent of contact with any supporting material (which excludes, inter alia, liquids, surface coatings dried or cured in situ such as paints or primers, and surface coatings without independent mechanical integrity).
  • hot melt processable in the context of one of the polymer-containing layers or films described herein means the polymer-containing composition includes little or no conventional solvent (which is various embodiments may be less than 5 weight percent, less than 3 weight percent, less than 1 weight percent, less than 0.5 weight percent, less than 0.1 weight percent, or less than 0.01 weight percent of conventional solvent), which may be hot melt processed under conventional conditions, where hot melt processes include hot melt blending and extruding.
  • solvent which is various embodiments may be less than 5 weight percent, less than 3 weight percent, less than 1 weight percent, less than 0.5 weight percent, less than 0.1 weight percent, or less than 0.01 weight percent of conventional solvent
  • (meth)acrylate” includes, separately and collectively, methacrylate and acrylate.
  • normal temperature and pressure means a temperature of 20°C (293.15 K, 68°F) and an absolute pressure of 1 atm (14.696 psi, 101.325 kPa).
  • dependent in the context of functional groups of a polymer or oligomer are functional groups that do not form a part of the backbone of the polymer or oligomer and are not terminal groups of the polymer.
  • structural adhesive means an adhesive that binds by irreversible cure.
  • PSAs Pressure sensitive adhesives
  • PSAs are well known to those of ordinary skill in the art to possess properties including the following: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and typically, (4) sufficient cohesive strength to be cleanly removable from the adherend.
  • PSAs are tacky and have the ability to adhere without activation by any energy source such as light, heat, or a chemical reaction.
  • Materials that have been found to function well as PSAs are polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power.
  • One method useful for identifying pressure sensitive adhesives is the Dahlquist criterion.
  • This criterion defines a pressure sensitive adhesive as an adhesive having a creep compliance of greater than 3 x 10 -6 cm 2 /dyne as described in Handbook of Pressure Sensitive Adhesive Technology, Donatas Satas (Ed.), 2nd Edition, p.172, Van Nostrand Reinhold, New York, NY, 1989.
  • pressure sensitive adhesives may be defined as adhesives having a storage modulus of less than about 3 x 10 5 N/m 2 .
  • glass transition temperature or “Tg” refers to the temperature at which a material changes from a glassy state to a rubbery state.
  • the term “glassy” means that the material is hard and brittle (and therefore relatively easy to break) while the term “rubbery” means that the material is elastic and flexible.
  • the Tg is the critical temperature that separates their glassy and rubbery behaviors. If a polymeric material is at a temperature below its Tg, large-scale molecular motion is severely restricted because the material is essentially frozen. On the other hand, if the polymeric material is at a temperature above its Tg, molecular motion on the scale of its repeat unit takes place, allowing it to be soft or rubbery. Any reference herein to the Tg of a monomer refers to the Tg of a homopolymer formed from that monomer.
  • the glass transition temperature of a polymeric material is often determined using methods such as Dynamic Mechanical Analysis (“DMA”) or Differential Scanning Calorimetry (e.g., Modulated Differential Scanning Calorimetry). Alternatively, the glass transition of a polymeric material can be calculated using the Fox Equation if the amount and Tg of each monomer used to form the polymeric material are known.
  • the term “alkyl” refers to a monovalent group which is a saturated hydrocarbon. The alkyl can be linear, branched, cyclic, or combinations thereof, and typically has 1 to 32 carbon atoms. Unless otherwise indicated, the alkyl group contains 1 to 25, 1 to 20, 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2-octyl and 2-propylheptyl.
  • aryl refers to a monovalent group that is aromatic and, optionally, carbocyclic. The aryl has at least one aromatic ring. Any additional rings can be unsaturated, partially saturated, saturated, or aromatic.
  • the aromatic ring can have one or more additional carbocyclic rings that are fused to the aromatic ring.
  • the aryl groups typically contain from 6 to 30 carbon atoms. In some embodiments, the aryl groups contain 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of an aryl group include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.
  • aralkyl refers to a monovalent group that is an alkyl substituted with an aryl group (e.g., as in a benzyl group).
  • alkaryl refers to a monovalent group that is an aryl substituted with an alkyl group (e.g., as in a tolyl group). In some embodiments, for both groups, the alkyl portion has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, and an aryl portion has 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • alkylene refers to a divalent group that is a radical of an alkane and includes groups that are linear, branched, cyclic, bicyclic, or a combination thereof.
  • the alkylene group typically has 1 to 30 carbon atoms. In some embodiments, the alkylene group has 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • alkylene groups include methylene, ethylene, propylene, 1,4-butylene, 1,4-cyclohexylene, and 1,4- cyclohexyldimethylene.
  • arylene refers to a divalent group that is aromatic and, optionally, carbocyclic. The arylene has at least one aromatic ring. Optionally, the aromatic ring can have one or more additional carbocyclic rings that are fused to the aromatic ring.
  • the arylene group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromatic ring.
  • the arylene group can be phenylene.
  • arylene groups have 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • aralkylene refers to a divalent group that is an alkylene group substituted with an aryl group or an alkylene group attached to an arylene group.
  • alkarylene refers to a divalent group that is an arylene group substituted with an alkyl group or an arylene group attached to an alkylene group.
  • the alkyl or alkylene portion has from 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • the aryl or arylene portion has from 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • the term “or” is generally employed in its usual sense including “and/or” unless the content clearly dictates otherwise.
  • the term “and/or” is used to indicate one or both stated cases may occur, for example A and/or B includes, (A and B) and (A or B).
  • room temperature refers to a temperature in the range of 20°C to 25°C.
  • the term “comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claims. Such terms will be understood to imply the inclusion of a stated step or element or group of steps or elements but not the exclusion of any other step or element or group of steps or elements.
  • a number e.g., up to 50
  • the recitations of numerical ranges by endpoints include all numbers subsumed within that range as well as the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.) and any sub-ranges (e.g., 1 to 5 includes 1 to 4, 1 to 3, 2 to 4, etc.).
  • the term “in the range” or “within a range” includes the endpoints of the stated range.
  • Reference throughout this specification to “some embodiments,” means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure.
  • FIG. l is a cross section of one embodiment of a tape useful in the adhesive system of the present disclosure.
  • FIG.2 is a cross section of another embodiment of a tape useful in the adhesive system of the present disclosure.
  • FIG.3 is a cross section of one embodiment of a construction using a tape of the type shown in FIG.2, activator compositions, and first and second substrates.
  • FIG.4 is a cross section of one embodiment of a double-sided tape with only one curable adhesive film layer, useful in the adhesive system of the present disclosure.
  • FIG.5 is a cross section of one embodiment of a double-sided multi-layer tape with a barrier film support layer, useful in the adhesive system of the present disclosure.
  • FIG.6 is a cross section of another embodiment of a construction using a tape of the type shown in FIG.2, an activator composition, and first and second substrates.
  • FIG.7 is a cross section of an embodiment of the adhesive system of the present disclosure covered with an oxygen-permeable liner.
  • FIG.8 is a cross section of another embodiment of the adhesive system of the present disclosure covered with an oxygen-permeable liner.
  • FIG.9 depicts an embodiment of a method for bonding two substrates using an embodiment of the adhesive system of the present disclosure.
  • FIG.10 depicts another embodiment of a method for bonding two substrates using an embodiment of the adhesive system of the present disclosure.
  • FIG.11 depicts yet another embodiment of a method for bonding two substrates using another embodiment of the adhesive system of the present disclosure.
  • FIG.12 is a side (part-sectional) elevational view of a container for holding a solid activator composition.
  • FIG.13 is a top view of a carrier which forms part of the container of FIG.12.
  • the tape of the present disclosure and/or useful in the adhesive system and method of the present disclosure includes a polymer blend comprising a (meth)acrylate copolymer and a nitrogen-containing polymer, unsaturated free-radically polymerizable groups, and a transition metal cation.
  • the unsaturated free-radically polymerizable groups may be bonded to the (meth)acrylate copolymer (i.e., a component of the (meth)acrylate copolymer) or may be in a species other than the (meth)acrylate copolymer.
  • the curable adhesive film also includes a redox accelerator such as a quaternary ammonium salt.
  • the tape is a multilayer curable adhesive film, wherein the curable adhesive film further comprises a support layer.
  • the support layer is a foam support layer, in some embodiments, a curable foam support layer.
  • the tape is a double-sided tape with a foam support layer (in some embodiments, a curable foam support layer), a first adhesive layer on a first side of the foam support layer, and a second adhesive layer on a second side of the foam support layer, opposite the first adhesive layer, wherein at least one of the first adhesive layer, the second adhesive layer, or the foam support layer independently comprises the polymer blend, the unsaturated free-radically polymerizable groups, the transition metal cation, and optionally, the quaternary ammonium salt.
  • a foam support layer in some embodiments, a curable foam support layer
  • first adhesive layer on a first side of the foam support layer
  • a second adhesive layer on a second side of the foam support layer, opposite the first adhesive layer
  • at least one of the first adhesive layer, the second adhesive layer, or the foam support layer independently comprises the polymer blend, the unsaturated free-radically polymerizable groups, the transition metal cation, and optionally, the quaternary ammonium salt.
  • each of the first adhesive layer, the second adhesive layer, and the foam support layer independently comprises the polymer blend, the unsaturated free- radically polymerizable groups, the transition metal cation, and optionally, the quaternary ammonium salt.
  • an embodiment of tape 110 includes a curable adhesive film 140 (having two major surfaces 142 and 144) adjacent to a support layer 150 (having two major surfaces 152 and 154).
  • the support layer 150 is a foam.
  • the support layer 150 is curable.
  • an embodiment of a tape, multilayer curable adhesive film 210 includes a first adhesive layer 240 (having two major surfaces 242 and 244) and a second adhesive layer 260 (having two major surfaces 262 and 264), each of which are adjacent to opposite sides of a support layer 250 (having two sides 252 and 254). More specifically, the first major surfaces 242 and 262 form the outer adhesive surfaces of multilayer curable adhesive film 210; the second major surface 244 of the first adhesive layer 240 is adjacent the first side of the support layer 250; and the second major surface 264 of the second adhesive layer 260 is adjacent the second side of the support layer 250.
  • the support layer 250 is a foam. In some embodiments, the support layer 250 is curable.
  • multilayer curable adhesive films in the tape of the present disclosure and/or useful in the adhesive system and method of the present disclosure may include two or more curable adhesive films having components that are the same or different (i.e., they are independently selected).
  • Multilayer curable adhesive films may include two or more curable foam support layers having components that are the same or different (i.e., they are independently selected).
  • the first and second adhesive layers independently comprises the polymer blend, the unsaturated free- radically polymerizable groups, the transition metal cation, and optionally, the redox accelerator.
  • each of the first adhesive layer, the second adhesive layer, or the foam support layer independently comprises the polymer blend, the unsaturated free-radically polymerizable groups, the transition metal cation, and optionally, the redox accelerator.
  • the unsaturated free-radically polymerizable groups may be bonded to the (meth)acrylate copolymer (i.e., a component of the (meth)acrylate copolymer) or may be in a species other than the (meth)acrylate copolymer.
  • the first adhesive layer 240 is borne on a first major surface 252 of the foam support layer 250, and the second adhesive layer 260 is borne on a second major surface 254 of the foam support layer 250. That is, the layers are typically made in one step, such as occurs in a coating or coextrusion process. In some embodiments of FIG.2, the first adhesive layer 240 is directly bound to a first major surface 252 of the foam support layer 250 and the second adhesive layer 260 is directly bound to a second major surface 254 of the foam support layer 250. That is, the layers are typically made in two or more steps, such as occurs in a lamination process. Such procedures are well- known in the preparation of tapes.
  • a major surface 244 of the first adhesive layer 240 is adjacent to a major surface 252 of the support layer 250.
  • the curable adhesive film useful in the tape, adhesive system, and method of the present disclosure comprises a (meth)acrylate copolymer.
  • the curable adhesive films are pressure sensitive adhesives before cure upon contact with the activator composition described herein. As such, they are capable of maintaining substrates in position before cure, for example, under shop or factory conditions, without clamps or other supports.
  • the (meth)acrylate copolymer comprises linear or branched alkyl (meth)acrylate ester monomer units selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, iso- pentyl (meth)acrylate, n-hexyl (meth)acrylate, iso-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, octyl (meth)acrylate, iso-octyl (meth)acrylate, 2-octyl(meth)acrylate, 2-ethylhexyl (me)acrylate,
  • the (meth)acrylate copolymer includes monomer units of at least one of 2-methylbutyl acrylate, isooctyl acrylate, lauryl acrylate, 4-methyl-2- pentyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, isodecyl acrylate, isodecyl methacrylate, or isononyl acrylate.
  • Suitable monomer units further include mixtures of at least two or at least three structural isomers of a secondary alkyl (meth)acrylate of Formula I: wherein R 1 and R 2 are each independently a C 1 to C 30 saturated linear alkyl group; the sum of the number of carbons in R 1 and R 2 is 7 to 31; and R 3 is H or CH 3 .
  • the sum of the number of carbons in R 1 and R 2 can be, in some embodiments, 7 to 27, 7 to 25, 7 to 21, 7 to 17, 7 to 11, 7, 11 to 27, 11 to 25, 11 to 21, 11 to 17, or 11.
  • the (meth)acrylate copolymer includes acidic monomer units.
  • Acidic monomer units can be incorporated into the (meth)arylate copolymer using monoethyleneically unsaturated monomers having a carboxylic acid, sulfonic acid, or phosphonic acid group, for example.
  • suitable acrylic monomers comprising a carboxylic acid group to provide acidic monomer units include methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, beta-carboxy ethyl acrylate, and ⁇ -methacryloyl oxyethyl hydrogen succinate.
  • the (meth)acrylate copolymer includes from 0.1 weight percent to 15 weight percent of (meth)acrylic acid monomer units, based on the weight of the (meth)acrylate copolymer. In some embodiments, the (meth)acrylate copolymer comprises at least 6% by weight, at least 8% by weight, or at least 10% by weight acrylic acid monomer units, each based on the total weight of the (meth)acrylate copolymer.
  • the alkyl (meth)acrylate ester monomer units described above may be copolymerized with one or more other monoethylenically unsaturated monomers that have polar groups such as acrylamide, methacrylamide, N-substituted acrylamides (for example, N,N-dimethyl acrylamide), acrylonitrile, methacrylonitrile, hydroxyalkyl acrylates, cyanoethyl acrylate, N-vinylpyrrolidone, N- vinylcaprolactam, and maleic anhydride.
  • polar groups such as acrylamide, methacrylamide, N-substituted acrylamides (for example, N,N-dimethyl acrylamide), acrylonitrile, methacrylonitrile, hydroxyalkyl acrylates, cyanoethyl acrylate, N-vinylpyrrolidone, N- vinylcaprolactam, and maleic anhydride.
  • these polar copolymerizable monomers are used in amounts of less than 20% by weight and/or at least 6%, at least 8%, or at least 10%, based on the total weight of the monomer units.
  • the (meth)acrylate copolymer may also include small amounts of other useful copolymerizable monoethylenically unsaturated monomers such as alkyl vinyl ethers, vinylidene chloride, styrene, and vinyltoluene.
  • the (meth)acrylate copolymer is a (meth)acrylate functional polymer, such as that made by adding (meth)acrylate end groups to (meth)acrylate copolymers bearing hydroxyl functional groups as described in the Examples of U.S. Pat. Appl. Pub. No.2021/0102097 (Ranade et al.).
  • the alkyl (meth)acrylate ester monomer units may be copolymerized with a crosslinking agent, such as 1,6-hexanediol diacrylate or any of the crosslinking monomers described below or with a photoactive triazine crosslinking agent such as taught in U.S. Pat.
  • Film-forming polymers can also be crosslinked with a heat- activatable crosslinking agent such as a lower-alkoxylated amino formaldehyde condensate having C 1-4 alkyl groups, for example, hexamethoxymethyl melamine or tetramethoxymethyl urea or tetrabutoxymethyl urea.
  • Crosslinking the film-forming polymer may also be achieved by irradiating the composition with electron beam (or “e-beam”) radiation, gamma radiation, or x-ray radiation.
  • the (meth)acrylate copolymer has a Tg of no greater than 0°C. In some embodiments, the (meth)acrylate copolymer has a Tg of -70°C to 0°C, -70°C to -10°C, -60°C to -10°C, -60°C to -20°C, -60°C to -30°C, -55°C to -35°C, or -50°C to -40°C.
  • the curable adhesive film typically contains at least 20 weight percent, not more than 98 weight percent, or in a range from 20 weight percent to 98 weight percent of the (meth)acrylate copolymer, based on the total weight of the curable adhesive film.
  • the amount of the (meth)acrylate copolymer can be at least 20, at least 50, at least 60, at least 70, or at least 75 weight percent and up to 98, up to 90, up to 80, up to 75, up to 70, up to 65, or up to 60 weight percent, based on the total weight of the curable adhesive film.
  • the polymer blend includes a first (meth)acrylate copolymer comprising from 0.1 weight percent to 12 weight percent of (meth)acrylic acid monomer units, based on the weight of the first (meth)acrylate copolymer; and a second (meth)acrylate copolymer comprising from 15 weight percent to 40 weight percent of (meth)acrylic acid monomer units, based on the weight of the second (meth)acrylate copolymer.
  • the first (meth)acrylate copolymer and/or the second (meth)acrylate copolymer can comprise, as main monomer units, any of those described above.
  • the first (meth)acrylate copolymer and/or the second (meth)acrylate copolymer comprise, as main monomer units, linear or branched alkyl (meth)acrylate ester monomer units selected from the group consisting of 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, iso-octyl (meth)acrylate, and any combinations or mixtures thereof.
  • the first (meth)acrylate copolymer has a Tg of no greater than 0°C and the second (meth)acrylate copolymer has a Tg of greater than 0°C.
  • the second (meth)acrylate copolymer has a Tg of no greater than 100°C, no greater than 80°C, no greater than 60°C, no greater than 50°C, no greater than 45°C, or no greater than 40°C.
  • the first (meth)acrylate copolymer has a Tg of -70°C to 0°C, -70°C to -10°C, -60°C to - 10°C, -60°C to -20°C, -60°C to -30°C, -55°C to -35°C, or -50°C to -40°C.
  • the second (meth)acrylate copolymer has a Tg of 2°C to 100°C, 2°C to 80°C, 2°C to 60°C, 2°C to 50°C, 2°C to 45°C, 5°C to 45°C, 5°C to 40°C, 5°C to 35°C, or 10°C to 30°C.
  • the curable adhesive film comprises from 60 to 97 weight percent, from 70 to 95 weight percent, from 75 to 95 weight percent, from 75 to 90 weight percent, or from 75 to 85 weight percent, of the first (meth)acrylate copolymer, wherein the weight percentages are based on the total weight of the curable adhesive film composition.
  • the curable adhesive film in the article of the present disclosure comprises from 1 to 35 weight percent, from 1 to 30 weight percent, from 2 to 25 weight percent, from 3 to 25 weight percent, from 3 to 20 weight percent, from 4 to 20 weight percent, or even from 4 to 15 weight percent, of the second (meth)acrylate copolymer, wherein the weight percentages are based on the total weight of the curable adhesive film composition.
  • these (meth)acrylate copolymers are described in U.S. Pat. Appl. Pub. No.2021/0102099 (Unverhau et al.).
  • the (meth)acrylate copolymer can be prepared by any suitable polymerization method.
  • Suitable polymerization methods include, but are not limited to, photopolymerization, thermal polymerization, or ionizing radiation polymerization. These methods can be carried out in solution, emulsion, or bulk without solvent. Bulk polymerization methods are described in U.S. Pat. No.5,804,610 (Hamer et al.).
  • photopolymerizable monomers may be partially polymerized to a viscosity of from 1000 cps to 40,000 cps to facilitate coating.
  • partial polymerization can be effected by heat. If desired, viscosity can also be adjusted by mixing monomers with a thixotropic agent such as fumed silica.
  • Photopolymerization can take place in an inert atmosphere such as under a blanket of nitrogen or argon gas.
  • an inert environment can be achieved by temporarily covering the photopolymerizable coating with a plastic film transparent to ultraviolet radiation and irradiating the coating through the film. If the polymerizable coating is not covered during photopolymerization, the permissible oxygen content of the inert atmosphere can be increased by mixing into the photopolymerizable composition an oxidizable tin compound such as disclosed in U.S. Pat. No.4,303,485 (Levens), which can enable relatively thicker coatings to be polymerized in air.
  • the (meth)acrylate copolymer is a statistical (meth)acrylate copolymer.
  • the term “statistical” refers to a copolymer that is formed from a polymerizable composition having a plurality of different types of monomers. Under some conditions, the statistical copolymer is a random copolymer. Under other conditions, however, the statistical copolymer may not be completely random because differences in concentration and reactivity of the monomers may create conditions where the early stages of polymerization may favor polymerization of one type of monomer in the polymerizable composition.
  • the terms “statistical” and “random” are often used interchangeably in polymeric publications.
  • the (meth)acrylate copolymer may be a random (meth)acrylate copolymer.
  • the polymer blend in the curable adhesive film of the tape, adhesive system, or method of the present disclosure includes a nitrogen-containing polymer.
  • Suitable nitrogen-containing polymers include aromatic or aliphatic polyurethanes (e.g., including those polyurethanes made with aliphatic or aromatic diols, polyamides, saturated and unsaturated polyesters, such as polybutylene terephthalate, polyethylene terephthalate, polyglycolic acid, polylactic acid, poly-2-hydroxy butyrate, polycaprolactone, and combinations containing maleic acid repeating units); amino resins (e.g., urea-formaldehyde resins, melamine-formaldehyde resins, and melamine-urea copolymer resins); polyethyleneimines, polyvinylpyrrolidones, polyvinylpyrrolidone copolymers
  • the nitrogen-containing polymer comprises at least one of amino or amido functional groups. In some embodiments, the nitrogen-containing polymer comprises at least one of a nitrogen-containing (meth)acrylate copolymer, a nitrogen-containing (meth)acrylate block copolymer, a polyvinylpyrrolidone polymer, or a polyvinylpyrrolidone copolymer. In some embodiments, the nitrogen-containing polymer is a nitrogen-containing (meth)acrylate copolymer, in some embodiments, comprising at least one of amino or amido functional groups.
  • the nitrogen-containing (meth)acrylate copolymer can include any of the alkyl (meth)acrylate ester monomer units described above for the (meth)acrylate copolymer.
  • the nitrogen-containing (meth)acrylate polymer further includes monomer units derived from a monomer or monomers having an ethylenically unsaturated group and at least one of a primary amido group, a secondary amido group, a tertiary amido group, a primary amino group, a secondary amino group, or a tertiary amino group.
  • suitable monomers with a primary amido group include (meth)acrylamide.
  • suitable monomers with secondary amido groups include N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-octyl (meth)acrylamide, and N-octyl (meth)acrylamide.
  • N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-octyl (meth)acrylamide, and N-octyl (meth)acrylamide.
  • Suitable monomers with a tertiary amido group include N-vinyl caprolactam, N-vinyl-2-pyrrolidone, 4-(meth)acryloyl morpholine, and N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, and N,N-dibutyl (meth)acrylamide.
  • Polar monomers with an amino group include various N,N- dialkylaminoalkyl (meth)acrylates and N,N-dialkylaminoalkyl (meth)acrylamides.
  • Examples include 2- (N,N-dimethylaminoethyl) (meth)acrylate, 2-(N,N-dimethylaminoethyl) (meth)acrylamide, 3-(N,N- dimethylaminopropyl) (meth)acrylate, 3-(N,N-dimethylaminopropyl) (meth)acrylamide, 2-(N,N- diethylaminoethyl) (meth)acrylate, 2-(N,N-diethylaminoethyl) (meth)acrylamide, 3-(N,N- diethylaminopropyl) (meth)acrylate, 3-(N,N-diethylaminopropyl) (meth)acrylamide, 2-(t- butylaminoethyl) (meth)acrylate, 2-(t-butylaminoethyl) (meth)acrylamide, N-(meth)acryloylpiperidine, and N-vinylpyridine.
  • the nitrogen-containing (meth)acrylate copolymer comprises at least one of N,N-dimethylacrylamide, 4-acryloylmorpholine, methacrylamide; N-alkyl substituted methacrylamides, vinylpyridine, or vinylpyrrolidinone monomer units.
  • the nitrogen-containing (meth)acrylate copolymer is a statistical (meth)acrylate copolymer as defined above. Nitrogen-containing (meth)acrylate copolymers can conveniently be made using any of the methods described above.
  • the nitrogen-containing polymer is a polyvinylpyrrolidone polymer or a polyvinylpyrrolidone copolymer.
  • Polyvinylpyrrolidone polymers with various molecular weights are commercially available from a variety of sources include Ashland, Inc., Wilmington, DE. Vinyl pyrrolidone can be copolymerized with any of the ethylenically unsaturated monomers described above.
  • the nitrogen-containing polymer is a copolymer of vinylpyrrolidone and vinyl acetate. A variety of such polymers can be obtained commercially, including from BASF, Ludwigshafen, Germany, under trade designations “KOLLIDON” and “SOKALAN”.
  • the nitrogen-containing polymer is a nitrogen-containing (meth)acrylate block copolymer, in some embodiments, comprising at least one of amino or amido functional groups.
  • block copolymer refers to a copolymer having a plurality of different polymeric segments, which are known as “blocks”. Each block can be a homopolymer (i.e., a polymeric segment formed from a single type of monomer) or a copolymer (i.e., a polymeric segment formed from multiple (i.e., two or more) different types of monomers and may be a statistical copolymer).
  • the boundary between adjacent blocks in the block copolymer can be sharp (i.e., the composition of the monomeric units changes abruptly at the boundary between two blocks) or tapered (i.e., the composition of the monomeric units does not change abruptly at the boundary between two blocks but is mixed in a transition region near the boundary; the transition region contains monomeric units from both adjacent blocks).
  • trim copolymer refers to a multi-block copolymer having three different polymeric blocks and the term “diblock copolymer” refers to a multi-block copolymer having two different polymeric blocks.
  • Both the triblock copolymer and the diblock copolymer contain polymeric blocks arranged in a linear manner relative to each other; thus, they can be referred to as linear block copolymers.
  • the block copolymer component of the polymer blend can include two or more block copolymers having different compositions, lengths, or architectures, such as a diblock copolymer and a triblock copolymer.
  • the nitrogen-containing (meth)acrylate block copolymer can be a triblock copolymer having an A-B-A structure with the A and B blocks selected to have solubility parameters that are sufficiently different to cause phase separation between the A blocks and the B block.
  • the two A blocks and the B block of the (meth)acrylic-based triblock copolymer A-B-A are typically selected to have different glass transition temperatures.
  • the A blocks which typically have a higher glass transition temperature than the B, can be referred to as “hard” blocks while the B block can be referred to as a “soft” block.
  • the A blocks are usually selected to be more rigid than the B block.
  • the A blocks can be thermoplastic and can provide semi-structural or structural strength and/or shear strength to the adhesive composition.
  • the B block can be a viscous material and can provide tack and adhesive strength to the adhesive composition.
  • the A blocks of the nitrogen-containing (meth)acrylate block copolymer A- B-A can have a glass transition temperature (Tg) equal to at least 50 ⁇ C, 60 ⁇ C, 70 ⁇ C, 75 ⁇ C, or 80 ⁇ C and not more than 200 ⁇ C, 180 ⁇ C, 175 ⁇ C, 150 ⁇ C, 140 ⁇ C, or 125 ⁇ C as measured using Dynamic Mechanical Analysis.
  • Tg glass transition temperature
  • the B block can have a glass transition temperature no greater than 20 ⁇ C, 10 ⁇ C, 5 ⁇ C, 0 ⁇ C, -10 ⁇ C, -20 ⁇ C, or -30 ⁇ C and at least -70 ⁇ C, -60 ⁇ C, -50 ⁇ C, or -40 ⁇ C as measured using Dynamic Mechanical Analysis.
  • the (meth)acrylic-based triblock copolymer A-B-A usually contains 10 to 55 weight percent A blocks and 45 to 90 weight percent B blocks based on a total weight of the (meth)acrylic-based triblock copolymer.
  • the (meth)acrylic-based block copolymer contains 15 to 55 weight percent A blocks and 45 to 85 weight percent B block, 20 to 55 weight percent A blocks and 45 to 80 weight percent B block, or 20 to 40 weight percent A block and 60 to 80 weight percent B block.
  • Each of the two A blocks of the (meth)acrylic-based triblock copolymer A-B-A can be about the same weight. That is, the weight ratio of the two A blocks of the (meth)acrylic-based triblock copolymer is often 1:1 or close to 1:1 such as greater than 0.9:1. However, other weight ratios can also be used such as in a range of 0.65:1 to 0.99:1.
  • Each A block of the (meth)acrylic-based triblock copolymer A-B-A is usually prepared from a monomer composition that includes an alkyl methacrylate.
  • Suitable alkyl methacrylates for preparing the A blocks often have an alkyl group with 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 5 carbon atoms, or 1 to 4 carbon atoms. If the alkyl group has 3 to 5 carbon atoms, it is typically branched. If the alkyl group has 6 to 10 carbon atoms, it is typically cyclic or bicyclic.
  • the A blocks are homopolymers and each homopolymer is a poly(alkyl methacrylate).
  • Example poly(alkyl methacrylates) include poly(methyl methacrylate), poly(ethyl methacrylate), poly(isopropyl methacrylate), poly(isobutyl methacrylate), poly(sec-butyl methacrylate), poly(tert-butyl methacrylate), poly(cyclohexyl methacrylate), poly(methylcyclohexyl methacrylate), poly(3,3,5-trimethylcyclohexyl methacrylate), and poly(isobornyl methacrylate). These homopolymers each have a glass transition temperature equal to at least 50 ⁇ C.
  • the first A block can be prepared from other optional monomers provided the resulting polymeric blocks have a glass transition temperature that is equal to at least 50 ⁇ C when measured using Dynamic Mechanical Analysis.
  • monomers include 2-methoxyethyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, cyclohexyl acrylate, isobornyl acrylate, styrene, styrene-type monomers (e.g., alpha-methyl styrene, 3-methyl styrene, 4-methyl styrene, ethyl styrene, isopropyl styrene, tert-butyl styrene, dimethyl styrene, 2,4,6-trimethyl styrene, and 4-methoxy styrene), and vinyl acetate
  • the A block further includes a monomer unit arising from a monomer having an ethylenically unsaturated group and at least one of a primary amido group, a secondary amido group, a tertiary amido group, a primary amino group, a secondary amino group, or a tertiary amino group. Examples of such monomers include any of those described above.
  • the A blocks are poly(methyl methacrylate) blocks.
  • the B block of the (meth)acrylic-based triblock copolymer A-B-A is typically formed from monomers that will provide polymeric blocks having a glass transition temperature no greater than 20 ⁇ C as measured using Dynamic Mechanical Analysis.
  • the B block is often prepared from a monomer composition that includes an alkyl acrylate.
  • Suitable alkyl acrylates for forming the B block often have an alkyl group with 2 to 20, 2 to 18, 2 to 12, or 2 to 10 carbon atoms.
  • the alkyl group can be linear, branched, cyclic, or a combination thereof (e.g., the alkyl can have a cyclic group plus a branched or linear group).
  • the B block is a homopolymer.
  • homopolymers include, but are not limited to, poly(ethyl acrylate), poly(n-propyl acrylate), poly(n-butyl acrylate), poly(isobutyl acrylate), poly(sec-butyl acrylate), poly(isoamyl acrylate), poly(n-hexyl acrylate), poly(2-methylbutyl acrylate), poly(4-methyl-2-pentyl acrylate), poly(cyclohexyl acrylate), poly(2-methylhexyl acrylate), poly(n-octyl acrylate), poly(2-octyl acrylate), poly(isooctyl acrylate), poly(2-ethylhexyl acrylate), poly(isononyl acrylate), poly(n-decyl acrylate), poly(isodecyl acrylate), poly(lauryl acrylate), poly(isotridecyl acrylate), poly(isoo
  • the B block is poly(n-butyl acrylate), poly(n-octyl acrylate), poly(2-octyl acrylate), poly(isooctyl acrylate), poly(2-ethylhexyl acrylate), or poly(isononyl acrylate).
  • the B block can further include other optional monomer units provided the resulting polymeric block has a glass transition temperature that is no greater than 20 ⁇ C when measured using Dynamic Mechanical Analysis.
  • Examples of monomers providing such monomer units include 2-ethoxy ethyl (meth)acrylate, 2-methoxy ethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-biphenylhexyl acrylate, benzyl acrylate, 2-phenoxy ethyl acrylate, n-decyl methacrylate, lauryl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, and n-hexyl methacrylate.
  • the B block further includes a monomer unit arising from a monomer having an ethylenically unsaturated group and at least one of a primary amido group, a secondary amido group, a tertiary amido group, a primary amino group, a secondary amino group, or a tertiary amino group.
  • a monomer unit arising from a monomer having an ethylenically unsaturated group and at least one of a primary amido group, a secondary amido group, a tertiary amido group, a primary amino group, a secondary amino group, or a tertiary amino group. Examples of such monomers include any of those described above.
  • the B block is poly(n-butyl acrylate), poly(n-octyl acrylate), poly(2-octyl acrylate), poly(isooctyl acrylate), poly(2- ethylhexyl acrylate), or poly(isononyl
  • the B block is poly(n-butyl acrylate).
  • the monomer unit including at least one of a primary amido group, a secondary amido group, a tertiary amido group, a primary amino group, a secondary amino group, or a tertiary amino group is usually present in an amount no greater than 10, no greater than 5, no greater than 2, or no greater than 1 weight percent based on a total weight of the monomer units in at least one of the A block or the B block.
  • each A block comprises monomeric units derived from methyl methacrylate and the B block comprises monomeric units derived from n-butyl (meth)acrylate, in some embodiments, n-butyl acrylate.
  • the nitrogen-containing (meth)acrylate block copolymer can be synthesized using any suitable technique. Examples of suitable techniques include anionic polymerization, radical polymerization, group transfer polymerization, and ring-opening polymerization reactions.
  • the polymerization can be a “living” or “controlled/living” polymerization, which can advantageously produce block copolymer structures that are well defined.
  • Specific synthesis methods include atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT) processes. Such processes are disclosed, for example, in U.S. Pat. Nos.7,255,920 (Everaerts et al.), 6,734,256 (Everaerts et al.), and 6,806,320 (Everaerts et al.).
  • Other synthesis methods include the use of controlled radical initiators that are bis-dithiocarbamate or bis-dithiocarbonate compounds such as those disclosed in U.S. Pat. Nos.
  • Living polymerizations can also provide block copolymers with relatively sharp transitions between the blocks. Such sharp transitions can be useful for achieving phase separation.
  • Suitable commercially available (meth)acrylic-based triblock copolymers can be obtained under the trade designation “KURARITY” from Kuraray Co., Ltd. (Tokyo, Japan) and under the trade designation “NANOSTRENGTH” from Arkema (Colombes, France).
  • the polymer blend can optionally include a nitrogen-containing (meth)acrylate diblock copolymer, which may be represented by the formula A-B, wherein A and B are as described above in any of their embodiments.
  • the diblock copolymer often contains 5 to 30 weight percent of the A block and 70 to 95 weight percent of the B block.
  • the polymer blend can also include a combination of a nitrogen-containing (meth)acrylate triblock copolymer and a nitrogen-containing (meth)acrylate diblock copolymer.
  • the nitrogen-containing polymer has a weight average molecular weight (Mw) that is at least 25,000, at least 30,000, at least 35,000, at least 40,000, at least 45,000 or at least 50,000 grams per mole (g/mol) and up to 200,000 up to 190,000 up to 180,000 up to 175,000 up to 170,000 up to 160,000 up to 150,000 up to 140,000 up to 130,000 up to 125,000 up to 120,000 up to 115,000 up to 110,000 up to 100,000 up to 90,000 up to 80,000 or up to 75,000 g/mol.
  • the weight average molecular weight is often in a range of 50,000 to 200,000, 50,000 to 175,000 or 50,000 to 150,000 g/mol.
  • the weight average molecular weight is typically determined using gel permeation chromatography with polystyrene standards.
  • the curable adhesive film typically contains at least 1 weight percent, not more than 40 weight percent, or in a range from 1 weight percent to 40 weight percent of the nitrogen-containing polymer, based on the total weight of the curable adhesive film.
  • the amount of the nitrogen-containing polymer can be at least 1, at least 5, at least 7.5, at least 10, or at least 15 weight percent and up to 40, up to 35, up to 30, up to 25, up to 20, up to 15, or up to 10 weight percent, based on the total weight of the curable adhesive film.
  • the curable adhesive film useful in the tape of the present disclosure includes unsaturated free- radically polymerizable groups, which may be bonded to the (meth)acrylate copolymer (i.e., a reactive polymer comprising unsaturated free-radically polymerizable groups) or in a species other than the (meth)acrylate copolymer.
  • unsaturated free-radically polymerizable groups include ethylenically unsaturated groups (e.g., vinyl-containing groups such as (meth)acrylate groups).
  • the unsaturated free-radically polymerizable groups are part of a crosslinker (i.e., crosslinkable species) distinct from the polymer blend making up the polymer film.
  • crosslinkers include two or more or three or more unsaturated free-radically polymerizable groups.
  • the crosslinker is a crosslinking monomer.
  • the crosslinker is an oligomer.
  • suitable crosslinkers include trimethylolpropane triacrylate (TMPTA), ethoxy trimethylolpropane triacrylate, propoxy glycerol triacrylate, pentaerythritol triacrylate, bistrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxy pentaerythritol tetraacrylate, trimethylolpropane trimethacrylate, ethoxy pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol dime
  • crosslinkers include other multifunctional polyol esters.
  • acrylic acid or methacrylic acid esters of a variety of polyols in which at least two hydroxy groups are esterified can be used as crosslinkers.
  • the curable adhesive film typically contains at least 1 weight percent, not more than 40 weight percent, or in a range from 1 weight percent to 40 weight percent of the crosslinkable species, which is not in the polymer blend, based on the total weight of the curable adhesive film.
  • the amount of the crosslinkable species can be at least 5, at least 7.5, at least 10, or at least 15 weight percent and up to 40, up to 35, up to 30, up to 25, up to 20, up to 15, or up to 10 weight percent, based on the total weight of the curable adhesive film.
  • the curable adhesive film useful in the tape of the present disclosure and/or useful in the adhesive system and method of the present disclosure additionally comprises a transition metal cation.
  • suitable transition metal cations include molybdenum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, or zinc.
  • the transition metal cation is a copper cation, such as Cu(II), such as may be found in copper(II) acetate monohydrate and copper (II) naphthenate.
  • the transition metal cation is an iron cation, such as Fe(II) or Fe(III), such as may be found in Black 11 (Fe 3 O 4 or FeO .
  • Useful transition metal complexes are described in U.S. Pat. No.11,370,940 (Townsend et al.), and have the general formula: [ML p ] n+ A ⁇ , wherein M represents a transition metal capable of participating in a redox cycle with an oxidizing agent and a reducing agent.
  • Useful transition metals, M may include the catalytically active valent states of Cu, Fe, Ru, Cr, Mo, Pd, Ni, Pt, Mn, Rh, Re, Co, V, Au, Nb, and Ag.
  • the transition metal cation is a low valent transition metal including Cu(II), Fe(II), Ru(II), and Co(II). Other valent states of these metals may be used, and the active low valent state may be generated in situ.
  • L represents a ligand.
  • the ligand, L may be used to solubilize the transition metal salts in a suitable solvent and adjust the redox potential of the transition metal for appropriate reactivity and selectivity.
  • the ligands can direct the transition metal complex to undergo a desired one-electron transfer process, rather than a two-electron process such as oxidative addition/reductive elimination.
  • the ligands may further enhance the stability of the complexes in the presence of different monomers and solvents or at different temperatures. Acidic monomers and monomers that strongly complex transition metals may still be efficiently polymerized by appropriate selection of ligands.
  • Useful ligands include those having one or more nitrogen, oxygen, phosphorus, and/or sulfur atoms which can coordinate to the transition metal through a sigma-bond, ligands containing two or more carbon atoms which can coordinate to the transition metal through a pi-bond, etc.
  • Such ligands may be monodentate or polydentate compounds, in some embodiments, containing up to about carbon atoms and up to 10 heteroatoms selected from aluminum, boron, nitrogen, sulfur, non- peroxidic oxygen, phosphorus, arsenic, selenium, antimony, and tellurium, where upon addition to the metal atom, following loss of zero, one, or two hydrogens, the polydentate compounds can form with the metal, M n+ , a 4-, 5-, or 6-membered saturated or unsaturated ring.
  • Suitable monodentate ligands are carbon monoxide; alcohols such as ethanol, butanol, and phenol; pyridine, nitrosonium (i.e., NO + ); compounds of Group 15 elements such as ammonia, phosphine, trimethylamine, trimethylphosphine, tributylphosphine, triphenylamine, triphenylphosphine, triphenylarsine, or tributyl phosphite; nitriles such as acetonitrile or benzonitrile; isonitriles such as phenylisonitrile or butylisonitrile; carbene groups such as ethoxymethylcarbene or dithiomethoxycarbene; alkylidenes such as methylidene or ethylidene.
  • nitriles such as acetonitrile or benzonitrile
  • isonitriles such as phenylisonitrile or butylisonit
  • polydentate compounds examples include dipyridyl, 1,2-bis(diphenyl- phosphino)ethane; 1,2-bis(diphenylarsino)ethane, bis(diphenylphosphino)methane, polyamines (e.g., ethylenediamine, propylenediamine, tetramethylethylenediamine, hexamethyl tris-aminoethylamine, diethylenetriamine, 1,3-diisocyanopropane, and hydridotripyrazolylborate), hydroxycarboxylic acids (e.g., glycolic acid, lactic acid, and salicylic acid), polyhydric phenols such as catechol and 2,2’- dihydroxybiphenyl, hydroxyamines (e.g., ethanolamine, propanolamine, and 2-aminophenol); dithiocarbamates such as diethyldithiocarbamate and dibenzyldithiocarbamate,
  • Suitable ligands that can coordinate to the transition metal through a sigma bond are the inorganic groups (e.g., F ⁇ , OH ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , and hydride) and organic groups (e.g., CN ⁇ , SCN ⁇ , acetoxy, formyloxy, and benzoyloxy).
  • inorganic groups e.g., F ⁇ , OH ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , and hydride
  • organic groups e.g., CN ⁇ , SCN ⁇ , acetoxy, formyloxy, and benzoyloxy.
  • the ligand can also be a unit of a polymer, for example, the amino group in poly(ethylenimine), the phosphino group in poly(4-vinylphenyldiphenylphosphine), the carboxylic acid group in poly(acrylic acid), and the isonitrile group in poly(4-vinylphenylisonitrile).
  • Useful ligands containing two or more carbon atoms that can coordinate to the transition metal through a pi-bond are provided by any monomeric or polymeric compound having an accessible unsaturated group, e.g., an ethylenic group, acetylenic group, or aromatic group which has accessible pi- electrons regardless of the total molecular weight of the compound.
  • pi-bond ligands include the linear and cyclic ethylenic and acetylenic compounds having less than 100 carbon atoms (when monomeric), in some embodiments, having less than 60 carbon atoms, and from zero to 10 heteroatoms selected from nitrogen, sulfur, non-peroxidic oxygen, phosphorous, arsenic, selenium, boron, aluminum, antimony, tellurium, silicon, germanium, and tin.
  • pi-bond ligands include ethylene, acetylene, propylene, methylacetylene, ⁇ -butene, 2-butene, diacetylene, butadiene, 1,2- dimethylacetylene, cyclobutene, pentene, cyclopentene, hexene, cyclohexene, 1,3-cyclohexadiene, cyclopentadiene, 1,4-cyclohexadiene, cycloheptene, 1-octene, 4-octene, 3,4-dimethyl-3-hexene, 1-decene; ⁇ 3 -allyl, ⁇ 3 -pentenyl, norbornadiene, ⁇ 5 -cyclohexadienyl, cycloheptatriene, and cyclooctatetraene.
  • pi-bond ligands include substituted and unsubstituted carbocyclic and heterocyclic aromatic ligands having up to 25 rings and up to 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, boron, aluminum, antimony, tellurium, silicon, germanium, and tin.
  • pi-bond ligands include ⁇ 5 - cyclopentadienyl, benzene, mesitylene, toluene, xylene, tetramethylbenzene, hexamethylbenzene, fluorene, naphthalene, anthracene, chrysene, pyrene, ⁇ 7 -cycloheptatrienyl, triphenylmethane, paracyclophane, 1,4-diphenylbutane, ⁇ 5 -pyrrolo, ⁇ 5 -thiophene, ⁇ 5 -furan, pyridine, ⁇ -picoline, quinaldine, benzopyran, thiochrome, benzoxazine, indole, acridine, carbazole, triphenylene, silabenzene, arsabenzene, stibabenzene, 2,4,6-triphenylphosphabenzene, ⁇ 5 -
  • ligands include unsubstituted and substituted pyridines and bipyridines, tertiary amines, including polydentate amines such as N,N,N’,N’-tetramethylethylenediamine and tris(N,N-dimethylamino-ethyl)amine, acetonitrile, phosphites (e.g., (CH 3 O) 3 P), 1,10-phenanthroline, porphyrin, cryptands and crown ethers (e.g., 18-crown-6 ether).
  • the ligand is a polydentate amine, bipyridine, or a phosphite.
  • Examples of useful anions, A ⁇ include halide (e.g., chloride, bromide, fluoride), alkoxy groups having from 1 to 6 carbon atoms (i.e., C 1 - C 6 alkoxy), nitrate, sulfate, phosphate, biphosphate, hexafluorophosphate, triflate, methanesulfonate, arenesulfonate, cyanide, alkanecarboxylates (e.g., acetate), and arenecarboxylates (e.g., benzenecarboxylate).
  • halide e.g., chloride, bromide, fluoride
  • alkoxy groups having from 1 to 6 carbon atoms i.e., C 1 - C 6 alkoxy
  • nitrate e.g., sulfate, phosphate, biphosphate, hexafluorophosphate, triflate, methanesulfonate,
  • n represents the formal charge on the transition metal having a whole number value of 1 to 7, in some embodiments, 1 to 3, and p is the number of ligands on the transition metal having a number value of 1 to 9, in some embodiments, 1 or 2.
  • the transition metal cation is used in an amount of not more than one weight percent, and typically at least 0.005 weight percent, based on the total weight of the curable adhesive film.
  • the curable adhesive film additionally includes a redox accelerator, such as a quaternary ammonium salt, amine hydrochloride, sodium chloride, or a phosphonium salt.
  • Suitable quaternary ammonium salts may be represented by formula (R 7 ) 4 N+ X-, wherein each R 7 is independently alkyl, aryl, or a combination thereof, any of which may be substituted or unsubstituted, and X is Cl, Br, F, SbF, BF, or PF.
  • suitable quaternary ammonium salts include dimethyl benzyl aniline chloride (DMBAC) and benzyltriethylammonium chloride.
  • Suitable phosphonium salts may be represented by formula (R 8 ) 4 P+ X-, wherein each R 8 is independently alkyl, aryl, or a combination thereof, any of which may be substituted or unsubstituted, and X is Cl, Br, F, SbF, BF, or PF. In some embodiments, each R 8 is independently phenyl or C 1 -C 5 alkyl.
  • Suitable phosphonium salts include allyltriphenylphosphonium bromide (ATPB), 2-(ethoxycarbonyl)ethyl-triphenylphosphonium bromide, 1-ethoxycarbonylethyl triphenylphosphonium bromide, 4-ethoxycarbonylbutyl triphenylphosphonium bromide, carbethoxymethyl triphenylphosphonium bromide, and methyltriphenylphosphonium bromide.
  • redox accelerators may be used if desired. In some embodiments, the redox accelerator is used in an amount of at least 0.25 weight percent, and typically up to 4 weight percent, based on the total weight of the curable adhesive film.
  • the oxidizing agent in the activator composition oxidizes the transition metal cation (e.g., Cu(I) to Cu(II)) forming radicals that initiate crosslinking of the crosslinkable species (typically catalytically) thereby forming a crosslinked network.
  • the redox accelerator when present, serves as a reducing agent of the initially provided Cu(II) cation to Cu(I).
  • the curable adhesive film useful in the article of the present disclosure is typically a room temperature solid and also a free-standing film as defined herein, regardless of any support layer that may be present.
  • the curable adhesive film may be made using conventional techniques such as solution coating onto a web.
  • the curable adhesive film is made from an adhesive film that is hot melt processable and is made in a hot melt process.
  • Hot melt processing such as hot melt blending or hot melt extrusion, may be accomplished by any suitable means, including those disclosed in U.S. Pat. Appl. Pub. No.2013/0184394 (Satrijo et al.).
  • adhesive films that may be hot melt processable comprise a blend of a reactive polymer comprising unsaturated free-radically polymerizable groups, which are typically pendant groups, and a transition metal cation.
  • adhesive films that may be hot melt processed comprise a blend of a film-forming polymer or oligomer, a reactive species comprising unsaturated free- radically polymerizable groups, and a transition metal cation.
  • the adhesive film further includes a redox accelerator (e.g., a quaternary ammonium salt).
  • the adhesive film made by hot melt processing can then be applied directly adjacent an activator on a substrate or release liner to provide some embodiments of the adhesive system of the present disclosure.
  • the curable or cured adhesive film in the article of the present disclosure may be of any suitable thickness.
  • the thickness is at least 20 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, at least 200 micrometers, at least 250 micrometers, at least 300 micrometers, or at least 350 micrometers. In some embodiments, the thickness is not more than 2000 micrometers, not more than 1000 micrometers, or not more than 500 micrometers.
  • the curable adhesive film can be cured when comes into contact with the activator composition in the adhesive system disclosed here, which includes an oxidizing agent. Typically, the oxidizing agent of the activator composition migrates into the curable adhesive films thereby initiating cure of the curable adhesive film or films, typically, in the absence of oxygen.
  • the activator composition is described in further detail below.
  • the curable adhesive film is a multilayer curable adhesive film, wherein the multilayer curable adhesive film further comprises a support layer.
  • the support layer is a foam support layer, in some embodiments, a curable foam support layer.
  • the curable support layer includes a base polymer.
  • the base polymer may be the same or different than the film-forming polymer useful for the film of the polymer in the curable adhesive film and may be any of those described above for the curable adhesive film and below for the activator composition.
  • the base polymer of the curable foam support layer may be the same as the polymer in the curable adhesive film, which may or may not include unsaturated free-radically polymerizable groups.
  • the base polymer can also be made and processed by any of the processes described above for the curable adhesive film.
  • the base polymer of the support layer which may be a foam support layer or a curable foam support layer, is a silicone polymer.
  • Suitable silicone polymers can include an MQ resin containing a resinous core and nonresinous polyorganosiloxane group terminated with a silicon-bonded hydroxyl group, a treated MQ resin, and a polydiorganosiloxane terminated with a condensation reactable group.
  • Such compositions may be used for structural glazing applications, as described in U.S. Pat.
  • the support layer which in some embodiments, is a foam support layer or a curable foam support layer, includes a crosslinker mixed therein.
  • the base polymer of the curable foam support layer does not include unsaturated free-radically polymerizable groups, in some embodiments, such groups may be provided by a distinct species within the curable foam support layer, or they may be provided by a species that migrates into the curable foam support layer.
  • suitable crosslinkers include those described above for the curable adhesive films.
  • the curable foam support layer includes a base polymer that is receptive to receiving a crosslinker that is migratable into the curable foam support layer.
  • the crosslinker migrates from the curable adhesive film into the curable foam support layer.
  • the crosslinker of the curable foam support layer is the same as the species comprising unsaturated free-radically polymerizable groups of the curable adhesive film.
  • the same crosslinker may also be separately loaded into the curable adhesive film and the curable foam support layer.
  • the crosslinker of the curable foam support layer may, in other embodiments, be different than the species comprising unsaturated free-radically polymerizable groups of the curable adhesive film.
  • the crosslinker that is included within the curable foam support layer and/or migrates into the curable foam support layer, and that is included within the curable adhesive film, is activated when the curable adhesive film contacts the activator composition, typically when oxygen is excluded from the curable adhesive film or multilayer curable adhesive film, to start the redox cycle, thereby initiating crosslinking.
  • This crosslinking of the crosslinker results in curing of both the curable adhesive film and the curable foam support layer. It is believed that an interpenetrating crosslinked network is formed in the bulk of the adhesive layers wherein the first network is that formed from the crosslinker(s) and the second network is that from the film-forming polymer(s).
  • the curable foam support layer includes a transition metal cation as described for the curable adhesive film.
  • the curable foam support layer also includes a redox accelerator as described for the curable adhesive film.
  • the curable adhesive film is a foam.
  • the curable adhesive film, the foam support layer, and/or the curable foam support layer of the multilayer curable adhesive film useful in some embodiments of the present disclosure may be a closed cell foam, an open cell foam, a syntactic foam, a non-syntactic foam, or a combination thereof.
  • foams can be made using chemical foaming agents, physical foaming agents, and mechanical foaming processes, for example.
  • the curable foam support layer includes a foaming agent and the same components as the first and/or second adhesive layer.
  • the foaming agent comprises at least one of expandable microspheres, hollow glass bubbles, or gas (e.g., nitrogen) bubbles, which are optionally surfactant stabilized.
  • a foam can be made from froth formed from physical agitation and stabilized with surfactant, such as a silicone or a fluorochemical known to be useful for foaming organic liquids that have low surface tension (e.g., those described in U.S. Pat. No.4,415,615 (Esmay et al.)).
  • the foam is a syntactic foam containing hollow microspheres, for example, hollow ceramic (e.g., glass) microspheres.
  • Useful hollow glass microspheres include those having a density of less than 0.4 gram per milliliter (g/mL) and having a diameter of from 5 to 200 micrometers.
  • the microspheres may be clear, coated, stained, or a combination thereof.
  • Useful hollow glass microspheres include those available under the trade designation “3M GLASS BUBBLES K37” from 3M Co., St Paul, MN).
  • the microspheres typically comprise from 5 to 65 volume percent of the foam composition. Examples of useful acrylic foams thus made are disclosed in U.S. Pat. No.4,415,615 (Esmay et al.) and U.S. Pat. No.6,103,152 (Gehlsen et al.).
  • foams are formed by blending expanded polymeric microspheres into a polymerizable composition.
  • foams are formed by blending expandable polymeric microspheres into a composition and expanding the microspheres.
  • An expandable polymeric microsphere includes a polymer shell and a core material in the form of a gas, liquid, or combination thereof. Upon heating to a temperature at or below the melt or flow temperature of the polymeric shell, the polymer shell expands to form the microsphere.
  • Suitable core materials include propane, butane, pentane, isobutane, neopentane, isopentane, and combinations thereof.
  • the thermoplastic resin used for the polymer microsphere shell can influence the mechanical properties of the foam, and the properties of the foam may be adjusted by the choice of microsphere, or by using mixtures of different types of microspheres.
  • expandable microspheres examples include those available under the trade designation “EXPANCEL” (e.g., under the trade designation “EXPANCEL 551 DE”) from Akzo Nobel Pulp, Duluth, GA, and Performance Chemicals AB, Sundsvall, Sweden. Methods of making foams containing expandable polymeric microspheres and particulars of these microspheres are described in U.S. Pat. No.6,103,152 (Gehlsen et al.). Foams may also be prepared by forming gas voids in a composition using a variety of mechanisms including, for example, mechanical mechanisms, chemical mechanisms, and combinations thereof.
  • Useful mechanical foaming mechanisms include, for example, agitating (for example, shaking, stirring, or whipping the composition, and combinations thereof), injecting gas into the composition (for example, inserting a nozzle beneath the surface of the composition and blowing gas into the composition), and combinations thereof.
  • agitating for example, shaking, stirring, or whipping the composition, and combinations thereof
  • injecting gas into the composition for example, inserting a nozzle beneath the surface of the composition and blowing gas into the composition
  • Methods of making the foams with voids formed via a foaming agent are described in U.S. Pat. No.6,586,483 (Kolb et al.).
  • the foam, the foam support layer, and/or the curable support foam layer has a foam density of from 320 kilograms per cubic meter (kg/m 3 ) to 1041 kg/m 3 , from 400 kg/m 3 to 880 kg/m 3 , or from 561 kg/m 3 to 800 kg/m 3 .
  • the curable or cured foam support layer in the article of the present disclosure may be of any suitable thickness. In some embodiments, the thickness is at least 20 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, at least 200 micrometers, at least 250 micrometers, at least 300 micrometers, or at least 350 micrometers.
  • the thickness is not more than 2000 micrometers, not more than 1000 micrometers, or not more than 500 micrometers.
  • the polymer used to make the curable foam support layer may be initially coated onto and polymerized against a flexible backing sheet (for example, a release liner) that has a low-adhesion surface from which the polymerized layer is readily removable. If the opposite face of the backing sheet also has a low adhesion surface, the backing sheet with its polymerized layer may be wound up in roll form for storage prior to assembly of the finished adhesive article.
  • the curable adhesive film which may or may not be a foam or comprise a foam support layer, may contain one or more optional additives.
  • additives can include fillers, antioxidants, viscosity modifiers, pigments (inorganic or organic), tackifying resins, fibers, flame retardants, antistatic and slip agents, thermally conductive particles, electrically conductive particles, continuous microfibers, filaments, and mixtures thereof.
  • Various additives may be used in amounts typical for adhesive tapes.
  • useful fillers include glass beads, metal oxide particles, silica particles (e.g., fumed silica), carbonates, metal oxides, silicates (e.g., talc, asbestos, clays, mica), sulfates (e.g., barium sulfate), metals in powder form (e.g., aluminum, zinc and iron), silicon dioxide, and aluminum trihydrate.
  • the solid or hollow filler particles comprise a polymer, glass, ceramic, or metal oxide material. Combinations of two or more fillers may be used if desired.
  • the filler comprises fumed silica.
  • Examples of useful organic pigments include halogenated copper phthalocyanines, aniline blacks, anthraquinone blacks, benzimidazolones, azo condensations, arylamides, diarylides, disazo condensations, isoindolinones, isoindolines, quinophthalones, anthrapyrimidines, flavanthrones, pyrazolone oranges, perinone oranges, beta-naphthols, BON arylamides, quinacridones, perylenes, anthraquinones, dibromanthrones, pyranthrones, diketopyrrolo-pyrrole pigments (DPP), dioxazine violets, copper and copper-free phthalocyanines, and indanthrones.
  • halogenated copper phthalocyanines aniline blacks, anthraquinone blacks, benzimidazolones, azo condensations, arylamides, diarylides, disazo
  • Examples of useful inorganic pigments include titanium dioxide, zinc oxide, zinc sulphide, lithopone, antimony oxide, barium sulfate, carbon black, graphite, black iron oxide, black micaceous iron oxide, brown iron oxides, metal complex browns, lead chromate, cadmium yellow, yellow oxides, bismuth vanadate, lead chromate, lead molybdate, cadmium red, red iron oxide, Prussian blue, ultramarine, cobalt blue, chrome green (Brunswick green), chromium oxide, hydrated chromium oxide, organic metal complexes, and laked dye pigments.
  • the adhesive system of the present disclosure includes an activator composition comprising an oxidizing agent. The activator composition is described in further detail below.
  • construction 300 includes tape 310 and substrates 320 and 330.
  • an activator composition 370 is applied to first substrate 320
  • an activator composition 380 is applied to second substrate 330.
  • the activator compositions 370 and 380 may be the same or different.
  • a double- sided tape 310 that includes curable adhesive films 340 and 360 adjacent to a support layer 350 is applied to activator 370 and 380 on substrates 320 and 330 such that the curable adhesive films 340 and 360 are in contact with the activator composition 370 and 380, respectively.
  • the assembly is held by external forces, e.g., a clamp, until the curable adhesive films become cured; however, in other embodiments the tackiness of the tape alone holds the assembly until cure.
  • the tape cures to form cured structural adhesive layers from curable adhesive films 340 and 360, which are adjacent to activator compositions 370 and 380.
  • the support layer 350 is also cured.
  • the support layer 350 is a foam support layer.
  • Activator composition 370 and 380 may be cured or not cured in the final construction, which, in the embodiment illustrated in FIG.3, includes two substrates bonded together by a double-sided tape using structural adhesive bonds.
  • the activator composition does not include unsaturated free-radically polymerizable groups.
  • the activator composition is not curable as applied and is not cured in the final bonded construction.
  • the first and second substrates in the methods of the present disclosure, as described above and below in any of their embodiments, may be composed of any suitable material.
  • Suitable substrate materials include metals (e.g., aluminum, titanium, stainless steel, and steel), polymeric materials (e.g., polyolefins, polyethylenes, polypropylenes, polystyrenes, poly(meth)acrylates, polyurethanes, natural or synthetic rubbers, and polydienes), natural materials (e.g., wood and stone) or derivatives thereof (e.g., composite board and concrete), glass material, and ceramic materials. If two substrates are bonded together in the articles and processes of the present disclosure, the two substrates are independently selected.
  • metals e.g., aluminum, titanium, stainless steel, and steel
  • polymeric materials e.g., polyolefins, polyethylenes, polypropylenes, polystyrenes, poly(meth)acrylates, polyurethanes, natural or synthetic rubbers, and polydienes
  • natural materials e.g., wood and stone
  • derivatives thereof e.g., composite board and concrete
  • At least one of the surfaces of the first substrate or the surface of the second substrate comprises at least one of metal, glass, a polymer, paper, a painted surface, a nonwoven or woven fabric, wood, foam, or a composite.
  • the material of the surface of the first and second substrate may be found throughout the substrate, or the surface may include a different material from the bulk of the substrate.
  • the surface of the first substrate and/or second substrate comprises at least one of metal (e.g., steel, stainless steel, or aluminum), glass (e.g., which may be coated with indium tin oxide, for example,), a polymer (e.g., a plastic, rubber, thermoplastic elastomer, or thermoset), paper, a painted surface, or a composite.
  • metal e.g., steel, stainless steel, or aluminum
  • glass e.g., which may be coated with indium tin oxide, for example,
  • a polymer e.g., a plastic, rubber, thermoplastic elastomer, or thermoset
  • paper e.g., a painted surface, or a composite.
  • a composite material may be made from any two or more constituent materials with different physical or chemical properties. When the constituents are combined to make a composite, a material having characteristics different from the individual components is typically achieved.
  • the surface of at least one of the first or second substrates may include polymers such as polyolefins (e.g., polypropylene, polyethylene, high density polyethylene, blends of polypropylene), polyamide 6 (PA6), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), PC/ABS blends, polyvinyl chloride (PVC), polyamide (PA), polyurethane (PUR), thermoplastic elastomers (TPE), polyoxymethylene (POM), polystyrene, polyester (e.g., polyethylene terephthalate), poly(methyl) methacrylate (PMMA), and combinations thereof.
  • polyolefins e.g., polypropylene, polyethylene, high density polyethylene, blends of polypropylene
  • PA6 polyamide 6
  • ABS acrylonitrile butadiene styrene
  • PC polycarbonate
  • PC PC/ABS blends
  • PVC polyvinyl chlor
  • the surface of at least one of the first or second substrate may also include a metal coating on such polymers.
  • at least one of the first or second substrate comprises a transparent material such as glass or a polymer (e.g., acrylic or polycarbonate).
  • a tape useful in the adhesive system of the present disclosure also includes one or more barrier film support layers (having two major surfaces), one or more conventional adhesive layers (having two major surfaces) that include an adhesive that is not curable upon contact with the activator, and/or a tape backing material or release liners commonly used in multilayer tapes.
  • a double-sided tape of the present disclosure may include only one curable adhesive film and, in some embodiments, a curable foam support layer, and may include a secondary adhesive layer that is not curable upon contact with the activator composition.
  • tape 410 includes a curable adhesive film 440, and a secondary adhesive layer 460, which may be any of a variety of conventional adhesives (e.g., pressure sensitive adhesives) that are not curable upon contact with the activator composition, each of which are adjacent to opposite surfaces of support layer 450.
  • Examples of conventional adhesives include pressure sensitive adhesives that are tacky and bond instantly when pressure is applied, thermoplastic adhesives that bond with applied heat and pressure and can be reversible with heat, and thermosetting adhesives that bond when subjected to heat and pressure for a predetermined period of time so as to cause some irreversible chemical reaction to occur.
  • secondary adhesive layer 460 is a conventional pressure sensitive adhesive, which achieves lower adhesion strength than the curable adhesive film 440 applied to an activator on a substrate.
  • barrier film support layers i.e., barrier layers
  • barrier layers may be used in the tape of the adhesive system of the present disclosure to provide a barrier, for example, to migration of the oxidizing agent and/or crosslinkable species, for example.
  • a tape of the type described in FIG.1 can further include a barrier film support layer adjacent the major surface of the support layer opposite that of the curable adhesive film, such that a 3-layer tape including curable adhesive/support layer/barrier is formed.
  • a tape of the type described in FIG.2 can further include a barrier film support layer disposed between the support layer and one of the curable adhesive films.
  • a first curable adhesive film is adjacent a support layer, which is adjacent a barrier film support layer, which is adjacent a second curable adhesive film, such that a 4-layer tape including curable adhesive/support layer/barrier/curable adhesive is formed.
  • the support layer is a foam. In some embodiments, the support layer is curable.
  • the first curable adhesive film is adjacent the curable foam support layer
  • the barrier film support layer is adjacent a surface of the curable foam support layer opposite the first curable adhesive film
  • the second curable adhesive film is adjacent a surface of the barrier film support layer opposite the curable foam support layer.
  • a multilayer tape can be prepared from two tapes of the type described in FIG.1 with a barrier film support layer disposed between the support layers of the two tapes, such that a 5-layer tape including curable adhesive film/support layer/barrier/support layer/curable adhesive film is formed.
  • the support layer is a foam.
  • the support layer is curable.
  • a multilayer tape can be prepared from two double-sided tapes of the type shown in FIG.2 with a barrier film support layer disposed between the two tapes, such that a 7-layer tape including curable adhesive film/support layer/curable adhesive film/barrier/curable adhesive film/support layer/curable adhesive film is formed. That is, in such an embodiment, a first curable adhesive film, a first support layer, a second curable adhesive film, a barrier film support layer, a third curable adhesive film, a second support layer, and a fourth curable adhesive film are sequentially stacked.
  • the support layer is a foam. In some embodiments, the support layer is curable.
  • the tape 510 includes a first curable adhesive film 540 (first adhesive layer), and a second curable adhesive film 560 (second adhesive layer), each of which are adjacent to the opposite major surfaces of a first support layer 550, in some embodiments, a foam support layer.
  • the tape 510 also includes a third curable adhesive film 540’, and a fourth curable adhesive film 560’, each of which are adjacent to the opposite major surfaces of a second support layer 550’.
  • the curable adhesive film 560 has a surface 562 that is adjacent a first surface 592 of barrier film support layer 590, and the curable adhesive film 560’ has a surface 562’ that is adjacent a second surface 594 of barrier film support layer 590.
  • Barrier film support layer 590 prevents migration of crosslinkable species and/or oxidizing agent across it.
  • different curing mechanisms and curable components can be used on either side of the barrier layer (i.e., within layers 540/550/560 as compared to layers 540’/550’/560’).
  • an activator composition is used when bonding tape 510 to a first substrate, for example, through third curable adhesive film 540’.
  • the layers 540’/550’/560’ cure to form cured structural adhesive layers while barrier 590 may prevent curing of layers 540/550/560.
  • Another, independently selected, activator composition may be used to bond tape 510 to a second substrate through first curable adhesive film 540.
  • the layers 540/550/560 may then cure to form structural adhesive layers.
  • a double-sided tape 610 that includes curable adhesive films 640 and 660 adjacent to a single support layer 650 is applied to second substrate 630 such that curable adhesive film 660 is in contact with second substrate 630.
  • the support layer is a foam.
  • the support layer is curable, for example, a curable adhesive film as described herein.
  • An activator composition 670 in the adhesive system of the present disclosure is applied to first substrate 620.
  • the activator 670 and the curable adhesive film 640 of the double-sided tape 610 are brought into contact. Once the activator 670 and the curable adhesive film 640 are brought into contact, curing begins and continues through foam support layer 650 and curable adhesive film 660.
  • the tape cures to form cured structural adhesive layers from curable adhesive films 640 and 660 and cured foam support layer 650.
  • the assembly is held by external forces, e.g., a clamp, until the curable adhesive films become cured; however, in other embodiments, the tackiness of the tape alone holds the assembly until cure.
  • Activator composition 670 may be cured or uncured in the final cured construction 600, which include two substrates bonded together by a double-sided tape including structural adhesive bonds.
  • the activator composition can be applied using a variety of methods as described below.
  • the tape may be attached to a substrate at the point of manufacture and bonded at a different time and/or place.
  • the tape may be attached to a first substrate at the point of manufacture, and the tape may optionally be covered with a conventional release liner for any period of time before bonding it to an activated second substrate.
  • the activator composition may be applied to a second substrate at a second point of manufacture, and the first substrate having the tape thereon and the activated second substrate may be bonded at the second point of manufacture or even at a third time and/or place.
  • the method includes applying a tape as described above in any of its embodiments to a first substrate, applying an activator composition as described above in any of its embodiments to a second substrate, and contacting the tape on the first substrate and the activator on the second substrate to bond the first and second substrates.
  • applying the tape is carried out at least 1, 3, or 5 days or at least 1, 2, 3, 4, 5, or 6 weeks before contacting the tape on the first substrate and the activator on the second substrate.
  • the tape is covered with a release liner, in some embodiments, for any of the times described above, and the release liner is removed before contacting the tape on the first substrate and the activator on the second substrate.
  • the article 700 shown in FIG.7 may be useful.
  • the article 700 includes a curable adhesive film 740 and an oxygen- permeable liner 725 on at least one side of the curable adhesive film.
  • the curable adhesive film 740 comprises the polymer blend described herein, unsaturated free-radically polymerizable groups, a transition metal cation, optionally a redox accelerator, and an oxidizing agent.
  • the embodiment illustrated in FIG.7 also includes a first substrate 720.
  • the illustrated embodiment may be made by a process including applying activator composition 730 to the substrate 720, wherein the activator comprises the oxidizing agent, applying an adhesive film directly adjacent the activator composition 730 on the substrate 720, and joining the adhesive film with the oxygen-permeable liner.
  • the curable adhesive film comprises the polymer blend disclosed herein, the unsaturated free-radically polymerizable groups, the transition metal cation, and optionally the redox accelerator.
  • the oxidizing agent of the activator composition 730 migrates into the curable adhesive film.
  • curing of the curable adhesive film is inhibited by oxygen. Therefore, while the oxygen-permeable liner is in place, the curable adhesive film does not cure for a period of several days or several weeks.
  • the process of making the illustrated embodiment includes forming the curable adhesive film on the oxygen- permeable liner and applying the curable adhesive film directly adjacent the activator while the adhesive film is in contact with the oxygen-permeable liner.
  • the article 800 shown in FIG.8 may be useful.
  • the article 800 includes a curable adhesive film 840 and an oxygen- permeable liner 825 on at least one side of the curable adhesive film.
  • the curable adhesive film 840 comprises the polymer blend describe herein, unsaturated free-radically polymerizable groups, which may be bonded to the polymer or in a species other than the polymer, a transition metal cation, optionally a redox accelerator, and an oxidizing agent.
  • the oxygen- permeable liner 825 comprises ridges 827 on at least one surface 826. The height of the ridges may be in a range from 4 micrometers ( ⁇ m) to 200 ⁇ m, from 8 ⁇ m to 100 ⁇ m, or from 10 ⁇ m to 30 ⁇ m.
  • the ridges can be considered microstructures.
  • the ridges may be in regular patterns or may appear randomly spaced and may have a variety of cross-sectional shapes.
  • the curable adhesive film 840 includes channels 843 corresponding to the ridges 827 in surface 846. Such channels are capable of aiding in the escape of air during the later application of the surface 846 to a substrate.
  • the channels, and methods of their production, may be as taught in U.S. Pat. No.6,655,281 (Jordan et al.).
  • the embodiment illustrated in FIG.8 also includes a release liner 815.
  • the illustrated embodiment may be made by applying an activator composition 830 to the release liner 815, wherein the activator composition comprises the oxidizing agent.
  • the adhesive film including the polymer blend, the unsaturated free-radically polymerizable groups, the transition metal cation, and optionally the redox accelerator conveniently formed on the oxygen-permeable liner including ridges can then be applied directly adjacent the activator 830 on the release liner.
  • the oxidizing agent of the activator 230 migrates into the adhesive film; however, curing of the curable adhesive film is inhibited by oxygen. Therefore, while the oxygen-permeable liner is in place, the curable adhesive film does not cure for a period of several days or several weeks.
  • air bleed channels 843 may also be formed in the opposing surface of the adhesive film, which may help to improve contact when it is applied to the activator composition.
  • FIG.9 illustrates another embodiment of the method of bonding a first substrate according to the present disclosure.
  • the method comprises bonding first and second substrates using an article 900 such as article 700 shown in FIG.7.
  • the process illustrated in FIG.9 includes removing oxygen-permeable liner 925 to expose curable adhesive film 940.
  • curable adhesive film 940 may also be the first layer of a multilayer curable adhesive film 110, 210 as shown in FIGS.1 or 2.
  • the process includes bonding second substrate 980 to curable adhesive film 940.
  • the bonded article is held by external forces, e.g., a clamp, until the curable adhesive film becomes cured; however, in other embodiments tackiness of the curable adhesive film alone holds the assembly until the curable adhesive film becomes cured.
  • the curable adhesive film 940 provides a structural adhesive layer.
  • the process for making bonded article 905 further comprises applying an optional activator composition 935 to the second substrate 980 before bonding second substrate 980 to curable adhesive film 940.
  • Optional activator composition 935 comprises a second oxidizing agent, wherein the second oxidizing agent is the same or different from the oxidizing agent in the first activator 930.
  • bonded article 905 includes first and second substrates 920, 980 bonded together with a structural adhesive made from first activator composition 930, curable adhesive film 940, and optional activator 935.
  • FIG.10 illustrates another embodiment of the method of bonding a first substrate according to the present disclosure. The method comprises bonding first and second substrates using two independently selected articles 1000, 1000a such as article 700 shown in FIG.7. The process illustrated in FIG.10 includes removing oxygen-permeable liner 1025 from two articles 1000, 1000a to expose curable adhesive film 1040 on both articles 1000 and 1000a.
  • the two articles 1000, 1000a may be the same or different from each other, including first and second substrates 1020, 1080, which may be the same or different from each other, curable adhesive films 1040, which may be the same or different from each other, and oxygen-permeable liners 1025, which may be the same or different from each other.
  • first and second substrates 1020, 1080 which may be the same or different from each other
  • curable adhesive films 1040 which may be the same or different from each other
  • oxygen-permeable liners 1025 which may be the same or different from each other.
  • one or more of the curable adhesive films 1040 may also be the first layer of a multilayer curable adhesive film 110, 210 as shown in FIGS.1 and 2. As shown in FIG.10, the curable adhesive films 1040 are positioned to contact each other once the oxygen-permeable films are removed and then bonded together.
  • FIG.11 illustrates another embodiment of the method of bonding a first substrate according to the present disclosure.
  • the method includes making a bonded article 1105 including two substrates using an embodiment of the article similar to that shown in FIG.8 except that no ridges 827 or channels 843 are shown in FIG.11.
  • curable adhesive film 840 may also be the first layer of a multilayer curable adhesive film 110, 210 as shown in FIGS.1 and 2.
  • the process illustrated in FIG.11 includes removing the release liner 1115 to provide a first adhesive surface 1148, removing the oxygen-permeable liner 1125 to provide a second adhesive surface 1146, bonding the first adhesive surface 1148 to a first substrate 1120, and bonding the second adhesive surface 1146 to a second substrate 1180.
  • Removing oxygen-permeable liner 1125 and release liner 1115 may be carried out simultaneously or sequentially in any order.
  • bonding first adhesive surface 1148 to a first substrate 1120 and bonding second adhesive surface 1146 to a second substrate 1180 can be carried out simultaneously or sequentially in any order. Bonding first adhesive surface 1148 to a first substrate 1120 can be carried out before removing the oxygen-permeable liner 1125, or bonding second adhesive surface 1146 to a second substrate 1180 can be carried out before removing release liner 1115.
  • the bonded article is held by external forces, e.g., a clamp, until the curable adhesive film becomes cured; however, in other embodiments, tackiness of the curable adhesive film alone holds the assembly until the curable adhesive film becomes cured. Once cured, the curable adhesive film 1140 provides a structural adhesive layer.
  • the process further comprises applying activator composition 1135 to at least one of first substrate 1120 or second substrate 1180 before bonding first and second adhesive surfaces 1148, 1146 to first and second substrates 1120, 1180, respectively.
  • activator composition 1135 is applied to only one of the first substrate 1120 or the second substrate 1180.
  • activator composition 1135 is applied to both the first substrate 1120 and the second substrate 1180.
  • Optional activator composition 1135 comprises a second oxidizing agent, wherein the second oxidizing agent is the same or different from the oxidizing agent in the first activator composition 1130.
  • the activator compositions 1135 and their components applied to first substrate 1120 and second substrate 1180 may be the same or different.
  • the oxidizing agent of the activator composition 1135 migrates into the curable adhesive film 1140 to participate in curing the curable adhesive film 1140 to form a structural adhesive layer.
  • the embodiment illustrated in FIG.11 does not include ridges on the oxygen-permeable liner 1125 or the release liner 1115.
  • one or both of oxygen-permeable liner 1125 or release liner 1115 has ridges on a surface that contacts curable adhesive film 1140 to provide channels in the curable adhesive film.
  • the surface without channels may be placed on a first substrate 820 and the second substrate 880 may then be brought into contact with the surface 846 including channels.
  • Any oxygen-permeable liner that allows sufficient oxygen to pass through to inhibit the curing of the unsaturated free-radically polymerizable groups may be useful in the articles and processes of the present disclosure.
  • Suitable materials for a liner include paper, polyvinyl chloride (PVC), polylactic acid (PLA), polyhydroxyalkanoates (PHA), polyhydroxybutyrate (PHB), polystyrene (PS), and polyolefins (e.g., polypropylene, high density polyethylene (HDPE), low density polyethylene (LDPE), biaxially oriented polypropylene (BOPP)).
  • the oxygen-permeable liner comprises at least one of paper or a polyolefin.
  • the oxygen-permeable liner may have a low-adhesion surface provided, for example, by a silicone, a fluoropolymer, a carbamate, an acrylic, a urethane, or a polyolefin.
  • useful release agents that may, in some embodiments, be coated on the oxygen-permeable liner include silicone copolymers (e.g., silicone acrylates, silicone polyurethanes, and silicone polyureas), fluorosilicones, perfluoropolyethers, polyethylene, polypropylene, low-density polyethylene), and combinations thereof.
  • the oxygen-permeable liner is poly coated kraft paper (i.e., paper coated with polyethylene), which may or may not be silicone-coated.
  • the curable adhesive film is stable at room temperature for at least two weeks.
  • applying the curable adhesive film covered with an oxygen-permeable liner is carried out at least 1, 3, or 5 days or at least 1, 2, 3, or 4 weeks before removing the oxygen- permeable liner and bonding the curable adhesive film to the second substrate.
  • applying the curable adhesive film covered with an oxygen-permeable liner is carried out at least 1, 3, or 5 days or at least 1, 2, 3, or 4 weeks before removing the oxygen- permeable liner and bonding the curable adhesive film to the second substrate.
  • a curable adhesive film containing no oxidizing agent may be attached to a first substrate at the point of manufacture, and an activator including an oxidizing agent may be applied to a second substrate and at a second point of manufacture, and the first substrate and the activated second substrate may be bonded at the second point of manufacture or even at a third time and/or place
  • the methods illustrated in FIGS.7 to 11 provide even greater flexibility, since it is possible that second substrate may not even need to be activated to achieve adequate bonding.
  • allowing more time for the oxidizing agent to migrate throughout the curable adhesive film while it is covered with an oxygen-permeable liner may provide stronger structural adhesive bonds more quickly once the oxygen- permeable liner is removed and the curable adhesive film is bonded to the second substrate.
  • U.S. Pat. Appl. Nos.2020/0362204, 2021/0102095, and 2021/0102097 each to Ranade et al., describe an adhesive system as described above in a construction that includes a release liner, the purpose of the release liner is to exclude oxygen. The release liner is said to preferably be left in place until cure is complete.
  • the ability of the oxygen-permeable liner in the article of the present disclosure to provide two or more weeks of stability of the curable adhesive film, which includes the unsaturated free- radically polymerizable groups, the transition metal cation, and the oxidizing agent, is quite unexpected.
  • the curable adhesive film is stable at room temperature for at least two weeks, it means that the dynamic shear adhesion on aluminum, measured as described in the Examples below, does not fall to lower than 90% of the initial adhesion value, measured on the day the curable adhesive film is applied to the activator.
  • the release liner as described above in connection with FIGS.8 and 11, may be an oxygen- permeable liner as describe above in any of its embodiments.
  • the release liner need not be oxygen-permeable and can include other materials, for example, ethylene vinyl acetate, polyurethanes, cellulose acetate, polyvinylidene fluoride, and polyesters such as polyethylene terephthalate.
  • the release liner may be coated with a layer of a release agent such as a silicone, a fluoropolymer, a carbamate, an acrylic, or a polyolefin, including any of those described above in connection with the oxygen-permeable liner. Coatings may be present on both sides of a release liner, and these liners may be the same or different.
  • Suitable release liners include commercially available liners that have a silicone release coating on polyethylene terephthalate film.
  • the release liner can have ridges on its surface as described above in any of their embodiments in connection with the oxygen-permeable liner.
  • the activator composition useful in the adhesive system and method of the present disclosure comprises an oxidizing agent. Any suitable oxidizing agent may be used including organic peroxides and hydroperoxides, inorganic peroxides, and persulfates. Suitable organic peroxides include hydroperoxides, di-peroxides, ketone peroxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates.
  • Suitable organic hydroperoxides include those represented by formula R-O-O-H with R being linear alkyl (e.g., C l -C 20 linear alkyls), branched alkyl (e.g., C 3 -C 20 branched alkyls), cycloalkyl (e.g., C 6 -C 12 cycloalkyls), alkaryl (e.g., C 7 -C 20 alkaryls), aralkyls (e.g., C 7 -C 20 aralkyls), and aryls (e.g., C 6 -C 12 aryls).
  • R being linear alkyl (e.g., C l -C 20 linear alkyls), branched alkyl (e.g., C 3 -C 20 branched alkyls), cycloalkyl (e.g., C 6 -C 12 cycloalkyls), alkaryl (e.g., C
  • organic hydroperoxides examples include t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, p-methane hydroperoxide, and l,l,3,3- tetramethylbutyl hydroperoxide.
  • Suitable organic peroxides include di-peroxides represented by formula R 1 -O-O-R 2 -O-O-R 3 , with R l and R 3 being independently selected from H, linear alkyls (e.g., C l -C 6 linear alkyls), branched alkyls (e.g., C l -C 6 branched alkyls), cycloalkyls (e.g., C 5 -C 10 cycloalkyls), alkaryls (e.g., C 7 -C 12 alkaryls), aralkyls (e.g., C 7 -C 20 aralkyls), or aryls (e.g., C 6 -C 10 aryls), and R 2 being selected from linear or branched alkylene (e.g., C l -C 6 linear or branched alkylene).
  • R l and R 3 being independently selected from H, linear alkyls (e
  • Suitable ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.
  • Suitable peroxyesters include alpha-cumylperoxyneodecanoate, t-butyl peroxypivarate, t-butyl peroxyneodecanoate, 2,2,4-trimethylpentylperoxy-2-ethyl hexanoate, t- amylperoxy-2-ethyl hexanoate, t-butylperoxy-2-ethyl hexanoate, di-t- butylperoxy isophthalate, di-t-butyl peroxy hexahydroterephthalate, t-butylperoxy-3,3,5- trimethylhexanoate, t-butylperoxy acetate, t- but
  • Suitable peroxydicarbonates include di-3-methoxy peroxidicarbonate, di-2-ethylhexyl peroxy-dicarbonate, bis(4-t- butylcyclohexyl)peroxidicarbonate, diisopropyl-l-peroxydicarbonate, di-n-propyl peroxidicarbonate, di-2-ethoxyethyl-peroxidicarbonate, and diallyl peroxidicarbonate.
  • Suitable diacyl peroxides include acetyl peroxide, benzoyl peroxide, decanoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroylperoxide.
  • Suitable dialkyl peroxides include di-t-butyl peroxide, dicumylperoxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5- di(t-butylperpoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t- butylperoxy)-3-hexane.
  • Suitable peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, and 4,4- bis(t-butylperoxy)valeric acid-n-butylester.
  • Suitable organic peroxides may additionally include t- butyl peroxy ethylhexyl carbonate, t-butyl peroxy trimethylhexanoate, t-butyl peroxy ethylhexanoate, t- amyl peroxy ethylhexanoate, t-octyl peroxy ethylhexanoate, t-amyl peroxy ethylhexyl carbonate, t-butyl peroxy isopropyl carbonate, t-butyl peroxyneodecanoate, and t-butyl peroxyisobutyrate.
  • the activator composition is liquid at normal temperature and pressure.
  • the activator composition comprises a liquid carrier.
  • the liquid carrier is a solvent.
  • the activator composition comprises 75 weight percent to 99 weight percent, or 93 weight percent to 98 weight percent, of the solvent, wherein the weight percentages are all based on the total weight of the activator composition.
  • the activator composition includes a plasticizer.
  • the plasticizer is of the following formula: (R—X—) n Z, wherein: each R may be hydrogen, C 1 -C 14 alkyl, aryl, alkaryl, or aralkyl, each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide; each X may be oxygen, nitrogen, carbonyl, carboxyl, or carbamide; Z may be a hydrogen, C 1 -C 14 alkyl, aryl, alkaryl, aralkyl, C 1 - C 14 alkylene, arylene, alkarylene, aralkylene, each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide; and n is an integer of 1 to 5.
  • n is an integer of 1 to 4.
  • the plasticizer comprises at least one of a benzoic acid ester, a myristic acid ester, a citric acid ester, an acetic acid ester, a succinic acid ester, a glutaric acid ester, an adipic acid ester, or a sebacic acid ester.
  • the plasticizer comprises at least one of a benzoic acid ester, a myristic acid ester, or a citric acid ester.
  • a citric acid ester may have one, two, three, or four R groups.
  • the activator composition further comprises a film-forming polymer.
  • the activator composition can be solid at normal temperature and pressure, and the activator composition may be in the form of a free-standing film.
  • suitable film-forming polymers useful for the activator include (meth)acrylate polymers such as any of those described above in any of their embodiments; aromatic or aliphatic polyurethanes (e.g., including those polyurethanes made with aliphatic or aromatic diols, polyamides, saturated and unsaturated polyesters, such as polybutylene terephthalate, polyethylene terephthalate, polyglycolic acid, polylactic acid, poly-2-hydroxy butyrate, polycaprolactone, and combinations containing maleic acid repeating units); polyethers (e.g., such as polyacetal and its copolymers, polyphenylene oxide, polyetherketone, polyetheretherketone); natural and synthetic rubbers (e.g., polyisoprene, polychloroprene, nitrile rubber, butadiene-based rubbers
  • the film-forming polymer or oligomer is a (meth)acrylate functional polymer, such as that made by adding (meth)acrylate end groups to polyester, polyurethane, polybutadiene, or polyether polymers. Various combinations of any of these film-forming polymers may be useful in the activator composition.
  • the film-forming polymer is a reactive polymer comprising unsaturated free-radically polymerizable groups, as described herein for the curable adhesive film. In some embodiments, the film-forming polymer does not comprise unsaturated free-radically polymerizable groups, as described herein for the curable adhesive film.
  • the activator composition may include a reactive species comprising unsaturated free-radically polymerizable groups, as described herein for the curable adhesive film. These components may be the same or different from these components in the curable adhesive film.
  • the film-forming polymer may include a rubber and/or a (meth)acrylate polymer.
  • the film-forming polymer is a (meth)acrylate polymer made from any of the monomers described above for the curable adhesive film and the curable foam support layer.
  • the (meth)acrylate polymer is any of the (meth)acrylate copolymers or nitrogen-containing (meth)acrylate copolymers described above for the curable adhesive film and the curable foam support layer.
  • the rubber comprises a block copolymer of a styrene and an alkene. In some embodiments, the rubber comprises a styrene-ethylene/butylene-styrene block copolymer grafted with maleic anhydride. In some embodiments, the rubber comprises at least one of a styrene-isoprene-styrene copolymer, styrene-butadiene-styrene copolymer, a styrene-ethylene-butylene-styrene copolymer. Linear and star block copolymers and combinations thereof can be useful.
  • the activator composition When containing a film-forming polymer, the activator composition may be a liquid at normal temperature and pressure, for example, if the film-forming polymer is dissolved in a solvent. In other embodiments, the activator composition may be applied as a free-standing film, as described herein for the curable adhesive film.
  • the free-standing film can include any of the film-forming polymers described above, any of the rubbers described above, any of the plasticizers or additives described above, and any of the oxidizing agents described above.
  • the free-standing film includes an amine- functional (meth)acrylate copolymer that is a polymerization reaction product of an amine-functional (meth)acryloyl compound (e.g., amine-functional (meth)acrylic acid esters and amides) and a non-amine- vinyl monomer.
  • an amine-functional (meth)acryloyl compound e.g., amine-functional (meth)acrylic acid esters and amides
  • the amine-functional (meth) acrylate copolymer has a calculated glass transition temperature (Tg) greater than or equal to 12°C.
  • Tg glass transition temperature
  • the amine- functional (meth) acrylate copolymer has a calculated Tg greater than or equal to 20°C.
  • the amine-functional (meth)acryloyl compound e.g., amine-functional (meth)acrylic acid esters and amides
  • the amine-functional (meth)acryloyl compound include 2-(N,N-dimethylaminoethyl) (meth)acrylate, 2-(N,N-diethylaminoethyl) (meth)acrylate, 2-(t-butylaminoethyl) (meth)acrylate, 2-(N,N-dimethylaminoethyl) (meth)acrylamide, 2- (N,N-diethylaminoethyl) (meth)acrylamide, 2-(t-butylaminoethyl) (meth)acrylamide, and N- (meth)acryloylpiperidine.
  • the non-amine-vinyl monomer is selected from the group consisting of a (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, a vinyl ester, a styrene, a (meth)acrylonitrile, and mixtures thereof.
  • the non-amine-vinyl monomer is a (meth)acrylic acid ester of a C1 to C18 alcohol.
  • the free-standing film is a pressure sensitive adhesive.
  • the activator composition is solid at normal temperature and pressure. In some embodiments, the solid activator composition is not a free-standing film.
  • a film of the solid activator composition lacks mechanical integrity independent of contact with any supporting material (e.g., a release liner or substrate to be bonded).
  • any supporting material e.g., a release liner or substrate to be bonded.
  • the solid activator composition can retain its shape; however, an intact film of the solid activator composition cannot be removed from a supporting material on which it is deposited.
  • the solid activator composition can be in the form of a crayon or paste, and applying the solid activator composition may be carried out by at least one of rubbing or spreading.
  • a crayon comprising the solid activator composition can be rubbed on substrates 320 and 330 as shown in FIG.3 or any of the substrates illustrated and described herein.
  • solid activator composition in the form of a paste can be spread on substrates 320 and 330 using any suitable implement.
  • the solid activator composition useful in the adhesive system and method of the present disclosure can include a variety of polymeric compositions.
  • the solid composition can contain starch derivatives, condensation products of an aldehyde and/or ketone with a polyol (e.g., the reaction product of sorbitol and benzaldehyde), or plasticized rubbers (e.g., natural or synthetic rubbers).
  • Useful crystalline monomer units include those from monomers in which a homopolymer thereof has a melting temperature in a range from 45 ⁇ C to 68 ⁇ C.
  • the crystalline monomeric unit can be made from a vinyl, acrylate, or methacrylate monomer.
  • the pendent alkyl chain has 16 to 40, 16 to 30, 16 to 22, or 18 to 22 carbon atoms.
  • Useful acrylate monomers for producing the crystalline monomer units include octadecyl acrylate, behenyl acrylate, tricontyl acrylate, tetracontyl acrylate, and pentacontyl acrylate, which have pendent alkyl chains having 18, 18 to 22, 26 to 34, 36 to 44, and 46 to 54 carbon atoms, respectively.
  • the at least one other monomeric unit in the acrylic polymer of the solid activator composition is a waxy monomeric unit with a pendent alkyl chain having 14 to 50 carbon atoms.
  • Useful waxy monomer units include those from monomers in which a homopolymer thereof has a melting temperature in a range from 25 ⁇ C to 44 ⁇ C.
  • the crystalline monomeric unit can be made from a vinyl, acrylate, or methacrylate monomer.
  • the pendent alkyl chain has 14 to 40, 14 to 30, 14 to 22, or 16 to 22 carbon atoms.
  • Useful monomers may have some branching and may be methacrylates, which can be useful for disrupting crystallinity.
  • Useful methacrylate monomers for producing the waxy monomer units include octadecyl methacrylate (i.e., stearyl methacrylate) and behenyl methacrylate.
  • the at least one other monomeric unit in the acrylic polymer of the solid activator composition is a monomer unit from a monomer that when homopolymerized provides a non- crystalline polymer.
  • the monomer units arise from a high Tg monomer.
  • the term “high Tg monomer” refers to a monomer that has a Tg greater than 30 ⁇ C, greater than 40 ⁇ C, or greater than 50 ⁇ C when homopolymerized (i.e., a homopolymer formed from the monomer has a Tg greater than 30 ⁇ C, greater than 40 ⁇ C, or greater than 50 ⁇ C).
  • Some suitable high Tg monomers have a single (meth)acryloyl group such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl (meth)acrylate, cyclohexyl methacrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, phenyl acrylate, benzyl methacrylate, 3,3,5 trimethylcyclohexyl (meth)acrylate, 2-phenoxyethyl methacrylate, N- octyl (meth)acrylamide, and mixtures thereof.
  • a single (meth)acryloyl group such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isoprop
  • Suitable high Tg monomers have a single vinyl group that is not a (meth)acryloyl group such as, for example, various vinyl ethers (e.g., vinyl methyl ether), vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrene (e.g., ⁇ -methyl styrene), vinyl halide, and mixtures thereof.
  • the at least one other monomeric unit in the acrylic polymer of the solid activator composition is a non-crystalline low Tg monomer.
  • low Tg monomer refers to a monomer having a Tg no greater than 20 o C when homopolymerized (i.e., a homopolymer formed from the low Tg monomer has a Tg no greater than 20 o C).
  • Suitable low Tg monomers are often selected from an alkyl (meth)acrylates, heteroalkyl (meth)acrylates, aryl substituted alkyl acrylate, and aryloxy substituted alkyl acrylates.
  • Examples of low Tg alkyl (meth)acrylate monomers often are non- tertiary alkyl acrylates but can be alkyl methacrylates having a linear alkyl group with at least 4 carbon atoms.
  • alkyl (meth)acrylates examples include n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, sec-butyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2- octyl acrylate, isooctyl acrylate, isononyl acrylate, isoamyl acrylate, n-decyl acrylate, isodecyl acrylate, n- decyl methacrylate, lauryl acrylate, isotridecyl acrylate, n-octadecyl acrylate, isostearyl acrylate,
  • heteroalkyl (meth)acrylate monomers often have at least 3 carbon atoms, at least 4 carbon atoms, or at least 6 carbon atoms and can have up to 30 or more carbon atoms, up to 20 carbon atoms, up to 18 carbon atoms, up to 16 carbon atoms, up to 12 carbon atoms, or up to 10 carbon atoms.
  • Specific examples of heteroalkyl (meth)acrylates include 2-ethoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-methoxyethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.
  • Examples of low-Tg aryl substituted alkyl acrylates or aryloxy substituted alkyl acrylates include 2-biphenylhexyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, and 2-phenylethyl acrylate.
  • the at least one other monomeric unit in the (meth)acrylate copolymer of the solid activator composition is derived from at least one of isooctyl acrylate, 2-ethyl hexyl acrylate, 2- octyl acrylate, n-octyl acrylate, n-butyl acrylate, sec-butyl acrylate, ethyl acrylate, diethyleneglycol methyl ether acrylate, triethyleneglycol methyl ether acrylate, allyl glycidyl ether, ethyl vinyl ether, 2- ethyl hexyl vinyl ether, hydroxyl ethyl acrylate, dodecyl methacrylate, dodecyl vinyl ether, polydimethylsiloxyl or amorphous polyether (meth)acrylates.
  • the at least one other monomeric unit in the acrylic polymer of the solid activator composition is an acrylic monomer unit comprising a carboxylic acid group.
  • suitable acrylic monomers comprising a carboxylic acid group to provide these monomer units include methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, beta-carboxy ethyl acrylate, and ⁇ -methacryloyl oxyethyl hydrogen succinate.
  • the acrylic monomer units comprising a carboxylic acid group are acrylic acid monomer units or methacrylic acid monomer units, in some embodiments, acrylic acid monomer units.
  • the at least one other monomeric unit in the acrylic polymer of the solid activator composition is a macromer monomeric unit.
  • Suitable macromers are prepared from the corresponding prepolymers of, for example, octadecyl acrylate (ODA), behenyl acrylate (BeA) and mixtures of tetradecyl acrylate (TDA), tetradecyl methacrylate (TDMA), hexadecyl acrylate (HDA), hexadecyl methacrylate (HDMA), ODA, octadecyl methacrylate (ODMA), eicosyl acrylate (ECA), eicosyl methacrylate (ECMA), and behenyl methacrylate (BeMA).
  • ODA octadecyl acrylate
  • BeA behenyl acrylate
  • TDA tetradecyl methacrylate
  • HDA hexadecyl acryl
  • the final macromer melting temperatures (T m ) is within the range of from about 35 °C to about 120 °C, about 35 °C to about 70 °C, or about 45 °C to about 60 °C.
  • the macromers are incorporated into the semi- crystalline polymers via standard polymerization techniques for the crayon or paste polymers described herein. Preparing a macromer can be carried out by polymerizing any of the monomers mentioned above in the presence of a functional chain-transfer agent, for example, 2-mercaptoethanol.
  • Hydroxy-terminated telechelic polymers can then be functionalized by reaction with acryloyl chloride, methacryloyl chloride, 2'-isocyanatoethyl methacrylate, 3-isopropenyl-alpha, or alpha-dimethylbenzyl isocyanate (IPDMBI), for example, as described in U.S. Pat. No.5,604,268 (Randen et al.).
  • IPDMBI alpha-dimethylbenzyl isocyanate
  • the acrylic polymer useful in the solid activator composition comprises from about 5 to about 96, or from about 5 to about 60, parts by weight per 100 parts by weight of acrylic polymer of at least one crystalline monomer having an alkyl carbon length of at least 16, typically not more than 50, carbon atoms; from about 4 to about 70, or from about 12 to about 59, parts by weight per 100 parts by weight of acrylic polymer of at least one non-crystalline monomer having a homopolymer Tg below about 80°C; from 0 to about 70 parts by weight per 100 parts by weight of acrylic polymer of at least one waxy monomer having an average pendant alkyl carbon length of at least 14, typically not more than 50, carbon atoms ; from 0 to about 10, or from about 0.5 to about 3, parts by weight per 100 parts by weight of acrylic polymer of at least one monomer having acid or base functionality; and from 0 to about 40, or from 0 to about 30, parts by weight per 100 parts by weight of acrylic polymer of at least one macromer unit having a melting temperature
  • the crystalline monomer component and non-crystalline monomer component can be selected such that when combined the non-crystalline component disrupts the crystallinity of the resultant adhesive polymer composition to an extent that the resultant composition will exhibit a melting temperature (Tm) of not more than 60 °C, 50 °C, or 40 °C as measured by Differential Scanning Calorimetry using the method described in U.S. Pat. No.11,267,997 (June et al.). In some embodiments, the composition will exhibit a major Tm in the range of about 25 °C to about 35 °C.
  • the acrylic polymer useful in the solid activator composition comprises monomeric units of octadecyl acrylate, octadecyl methacrylate, a macromer octadecyl acrylate, acrylic acid, and at least one of isooctyl acrylate (homopolymer, T g about -54°C), butyl methacrylate (homopolymer, T g about 20°C), or benzyl methacrylate (homopolymer, T g about 54°C).
  • Acrylic polymers can conveniently be made by any of the methods described above for making acrylic polymers.
  • tackifiers may be present in the activator composition useful in the adhesive system or method of the present disclosure.
  • the tackifier comprises at least one of a polyterpene (e.g., those based on ⁇ -pinene, ⁇ -pinene, or limonene), a terpene phenolic tackifier, a rosin acid, a rosin ester, an aliphatic hydrocarbon resin (e.g., those based on cis- or trans- piperylene, isoprene, 2-methyl-but-2-ene, cyclopentadiene, dicyclopentadiene, or combinations thereof), an aromatic resin (e.g.
  • the aromatic hydrocarbon resins may be C9-type petroleum resins obtained by copolymerizing a C9 fraction produced by thermal decomposition of petroleum naphtha, and aliphatic hydrocarbon resins may be C5-type petroleum resins obtained by copolymerizing a C5 fraction produced by thermal decomposition of petroleum naphtha.
  • Mixed aliphatic/aromatic resins may be C5/C9-type petroleum resins obtained by polymerizing a combination of a C5 fraction and C9 fraction produced by thermal decomposition of petroleum naphtha. Any of these tackifiers may be hydrogenated (e.g., partially or completely).
  • rosin includes natural rosin, refined or unrefined (refined rosin will usually contain, by weight, about 90% of rosin acids and about 10% of inert material), such as natural wood rosin, natural gum rosin, and tall oil rosin; modified rosin, refined or unrefined, such as disproportionated rosin, hydrogenated rosin, and polymerized rosin; and the pure or substantially pure acids, of which rosin is comprised, alone or in admixture.
  • natural rosin refined or unrefined
  • inert material such as natural wood rosin, natural gum rosin, and tall oil rosin
  • modified rosin, refined or unrefined such as disproportionated rosin, hydrogenated rosin, and polymerized rosin
  • pure or substantially pure acids of which rosin is comprised, alone or in admixture.
  • the rosin includes the rosin acid C 19 H 29 COOH, in some embodiments, at least one of abietic acid, neoabietic acid, palustric acid, levopimaric acid, pimaric acid, or an isopimaric acid.
  • the rosin comprises dehydro- or hydrogenated rosin acids, for example, dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid.
  • the tackifier can also include a metal rosinate (sometimes referred to in the art as a metal resinate).
  • the metal rosinate can be metal salt (e.g., zinc, calcium, or magnesium) of any of the rosins described above.
  • the solid activator composition comprises 0 to about 50, or from about 5 to about 40, parts by weight per 100 parts by weight of the solid activator composition of at least one tackifier.
  • Crystalline additives with varying functionality such as acids, diacids, alcohols, diols, and waxes based on linear hydrocarbons can be added to the solid activator composition useful in the adhesive system or method of the present disclosure. Crystalline additives can be selected so that they are melt miscible with the acrylic polymers described above (i.e., will form a transparent single phase system when molten). Upon cooling, such additives can partially or completely crystallize and form finely dispersed phases in the polymer.
  • Crystalline additives can provide improved storage stability (i.e., resistance to creep and flow) to the polymers up to the melting point of the crystalline additives.
  • about 3 to about 50 wt. % may be included in the solid activator composition.
  • the additives have an n-alkyl chain length of at least 20 carbons and may have a melting point of at least about 50°C or at least about 70°C.
  • suitable crystalline additives include stearic acid, zinc stearate, calcium stearate, stearyl alcohol, behenyl alcohol, behenic acid, C-30 alcohol, or a C-50 alcohol.
  • the solid activator composition comprises 0 to about 50, 3 to 50, or 0 to about 30, parts by weight per 100 parts by weight of solid activator composition of at least one crystalline additive. In some embodiments, the solid activator composition comprises from 0 to about 30, or about 1 to about 10, parts by weight of oil per 100 parts by weight of solid activator composition. Examples of useful oils include olive oil, glycerin, mineral oil, low molecular weight polyethylene oxide, and low molecular weight polypropylene oxide. In some embodiments, the solid activator composition comprises from 0 to about 50, or from about 10 to about 40, parts by weight of surfactant per 100 parts by weight of solid activator composition.
  • useful surfactants include anionic, non-ionic, and cationic surfactants such as stearic acid, block copolymers of ethylene oxide, propylene oxide, and blends thereof; C12 to C50 alcohol ethoxylates, alkylphenol ethoxylates, ethoxylated fatty acid esters, fatty acids, and ethoxylated fatty acids.
  • Examples of commercially available surfactants suitable for practicing the present disclosure include UNITHOXTM 420, 450, 480, 490, 550, 720, and 750 (from Baker Hughes), TERGITOLTM 15-S-3 and 15- S-20 (from Dow Chemical), PLURONIC® F38, F87, F68, F98, F127, and P85 (from BASF), and TETRONIC® 904, 908, 1107, 1304 (from BASF).
  • Fillers such as calcium carbonate, silica, bentonite clays, glass spheres and bubbles, and wood flour can be included in the solid activator composition. Dyes, pigments, and antioxidants can also be included.
  • the solid activator composition useful in the adhesive system and method of the present disclosure comprises 0 to about 50 parts by weight per 100 parts by weight of solid activator composition of at least one filler.
  • the solid activator composition includes a plasticizer, which may be any of those described above.
  • the solid activator composition further comprises a film- forming polymer.
  • the film-forming polymer can be any of these described above.
  • the film-forming polymer may include a rubber and/or a (meth)acrylate copolymer as described above.
  • the rubber useful in the solid activator composition comprises a block copolymer of a styrene and an alkene.
  • the rubber comprises a styrene- ethylene/butylene-styrene triblock copolymer. In some embodiments, the rubber comprises a styrene- ethylene/butylene-styrene block copolymer grafted with maleic anhydride. In some embodiments, the rubber comprises at least one of a styrene-isoprene-styrene copolymer, styrene-butadiene-styrene copolymer, a styrene-ethylene-butylene-styrene copolymer. Linear and star block copolymers and combinations thereof can be useful.
  • the activator composition may be applied any suitable thickness.
  • the thickness is at least 1 micrometer, at least 2 micrometers, at least 3 micrometers, at least 4 micrometers, or at least 5 micrometers.
  • thickness is not more than 20 micrometers, not more than 15 micrometers, or not more than 10 micrometers.
  • the solid activator composition is applied in an amount of not more than 3 milligrams per square centimeter. If the activator composition is a free-standing film, it can have any of the thicknesses described above for the curable adhesive film.
  • the solid activator composition for example, in the form of a free-standing film, crayon, or paste, need not include organic solvent.
  • the solid activator composition comprises less than 5 weight percent, less than 3 weight percent, less than 1 weight percent, less than 0.5 weight percent, less than 0.1 weight percent, or less than 0.01 weight percent of organic solvent.
  • the oxidizing agent is present in the activator composition as described above in any of its embodiments in an amount of at least 0.5 weight percent, at least 1 weight percent, at least 2 weight percent, or at least 4 weight percent, based on the total weight of the activator composition.
  • the oxidizing agent is present in the activator composition in an amount of up to 20 weight percent, up to 15 weight percent, up to 10 weight percent, or up to 5 weight percent, based on the total weight of the activator composition.
  • the activator composition also includes a transition metal cation, which may be one or more of any of those described herein for the curable adhesive film.
  • the activator further includes a silane (e.g., epoxy silane).
  • the activator composition includes no tackifier, or no species comprising unsaturated free-radically polymerizable groups, or both no tackifier and no species comprising unsaturated free-radically polymerizable groups.
  • the adhesive system of the present disclosure can conveniently be provided as a kit.
  • the kit comprises the tape as described above in any of its embodiments.
  • the kit also includes the activator composition, which may be in the form of a liquid, free-standing film, crayon, or paste as described above in any of their embodiments.
  • the solid activator composition is in the form of a crayon.
  • the crayon can have any suitable shape, such as a cylinder or prism with any desirable cross- sectional shape such as rectangle, triangle, or square. The shape at an end of the crayon can be adjusted, for example, for ease of writing although this is not a requirement.
  • the kit of the present disclosure can include the tape and the crayon. The crayon can be useful with or without a container.
  • the crayon can also be referred to as a stick.
  • the kit can include the tape and the stick.
  • An embodiment of a container useful for holding a solid activator composition useful in the adhesive system and method of the present disclosure is shown in FIG.12.
  • the container 1 is cylindrical in cross-section having cylindrical side walls 2.
  • On the base of the container is a knurled wheel 3 which forms part of a propulsion mechanism for the solid activator composition 4 in a generally cylindrical shape.
  • the container further comprises a cap 5 which is snap-fit engageable over the top end 6 of the container 1.
  • the top end 6 can be of lesser diameter than the side walls 2 and has a rim 7 which engages in a corresponding recess on the underside of the cap 5 to secure the cap 5 in place.
  • the knurled wheel 3 is attached to an elongate drive or winding shaft 8 which is centrally located within the housing formed by the side walls of the container.
  • a moveable carrier 9 On the winding shaft 8 is located a moveable carrier 9.
  • the carrier 9 is generally cylindrical (from an end view thereof—see for example FIG.13) and has a short peripheral upstanding wall 10 formed on its base 11.
  • the solid activator composition may be formed with the carrier 9, optionally the shaft 8, and optionally the wheel 3 in place.
  • the carrier 9 has a central threaded aperture 13 in which the threads 16 of the shaft 8 engage.
  • the knurled wheel 3 and the shaft 8 are both mounted for relative rotation to the container body.
  • the wheel 3 When the wheel 3 is turned it moves the carrier up or down the shaft 8 thus controlling the relative position of the mass and the container.
  • the carrier In the position shown the carrier has travelled part way up the shaft, moving the solid activator composition 4 to a position where it protrudes from the container.
  • the solid activator composition can then be applied by rubbing the mass against a substrate by manual force. Sufficient shearing of the mass takes place to allow it to rub off onto the substrate.
  • elongate ribs 14 are provided on opposing sides of the internal wall of the container. The ribs 14 run from the base of the container to a position proximate to the mouth if the container.
  • the ribs 14 each engage one of corresponding grooves 15 in the carrier 9 thus preventing relative rotation of the container and the carrier and ensuring that the carrier moves upwardly or downwardly when the shaft 8 turns.
  • the adhesive systems and methods of the present disclosure do not require mixing of separate components; rather, the solid activator composition is applied to a substrate or release liner, and the activator-coated substrate or release liner is contacted with the tape described above in any of its embodiments into which the oxidizing agent from the activator migrates.
  • An oxygen-permeable liner can be kept in place on the curable adhesive film until the curable adhesive film is ready to bond. Upon joining of the substrates to be adhered, thereby excluding oxygen, the curable adhesive film begins to cure, resulting in structural adhesive bonds.
  • cure can be achieved at normal temperature and pressure, without heat or autoclave. Likewise, in some embodiments of the adhesive systems and methods of the present disclosure, cure can be achieved without UV or other radiation treatment, and cure propagates well to areas inaccessible to radiation cure. In some embodiments of the present adhesive systems and methods, the curable adhesive film and the activator composition need not be refrigerated or kept in dark storage. In some embodiments of the method of the present disclosure, including the methods described above in any of their embodiments, the activator composition is applied onto intermittent portions of the first substrate or the second substrate while not applying the activator composition to other portions of the first substrate or the second substrate.
  • the curable adhesive film Upon contact with the activator composition, the curable adhesive film begins to cure, forming structural adhesive domains; however, the present investigators have found that this cure demonstrates limited propagation in the plane of the adhesive film.
  • cured structural adhesive domains are formed adjacent to the solid activator composition while uncured pressure sensitive adhesive domains can remain over the portions of the first substrate to which the solid activator composition was not applied.
  • the structural adhesive domains may constitute 1% to 99%, 1% to 75%, 1% to 50%, 1% to 25%, 75% to 99%, 50% to 99%, 25% to 99% or any desired portion of the adhesive film with the remainder of the adhesive film being pressure sensitive adhesive domains.
  • any suitable pattern of structural adhesive domains may be used, such as straight, curved, angled or broken lines; square, rectangular, triangular, hexagonal, or other polygonal grids; or random or ordered spots which may be circular, elliptical, polygonal, or other shapes. Pattern features may have any desired width and/or pitch dimensions.
  • the structural adhesive domains may be continuous or discontinuous and the pressure sensitive adhesive domains may be continuous or discontinuous.
  • the structural adhesive domains are discontinuous and surrounded by a continuous pressure sensitive adhesive domain, e.g., an arrangement of distinct posts of structural domain separated by a continuous pressure sensitive adhesive domain.
  • discontinuous pressure sensitive adhesive domains are surrounded by a continuous structural adhesive domain.
  • the present disclosure provides a tape comprising a curable adhesive film comprising a polymer blend comprising a (meth)acrylate copolymer comprising and a nitrogen- containing polymer, wherein the (meth)acrylate copolymer comprises acidic monomer units; unsaturated free-radically polymerizable groups, which may be bonded to the (meth)acrylate copolymer or in a species other than the (meth)acrylate copolymer; and a transition metal cation.
  • the present disclosure provides the tape of the first embodiment, wherein the curable adhesive film further comprises a quaternary ammonium salt.
  • the present disclosure provides the tape of the first or second embodiment, wherein the nitrogen-containing polymer comprises at least one of amino or amido functional groups.
  • the present disclosure provides the tape of any one of the first to third embodiments, wherein the nitrogen-containing polymer comprises at least one of a nitrogen-containing (meth)acrylate copolymer, a nitrogen-containing (meth)acrylate block copolymer, a polyvinylpyrrolidone polymer, or a polyvinylpyrrolidone copolymer.
  • the present disclosure provides the tape of any one of the first to fourth embodiments, wherein the unsaturated free-radically polymerizable groups are in a species other than the (meth)acrylate copolymer, and wherein the species is a crosslinking monomer, and wherein the polymer does not comprise unsaturated free-radically polymerizable groups.
  • the present disclosure provides the tape of any one of the first to fifth embodiments, wherein the nitrogen-containing block copolymer is present at an amount of at least 1 weight percent, not more than 40 weight percent, or in a range from 1 weight percent to 40 weight percent, based on the total weight of the curable adhesive film.
  • the present disclosure provides the tape of any one of the first to sixth embodiments, wherein the curable adhesive film is hot melt processable.
  • the present disclosure provides the tape of any one of the first to seventh embodiments, further comprising a foam support layer.
  • the present disclosure provides the tape of the eighth embodiment, wherein the curable adhesive film is borne on a first major surface of the foam support layer.
  • the present disclosure provides the tape of the eighth embodiment, wherein the curable adhesive film is directly bound to (e.g., laminated to) a first major surface of the foam support layer.
  • the present disclosure provides the tape of any one of the first to seventh embodiments, wherein the curable adhesive film is a foam adhesive.
  • the present disclosure provides tape of any one of the first to seventh embodiments, wherein the curable adhesive film comprises a foam support layer, a first adhesive layer on a first side of the foam support layer, and a second adhesive layer on a second side of the foam support layer, opposite the first adhesive layer, wherein at least one of the first adhesive layer, the second adhesive layer, or the foam support layer independently comprises the polymer blend, the unsaturated free-radically polymerizable groups, the transition metal cation, and optionally the quaternary ammonium salt.
  • the present disclosure provides the tape of the twelfth embodiment, wherein each one of the first adhesive layer, the second adhesive layer, and the foam support layer independently comprises the polymer blend, the unsaturated free-radically polymerizable groups, the transition metal cation, and optionally the quaternary ammonium salt.
  • the present disclosure provides the tape of the twelfth or thirteenth embodiment, wherein the first adhesive layer is borne on the first side of the foam support layer and the second adhesive layer is borne on the second side of the foam support layer.
  • the present disclosure provides the tape of the twelfth or thirteenth embodiment, wherein the first adhesive layer is directly bound to the first side of the foam support layer and the second adhesive layer is directly bound to the second side of the foam support layer.
  • the present disclosure provides the tape of any one of the twelfth to fifteenth embodiments, wherein the first adhesive layer, foam support layer, and second adhesive layer each comprise the same polymer blend.
  • the present disclosure provides tape of any one of the twelfth to sixteenth embodiments, wherein the foam support layer comprises a crosslinking monomer within the foam support layer.
  • the present disclosure provides the tape of the seventeenth embodiment, wherein the crosslinking monomer is different from the species comprising unsaturated free-radically polymerizable groups in the first and second adhesive layers.
  • the present disclosure provides tape of the seventeenth embodiment, wherein the crosslinking monomer migrates and/or has migrated into the foam support layer from at least one of the first adhesive layer or second adhesive layer.
  • the present disclosure provides the tape of any one of the twelfth to nineteenth embodiments, wherein the foam support layer comprises a foaming agent and the same components as the at least one of the first adhesive layer or second adhesive layer.
  • the present disclosure provides the tape of the twentieth embodiment, wherein the foaming agent comprises at least one of expandable microspheres, hollow glass bubbles, or gas bubbles optionally stabilized with a surfactant.
  • the present disclosure provides the tape of any one of the eighth to twenty-first embodiments, wherein the foam support layer or the foam adhesive comprises at least one of a closed cell foam or a syntactic foam.
  • the present disclosure provides an adhesive system comprising the tape of any one of the first to twenty-second embodiments and an activator composition comprising an oxidizing agent.
  • the present disclosure provides a method for bonding a first substrate, the method comprising applying an activator composition onto a surface of the first substrate, the activator composition comprising an oxidizing agent, and contacting the activator composition with a first surface of the tape of any one of the first to twenty-second embodiments.
  • the present disclosure provides the method of the twenty-fourth embodiment, further comprising bonding a second surface of the tape to a second substrate.
  • the present disclosure provides the method of the twenty-fourth embodiment, further comprising bonding a second surface of the tape to an oxygen-permeable liner.
  • the present disclosure provides the method of the twenty-sixth embodiment, wherein contacting the activator composition with a first surface of a tape is carried out while the second surface of the tape is attached to the oxygen-permeable liner.
  • the present disclosure provides the method of the twenty-sixth or twenty-seventh embodiment, the method comprising removing the oxygen-permeable liner from the second surface of the tape and bonding a second surface of the tape to the second substrate.
  • the present disclosure provides the method of the twenty-fifth or twenty-eighth embodiment, further comprising applying the activator composition onto a surface of the second substrate and contacting the activator composition on the second substrate with the second surface of the tape.
  • the present disclosure provides the method of any one of the twenty-fourth to twenty-ninth embodiments, wherein the first substrate is a release liner.
  • the present disclosure provides the method of the thirtieth embodiment, the method comprising removing the release liner to provide the first surface of the tape and bonding the first surface of the tape to a surface of a substrate.
  • the present disclosure provides the method of the thirty-first embodiment, further comprising applying a second activator composition to the surface of the substrate before bonding the first surface of the tape, wherein the second activator composition comprises a second oxidizing agent, wherein the second activator composition is the same or different from the activator composition.
  • the present disclosure provides the method of any one of the twenty-fourth to thirty-second embodiments, wherein applying the activator composition onto at least one of the surface of the first substrate or the surface of the second substrate comprises applying the activator composition onto intermittent portions of the first substrate or the second substrate while not applying the activator composition to other portions of the first substrate or the second substrate.
  • the present disclosure provides the tape of any one of the first to twenty-second embodiments, further comprising a release liner.
  • the present disclosure provides the tape of any one of the first to twenty-second embodiments or system of the twenty-third embodiment, further comprising an oxygen-permeable liner.
  • the present disclosure provides the method of any one of the twenty-sixth to thirty-third embodiments or the tape of the thirty-fifth embodiment, wherein the oxygen-permeable liner comprises at least one of paper or a polyolefin.
  • the present disclosure provides the method or tape of any one of the twenty-sixth to thirty-third, thirty-fifth, or thirty-sixth embodiments, wherein the oxygen-permeable liner comprises ridges on at least one surface.
  • the present disclosure provides method or tape of the thirty-seventh embodiment, wherein the curable adhesive film comprises an outer surface bearing channels corresponding to the ridges, wherein the channels are capable of aiding in escape of air during application of the outer surface to a substrate.
  • the present disclosure provides the adhesive system or method of any one of the twenty-third to thirty-third or thirty-fifth to thirty-eighth embodiments, wherein the activator composition does not include unsaturated free-radically polymerizable groups.
  • the present disclosure provides the adhesive system or method of any one of the twenty-third to thirty- third or thirty-fifth to thirty-ninth embodiments, wherein the oxidizing agent is an organic peroxide, an organic hydroperoxide, an inorganic peroxide, or a persulfate.
  • the present disclosure provides the adhesive system or method of any one of the twenty-third to thirty-third or thirty- fifth to fortieth embodiments, wherein the activator composition is a liquid at normal temperature and pressure.
  • the present disclosure provides the adhesive system or method of any one of the twenty-third to thirty-third or thirty-fifth to forty-first embodiments, wherein the activator composition comprises no tackifier.
  • the present disclosure provides the adhesive system or method of any one of the twenty-third to thirty-third or thirty-fifth to forty-second embodiments, wherein the activator composition comprises at least one of organic solvent or a plasticizer.
  • the present disclosure provides the adhesive system or method of any one of the twenty-third to thirty-third or thirty-fifth to forty-third embodiments, wherein the activator composition comprises a film-forming polymer.
  • the present disclosure provides the adhesive system or method of any one of the twenty-third to thirty-third or thirty- fifth to fortieth embodiments, wherein the activator composition is a solid at normal temperature and pressure, wherein the solid is in the form of a film, crayon, or paste.
  • the present disclosure provides the adhesive system or method of the forty-fifth embodiment, wherein the solid activator composition comprises an acrylic polymer comprising a crystalline monomeric unit having from 16 to 50 carbon atoms.
  • the present disclosure provides the adhesive system or method of the forty-fifth or forty-sixth embodiment, wherein the solid activator composition comprises at least one of a tackifier or inorganic filler.
  • the present disclosure provides the adhesive system or method of any one of the forty-fifth to forty-seventh embodiments, wherein the solid activator composition comprises at least one of a fatty acid, a fatty acid salt, or a fatty acid ester.
  • the present disclosure provides the adhesive system or method of the forty-fifth embodiment, wherein the solid activator composition comprises a polymer film.
  • the present disclosure provides the adhesive system or method of the forty-ninth embodiment, wherein the polymer film is at least one of an adhesive film or a hot-melt processable film.
  • DTMPTA Ditrimethylolpropane tetraacrylate available under the trade designation “MIRAMER M410” from Miwon Specialty Chemical Co., Ltd., Exton, PA, USA BTEAC Benzyltriethylammonium chloride available from Lindau Chemicals, Inc., Columbia, SC.
  • ADDITIVE 2 A non-functional block copolymer consisting of polymethylmethacrylate-b- polybutylacrylate-b-polymethylmethacrylate with no polarity modifier obtained under the trade designation NANOSTRENGTH M65 from ARKEMA, Colombes, France ADDITIVE 3
  • An acid functional block copolymer consisting of polymethylmethacrylate-b- polybutylacrylate-b-polymethylmethacrylate obtained under the trade designation NANOSTRENGTH M65A from ARKEMA.
  • ADDITIVE 4 A functional block copolymer of polymethylmethacrylate-b-polybutylacrylate-b- polymethylmethacrylate obtained under the trade designation NANOSTRENGTH M65N from ARKEMA.
  • ADDITIVE 5 A functional block copolymer of polymethylmethacrylate-b-polybutylacrylate-b- polymethylmethacrylate obtained under the trade designation NANOSTRENGTH M22N from ARKEMA. This is a nitrogen-containing polymer.
  • ADDITIVE 6 A spray dried polymer powder of a copolymer derived from the monomers N- vinylpyrrolidone and vinyl acetate with a weight ratio of approximately 6:4 obtained under the trade designation KOLLIDON VA64 from BASF.
  • a DDITIVE 7 A hygroscopic, amorphous polyvinylpyrrolidone polymer supplied as a white, free-flowing powder having a molecular weight of 6000-15000g/mol obtained under the trade designation PVP K-15 from Ashland Inc., Wilmington, DE.
  • a DDITIVE 8 A hygroscopic, amorphous polyvinylpyrrolidone polymer supplied as a white, free-flowing powder having a molecular weight of 60000g/mol obtained under the trade designation PVP K-30 from Ashland Inc.
  • ADDITIVE 9 A nonionic vinylpyrrolidone/vinylacetate copolymer having a molecular weight of 65,000 g/mol obtained under the trade designation SOKALAN VA64P from BASF.
  • BP Black color concentrate mixture consisting of a 50/50 blend of carbon black in ethylene vinyl acetate copolymer resin obtained under the trade designation 4105 VAC BLACK from Aduc, Avon Lake, OH DENSITY
  • An expandable microsphere obtained under the trade designation DUALITE MODIFIER U010-185D from Chase Corporation, Westwood, MA.
  • MEK Methyl ethyl ketone obtained from Avantor Performance Materials, Center Valley, PA.
  • acetone Acetone obtained from Sigma Aldrich.
  • IOA Isooctyl acrylate obtained from 3M Company, St. Paul, MN.
  • NVC N-vinylcaprolactam obtained under the trade designation NVC from BASF.
  • AIBN 2,2′-Azobis(2-methylpropionitrile) obtained under the trade designation VAZO- 64 from E. I. du Pont de Nemours & Company, Wilmington, DE.
  • TBEC Tert-Butylperoxy 2-ethylhexyl carbonate, obtained under the trade designation “LUPEROX TBEC” from Arkema Inc., King of Prussia, PA.
  • Polymer 2 A clear, linear triblock copolymer based on styrene and ethylene/butylene obtained under the trade designation KRATON FG1901 from Kraton Polymers US LLC, Houston, TX. OB 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole) obtained under the trade designation TINOPAL OB from BASF, Florham Park, NJ.
  • Illustrative Example 1 Illustrative Example 1 was made by combining Polymer 1, BP, and a liquid blend. Polymer 1 was prepared as described in Synthesis Example S1 of U.S. Pat. Pub.
  • the liquid blend was prepared by using a diaphragm pump (Wilden Pump and Engineering, Grand Terrace, CA, USA) to add 132.8 pounds (lbs) (60.2 kilograms (kg)) of DTMPTA to a HM-2.5 basketmill (Hockmeyer Equipment Corporation, Elizabeth City, NC, USA) with 9-spindle hub having been preloaded with clean Zirmil 1.5 millimeter (mm) bead media and equipped with a 0.5 mm Tungsten coated screen and HM-2.5 turbo prop.
  • HM-2.5 basketmill Hockmeyer Equipment Corporation, Elizabeth City, NC, USA
  • 9-spindle hub having been preloaded with clean Zirmil 1.5 millimeter (mm) bead media and equipped with a 0.5 mm Tungsten coated screen and HM-2.5 turbo prop.
  • 17.2 lb (7.8 kg) of BTEAC was added to the basketmill using a paddle mixer to incorporate.
  • the mixture was milled for 3 hours at 800 revolutions per minute (rpm) with cooling jacket set at 70 °F (21 °C). Particle size was measured as described in the test methods under Particle Size Measurement. Milled material was further diluted by addition of 254.1 lbs (115.3kg) of DTMPTA for every 45.9 lbs (20.8 kg) of milled material. This diluted material, a liquid blend, was combined with Polymer 1 and BP then compounded and extruded in a 30 mm diameter co-rotating twin screw extruder, available as "ZSK-30" from Werner & Pfleiderer, Ramsey, N.J.
  • the extruder had 5 zones, each corresponding to one fifth of the length of the screw, and a length to diameter ratio of 15:1.
  • the twin screw extruder was operated with melt temperatures of 270° F (132° C.). All the ingredients of the composition were fed into the extruder manually via an open port. The composition was mixed in the extruder for 3 minutes at a screw speed of 300 rpm with the extruder outlet closed. Then the screw speed was reduced to 100 rpm and the extruder outlet was opened to coat the pressure sensitive adhesive on a silicone-coated release liner to create Illustrative Example 1.
  • Illustrative Examples 2-4 and Examples 5 to 9 Illustrative Examples 2 to 4 and Examples 5-9 were prepared as described in Illustrative Example 1 except that ADDITIVE 1-8, respectively, were added to the twin screw extruder along with Polymer 1, the liquid blend, and BP.
  • the adhesive compositions for Illustrative Examples 1 to 4 and Examples 5-9 are shown in Table 1. The amounts are listed in weight percentages (parts by weight for a total of 100 parts).
  • Example 10 Example 10 was carried out using a Plasti-corder EPL-V3302 (C.W. Brabender, Hackensack, NJ) equipped with an electrically heated three-part mixer with a capacity of approximately 250 cm 3 and high shear counter-rotating blades.
  • the mixer was preheated to 257 °F (125 °C) and set at a mixing speed of 60 rpm. Charged to the chamber was 25.47 grams (g) of Polymer 1 described in Illustrative Example 1 and 0.27 g BP, and these were allowed to mix for two minutes before 4 g of ADDITIVE 9 was added. The mixture was mixed an additional 5 minutes before adding 10.26 g of the liquid blend described in Illustrative Example 1 and then mixed a final 10 minutes. The system was cooled to 176 °F (80 °C) under a mixing speed of 30 rpm for adhesive removal from the chamber. After removal from the mixer, a hot press was used to press a portion of the material to a 12-mil thickness between silicone-coated release liners.
  • the twin screw extruder had 12 zones, each corresponding to one twelfth of the length of the screw, and a length to diameter ratio of 36:1.
  • the twin screw extruder was operated at 450 rpm and temperature controlled to maintain a melt temperature of 280° F (138° C).
  • Polymer 1 described in Example 1 was fed into a 2 inch (51 mm) Single Packer Extruder commercially available from Bonnot, Uniontown, OH.
  • the Single Packer Extruder masticated the polymer and fed it into zone 2 of the twin screw extruder at a rate of 45.9 grams/minute.
  • ADDITIVE 4 and BP were fed at a rate of 7.6 grams/minute and 0.6 grams/ minute, respectively, into zone 1 of the extruder from a pair of Coperion K-Tron Twin Screw Feeders from Coperion GmbH, Stuttgart, Germany.
  • the liquid blend described in Example 1 was delivered via a split stream at a rate of 21.6 grams/minute into zones 7 and 9 of the extruder from a MasterFlex P/S Easy Load II peristaltic pump (Thermo Scientific, Barrington, IL).
  • the melt mixture passed from the extruder into a polymer melt pump set at 270° F (132° C) (commercially available as “PEP-II 3 cc/rev” from Zenith Pumps of Monroe, NC) which pumped it at a rate of 2.92 cubic centimeters (cm 3 )/revolution into a drop die set to 270° F. (132° C.).
  • the melt mixture was coated onto a silicone-coated, kraft paper release liner as a continuous sheet of pressure sensitive adhesive having about 12 mil (0.30 mm) thickness.
  • the compositions for Examples 11 and 12 are shown in Table 2. The amounts are listed in weight percentages (parts by weight for a total of 100 parts).
  • Example 13-16 were prepared as in Examples 11 and 12 except that a second extruder/feeder/pump setup was arranged to deliver a second stream into an ABA multi-manifold die to generate a multilayer construction of ABA format and an additional Brabender feeder (C.W. Brabender, Hackensack, NJ) was setup to deliver DENSITY MODIFIER to zone 11 of the feed creating the B layer at a rate of 1.5 grams/minute.
  • the adhesive compositions are shown in Table 2. The amounts are listed in weight percentages (wt%). Table 2.
  • Particle size of the liquid blend described in Example 1 was measured by laser diffraction using Horiba LA-960 (Horiba, Kyoto, Japan). The following refractive index values were used for the calculation: MEK (1.3791) and BTEAC (1.4790). The second differential method was used for smoothing based on 150 iterations. The dispersion was diluted to approximately 1 weight percent solids with MEK. The diluted sample was then added to the measurement cell which was filled with MEK until the transmittance was between the recommended levels of 85-95%. D99.9, D90 and D50 were measured. (e.g.
  • the D90 is the maximum particle size below which 90% of the sample volume exists.
  • Creep Resistance Test Method The examples were analyzed using a DHR-3 parallel plate rheometer equipped with a Peltier plate accessory (TA Instruments, New Castle, DE, USA) to characterize the creep properties of each sample as a function of time. Rheology samples were formed into an adhesive film approximately 1 mm thick between silicone coated release liners. Samples were then punched out with an 8 mm circular die, removed from the release liners, centered onto the 8 mm diameter parallel plate upper fixture of the rheometer, and compressed down to the Peltier plate until the edges of the sample were uniform with the edges of the top plate.
  • the samples were conditioned at the test start temperature of 25°C under an axial force control of 40 g with a sensitivity of +/- 30 g for 120 seconds and then the axial force adjustment was disabled to hold the plates at a fixed gap for the remainder of the test. A fixed stress of 8,000 Pascals (Pa) was then applied for 600 seconds. While many physical parameters of the material are recorded during the creep test, Compliance (J) is of primary importance in the characterization of the adhesives of this invention.
  • the Creep Resistance of the polymer is a term used to describe the long-time creep behavior of the material by measuring the slope of the compliance versus time and inverting that value to yield a viscosity (Pascal-seconds (Pa-s)).
  • Creep Resistance [(Compliance (1/Pa) at 600s – Compliance (1/Pa) at 541 s) ⁇ (600 s – 541 s)] ⁇ -1 Uncured Static Shear Creep Test Samples were prepared for static shear adhesion using stainless steel substrates 2 inch by 3 inch by 0.052 inch (5.0 cm by 7.5 cm by 1.3 mm) that were washed with MEK, then 50/50 water/IPA solution, and then three times with acetone, followed by air-drying for at least 2 minutes.
  • Specimens were made by cutting a 1-inch (2.5-cm) strip of adhesive which was laid across the substrate, centered along the 2-inch edge and extending about 2 inches onto the substrate. Excess adhesive hanging off the substrate was trimmed flush with the 2-inch edge and a 2-inch (5.1-cm) firm rubber roller (MARSHALLTOWN, Marshalltown, IA) was used on the remaining adhesive to insure full contact. The release liner was removed, and a strip of aluminum foil 1.25 inch by 8 inch by 2 mil (3.175 cm by 20.32 cm by 0.05 mm) was laid across the exposed adhesive with about 6 inches (15.2 cm) of foil extending beyond the edge of the substrate. The rubber roller was used again to insure contact between the foil and adhesive.
  • a 1-inch (2.5-cm) cut block was used to trim the excess adhesive from the substrate leaving a 1-inch by 1-inch (2.5-cm by 2.5-cm) square of adhesive.
  • the aluminum foil was threaded through a shear hook and folded over itself to form a loop.
  • the loop was closed using filament tape and staples to ensure the loop remained intact throughout the duration of the test.
  • Samples were then rolled down 2 times using a mechanical roller with a weight of 4.5 pounds operating at 12 inches per minute (30.5 cm per minute.) Samples were dwelled at room temperature (71°F (22°C)) for 15 minutes prior to testing.
  • the static shear test was conducted by hanging the test specimens on a shear stand and hanging an 8.8-ounce (250-gram) weight on the attached shear hook.
  • Examples were prepared for dynamic shear adhesion using 1-inch by 4-inch by 0.064-inch (2.5- cm by 10-cm by 1.6-mm) aluminum substrates that were washed with MEK, then 50/50 water/IPA solution, and then three times with acetone, followed by air-drying for at least 2 minutes.
  • the substrates were then activated with activator. Activating was done by folding a small lab wipe three times to make about a one-inch strip which was dipped into the activator solution and wiped from the end of the substrate to the middle so that about two inches was coated.
  • Activated substrates were allowed to air dry a minimum of two minutes before adhesive application. Specimens were made by cutting a 1-inch (2.5- cm) strip of multilayer tape described previously.
  • a 2-inch (5.1-cm) firm rubber roller (MARSHALLTOWN, Marshalltown, IA) was used to insure full contact of the adhesive. Bond assembly occurred by removing the top release liner exposing the adhesive and introducing it to a second activated substrate. The closed bond was then subjected to applied pressure of about 20 (pounds per square inch) psi inside a pneumatic driven hydraulic press (Fred S. Carver, Inc. Hydraulic Equipment, Menomonee Falls, WI) between two rubber gaskets for 15 seconds. The bonded test assembly was dwelled at room temperature (71°F /22°C) for 3 days prior to testing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)

Abstract

Un ruban comprend un film adhésif durcissable qui comprend un mélange de polymères comportant un copolymère de (méth)acrylate et un polymère contenant de l'azote, des groupes insaturés polymérisables par voie radicalaire qui peuvent être liés au copolymère de (méth)acrylate ou dans une espèce autre que le copolymère de (méth)acrylate, et un cation de métal de transition. Le copolymère de (méth)acrylate comprend des unités monomères acides. Un système adhésif comprend le ruban et une composition d'activateur comportant un agent oxydant. Un procédé de liaison d'un premier substrat consiste à appliquer une composition d'activateur sur une surface du premier substrat et à mettre en contact la composition d'activateur avec une première surface du ruban. La composition d'activateur comprend un agent oxydant.
PCT/IB2024/060235 2023-10-20 2024-10-18 Ruban comprenant un film adhésif durcissable, ainsi que système et procédé adhésifs associés Pending WO2025083620A1 (fr)

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US202363545058P 2023-10-20 2023-10-20
US63/545,058 2023-10-20

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WO2023022185A1 (fr) * 2021-08-20 2023-02-23 日東電工株式会社 Feuille adhésive
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