Electrochemically Removable Adhesive Composition

Abstract

The present invention relates to a curable, electrochemically releasable adhesive composition comprising, based on the weight of the composition, a) 40 to 99 wt. % of at least one ethylenically unsaturated nonionic monomer; b) 0.9 to 50 wt. % of at least one polymerizable ionic compound; and c) 0.1 to 10 wt. % of at least one free radical initiator, wherein the polymerizable ionic compound comprises b1) at least one compound of general formula IV and / or b2) at least one compound of general formula V TIFF2023530767000030.tif37113

Description

[Technical Field]

[0001] The present invention is directed to curable adhesive compositions that are releasable from the particular substrate to which they are applied. More specifically, the present invention is directed to curable, electrochemically releasable adhesive compositions comprising a polymerizable electrolyte. [Background technology]

[0002] Adhesive bonds and polymer coatings are commonly used in product assembly and finishing. They replace mechanical fasteners such as screws, bolts, and rivets, providing joints with reduced machining costs and improved compatibility in manufacturing processes. Adhesive bonds distribute stress evenly, reducing the potential for fatigue and sealing the joint from corrosive species.

[0003] While adhesive bonding offers many advantages over mechanical fasteners, it tends to be difficult to disassemble the adhesively bonded objects, which is necessary for practical applications, such as recycling the bonded primary materials. Removal of the adhesive by mechanical processes such as sandblasting or wire brushing is often ruled out, in part because the adhesive is located between the substrates and is difficult or impossible to ablate without damaging the substrate surfaces. Disassembly by application of chemicals and / or high temperatures, as disclosed in U.S. Pat. No. 4,171,240 (Wong) and U.S. Pat. No. 4,729,797 (Linde et al.), may be effective but can be time-consuming and complicated to implement. Furthermore, aggressive chemicals and / or the harsh conditions required can damage the separated substrates, rendering them unsuitable for subsequent applications.

[0004] Some authors have addressed these problems and considered the development of electrochemically releasable adhesive compositions in which the passage of an electric current through the cured composition acts to destroy the bond at the interface between the adhesive and the substrate.

[0005] US 2007 / 0269659 (Gilbert) discloses an adhesive composition releasable at two interfaces, which (i) comprises a polymer and an electrolyte, (ii) facilitates bonding of two surfaces, and (iii) releases from both an anodic surface and a cathodic surface in response to a voltage applied to both surfaces such that an anodic interface and a cathodic interface are formed.

[0006] US 2008 / 0196828 (Gilbert) discloses a hot melt adhesive composition comprising a thermoplastic component and an electrolyte, the electrolyte enabling a faradaic reaction at the bond formed between the composition and a conductive surface and providing the composition with sufficient ionic conductivity to enable peeling of the composition from the surface.

[0007] WO 2007 / 142600 (Stora Enso AB) discloses an electrochemically weakenable adhesive composition that provides an adhesive bond to an electrically conductive surface and sufficient ionically conductive properties to allow weakening of said adhesive bond when a voltage is applied to the adhesive composition, said composition comprising at least one ionic compound in an amount sufficient to provide said ionically conductive properties, said ionic compound having a melting point of 120°C or less.

[0008] EP 3363875 A (Nitto Denko Corporation) discloses an electrically peelable adhesive composition that can be easily peeled off by applying a voltage for a short time and forms an adhesive layer with high adhesive strength. The electrically peelable adhesive composition in this document contains a polymer and 0.5 to 30 wt % of an ionic liquid based on the weight of the polymer, and the anion of the ionic liquid is a bis(fluorosulfonyl)imide anion.

[0009] WO 2013 / 135677 (Henkel AG & Co. KGaA) discloses a hot melt adhesive comprising 20 to 90 wt. % of at least one polyamide having a molecular weight (Mw) of 10,000 to 250,000 g / mol; 1 to 25 wt. % of at least one organic or inorganic salt; and 0 to 60 wt. % of further additives, and having a softening point of 100°C to 220°C.

[0010] WO 2016 / 135341 (Henkel AG & Co. KGaA) discloses a reactive hot melt adhesive composition that, upon application of an electric voltage, at least partially loses adhesive strength, thereby enabling delamination of substrates joined using the adhesive. More specifically, the reactive hot melt adhesive composition comprises: a) at least one isocyanate-functional polyurethane polymer; and b) at least one organic or inorganic salt.

[0011] WO 2017 / 133864 (Henkel AG & Co. KGaA) discloses a method for reversibly bonding a first substrate and a second substrate, wherein at least the first substrate is a non-conductive substrate, the method comprising: a) coating a surface of the non-conductive substrate with a conductive ink; b) applying an electrically releasable hot melt adhesive composition to the conductive ink-coated surface of the first substrate and / or the second substrate; c) contacting the first substrate and the second substrate such that the electrically releasable hot melt adhesive composition is interposed between the two substrates; d) allowing the formation of an adhesive bond between the two substrates to provide a bonded substrate; and e) applying a voltage to the bonded substrates such that the bond at at least one interface between the electrically releasable hot melt adhesive composition and the substrate surface is substantially weakened. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] U.S. Patent No. 4,171,240 [Patent Document 2] U.S. Patent No. 4,729,797 [Patent Document 3] US 2007 / 0269659 [Patent Document 4] US 2008 / 0196828 [Patent Document 5] WO 2007 / 142600 [Patent Document 6] EP 3363875 A [Patent Document 7] WO 2013 / 135677 [Patent Document 8] WO 2016 / 135341 [Patent Document 9] WO 2017 / 133864 Summary of the Invention [Problem to be solved by the invention]

[0013] When an ionic liquid or electrolyte is included in the adhesive composition, it can be difficult to achieve compatibility between the electrolyte and the polymer matrix. Electrolyte leakage and phase separation from the cured polymer matrix have been recognized in the known art as drawbacks in the application of electrically releasable adhesives.

[0014] There remains a need in the art to provide adhesive compositions that can be conveniently applied to the surfaces of the substrates to be joined, and upon curing, provide effective bonds within composite structures that include said substrates, but that can be effectively released from these substrates by easily applying an electrical potential to the cured adhesive. The cured adhesive should also provide a stable polymer matrix that minimizes leakage of components and does not undergo phase separation. [Means for solving the problem]

[0015] According to a first embodiment of the present invention, there is provided a curable, electrochemically releasable adhesive composition comprising, based on the weight of the composition: 40 to 99% by weight, preferably 45 to 90% by weight, of a) at least one ethylenically unsaturated nonionic monomer; 0.9 to 50% by weight, preferably 5 to 30% by weight, of b) at least one polymerizable ionic compound; and 0.1 to 10% by weight, preferably 0.1 to 5% by weight of c) at least one free radical initiator The polymerizable ionic compound comprises b1) at least one compound of general formula IV: The compound identified in TIFF0007804594000001.tif2280, and / or b2) at least one compound of general formula V: TIFF0007804594000002.tif2369[where, R 7 is C1-C 30 Alkyl; C2-C8 Alkenyl; C1-C 30 Heteroalkyl; C3-C 30 Cycloalkyl; C6-C 18 Aryl; C1-C9 Heteroaryl; C7-C 18 Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is a C1-C6 alkylene group, and R b is a C1-C6 alkyl group; Each R 8 are independently H, C1-C 18 Alkyl, C1-C 18 Heteroalkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 selected from alkylaryl or C2-C5 heterocycloalkyl; R 9 is H or C1-C4 alkyl; Each R 10 are independent, C1-C 30 Alkyl; C1-C 30 Heteroalkyl; C3-C 30 Cycloalkyl; C6-C18 Aryl; C1-C9 Heteroaryl; C7-C 18 Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is a C1-C6 alkylene group, and R b is a C1-C6 alkyl group; A is a non-polymerizable anion; T is an ethylenically unsaturated anion; d and m are each an integer of at least 1; e and n are values ​​such that the compound is electrically neutral; TIFF0007804594000003.tif52 is a covalent bond, C1-C2 alkylene, -CH2OC(=O)-, -CH2CH2OC(=O)-, p-benzyl, or p-tolyl.] An adhesive composition is provided comprising a compound represented by the formula: [Brief explanation of the drawings]

[0016] [Figure 1a] FIG. 1a shows a joint structure according to a first embodiment of the invention. [Figure 1b] FIG. 1b shows a joint structure according to a second embodiment of the invention. [Figure 2a] FIG. 2a shows the initial delamination of the structure of the first embodiment when a voltage is applied to the structure of the first embodiment. [Figure 2b] FIG. 2b shows the initial delamination of the structure of the second embodiment when a voltage is applied to the structure of the second embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0017] The adhesive composition can be prepared as a one-component (1K), two-component (2K) or multi-component composition. Part b) consisting of said compounds according to part b1) and / or part b2) can be suitable.

[0018] In one embodiment of the composition, part a) thereof comprises 40 to 95% by weight, preferably 45 to 90% by weight, based on the weight of the composition, of a1) a compound of formula (I): H2C=CGCO2R 1 (I) wherein G is hydrogen, halogen, or a C1-C4 alkyl group; R 1 is C1-C 30 Alkyl, C2-C 30 Heteroalkyl, C3-C 30 Cycloalkyl; C2-C8 heterocycloalkyl; C2-C 20 Alkenyl and C2-C 12 alkynyl] The (meth)acrylate monomer comprises at least one (meth)acrylate monomer represented by the formula:

[0019] Part a) of the composition may further comprise 0 to 30% by weight, for example 0 to 15% by weight, based on the weight of the composition, of a2) a compound of formula (II): H2C=CQCO2R 2 (II) wherein Q can be hydrogen, halogen, or a C1-C4 alkyl group; R 2 is C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 Alkaryl and C7-C 18 aralkyl] The composition may be characterized by comprising at least one (meth)acrylate monomer represented by the formula:

[0020] In another embodiment of the composition, which is not intended to mutually exclude the above embodiments, part a) thereof comprises 0 to 50 wt. %, preferably 5 to 25 wt. %, based on the weight of the composition, of a3) at least one (meth)acrylate-functionalized oligomer.

[0021] In consideration of the electrolyte b) of the curable electrochemically strippable composition, both the ionic compounds of formulas IV and V described above and below contain a functional group reactive to radical polymerization, preferably a vinyl, allyl, or acrylic functional group, such that the polymerizable electrolyte will polymerize with any of the monomers a) described above.

[0022] For compounds of formula IV(b1), the cation is based on an imidazolium ring and is covalently bound to the adhesive matrix upon completion of the selected curing profile; the counteranion (A) is free to move within the polymer matrix. Conversely, for compounds of formula V(b2), the anion of the polymerizable electrolyte is covalently bound to the adhesive matrix upon curing, while the cation based on an imidazolium ring is free to move within the matrix.

[0023] Preferred compounds b1), which may be present alone or in combination, include, but are not limited to: 1H-imidazolium, 3-ethenyl-1-methyl-, iodide; 1H-imidazolium, 3-ethenyl-1-methyl-, chloride; 1H-imidazolium, 3-ethenyl-1-methyl-, bromide; 1H-imidazolium, 3-ethenyl-1-methyl-, methanesulfonate; 1H-imidazolium, 3-ethenyl-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-methyl-, Hexafluorophosphate;1H-Imidazolium, 3-ethenyl-1-methyl-, 4-methylbenzenesulfonate;1H-Imidazolium, 3-ethenyl-1-methyl-, tetrafluoroborate;1H-Imidazolium, 3-ethenyl-1-ethyl-, iodide;1H-Imidazolium, 3-ethenyl-1-ethyl-, bromide;1H-Imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 3-ethenyl-1-ethyl-, hexafluorophosphate;1H-Imidazolium, 3-ethenyl-1-ethyl-, tetrafluoroborate;1H-Imidazolium, 3-Ethenyl-1-(1-methylethyl)-, bromide;1H-Imidazolium, 3-(1,1-dimethylethyl)-1-ethenyl-, bromide;1H-Imidazolium, 3-ethenyl-1-propyl-, bromide;1H-Imidazolium, 3-ethenyl-1-(phenylmethyl)-, bromide;1H-Imidazolium, 1-ethenyl-3-(4-methylphenyl)-, chloride;1H-Imidazolium, 3-ethenyl-1-(1-methylpropyl)-, chloride;1H-Imidazolium, 1-butyl-3-ethenyl-, bromide;3-[(4-ethenylphenyl)methyl]-1-methyl-, iodide;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, chloride;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, hexafluorophosphate;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, tetrafluoroborate;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-ethyl-, chloride;1H-Imidazolium, 1-[(4-ethenylphenyl)methyl]-3-ethyl- 1,1,1-Trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide salt; 1H-Imidazolium, 1-(3-aminopropyl)-3-[(4-ethenylphenyl)methyl]-, chloride; 1H-Imidazolium, 1-butyl-3-[(4-ethenylphenyl)methyl]-, chloride.

[0024] Preferred compounds b2), which may be present alone or in combination, include, but are not limited to: 1H-imidazolium, 1-methyl-3-hexyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-dodecyl-3-ethenyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-methyl-3-propyl-, 4-ethenylbenzenesulfonate; and 1H-imidazolium, 3-ethyl-1-methyl-, 4-(1-methylethenyl)benzenesulfonate.

[0025] In particular, good results have been obtained when part b) of the composition comprises or consists of at least one compound selected from the group consisting of 1H-imidazolium, 3-methyl-1-hexyl-4-ethenylbenzenesulfonate; 1H-imidazolium, 3-ethenyl-1-ethyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; and 1H-imidazolium, 3-methyl-1-butyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide.

[0026] According to a second embodiment of the present invention, there is provided a bonded structure comprising a first material layer having an electrically conductive surface and a second material layer having an electrically conductive surface, with the electrochemically releasable cured adhesive composition described above and claimed in the appended claims disposed between the first and second material layers.

[0027] According to a third embodiment of the present invention, i) applying a voltage to both surfaces to form an anodic interface and a cathodic interface; and ii) peeling these surfaces There is provided a method for delaminating a bonded structure as described above and as claimed in the accompanying claims, comprising:

[0028] Step i) of this method preferably comprises: a) an applied voltage of 1 to 100 V; and b) Voltage application for 1 second to 180 minutes It is characterized by at least one of the following.

[0029] The adhesive properties of the composition are destroyed by the application of an electric potential to the bond line between the composition and the conductive surface. Without intending to be bound by theory, it is believed that a Faradaic reaction occurring at the interface between the adhesive composition and the conductive surface destroys the interaction between the adhesive and the substrate, thereby weakening the bond therebetween. This interfacial destruction can be the result of one or more processes, such as chemical decomposition of the releasable material, gas evolution at the interface, and / or material embrittlement due to changes in the crosslink density of the adhesive composition.

[0030] definition As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. As used herein, the terms "comprise," "include," and "including" are synonymous with "include," "included," "contain," or "comprise," and are inclusive or open-ended and do not exclude additional, unrecited components, elements, or method steps. As used herein, the term "consisting of" excludes any unspecified elements, components, materials, or method steps. When amounts, concentrations, dimensions and other parameters are expressed in the form of ranges, preferred ranges, upper limits, lower limits, preferred upper limits and preferred lower limits, it should be understood that the range obtained by combining the upper or preferred value with the lower or preferred value is also specifically disclosed, whether or not the context clearly dictates otherwise. Also, in accordance with standard understanding, weight ranges expressed as "0 to x" specifically include 0% by weight: the component defined by said range may be absent from the composition or may be present in the composition in an amount up to x% by weight. The terms "preferred," "preferably," "suitably," and "particularly" are frequently used herein to refer to embodiments of the present disclosure that may offer particular benefits, under particular circumstances. However, the recitation of one or more preferred, preferred, or particular embodiments does not imply that other embodiments are not useful, and is not intended to exclude such other embodiments from the scope of the disclosure. Throughout this specification, the term "may" is used in a permissive rather than mandatory sense, i.e., in the sense of possibility. As used herein, room temperature is 23° C.±2° C. As used herein, "ambient conditions" refers to the temperature and pressure of the environment in which the composition resides, or the environment in which the coating layer or substrate for said coating layer resides.

[0031] In this specification, a "two-component (2K) composition" is understood to be a composition in which the first component (1) and the second component (2) must be stored in separate containers due to their (high) reactivity. The two parts are mixed only immediately before application, and then react, typically without additional activation, to form bonds, thereby forming a polymer network. In the present invention, a higher temperature may be applied to accelerate the crosslinking reaction. As used herein, the term "electrochemically releasable" means that, after the adhesive has cured, the bond strength can be weakened by at least 50% when a potential of 50 V is applied for 60 minutes. The cured adhesive is applied between two substrates to be joined by the adhesive, and an electric current is passed through the adhesive bond line. Bond strength is measured by a tensile lap shear (TLS) test performed at room temperature in accordance with ASTM D3163-01, "Standard Test Method for Determining the Strength of Adhesively Bonded Rigid Plastic Lap Shear Joints in Shear Under Tensile Load." The bond overlap area was 2.5 cm x 1.0 cm (1 in x 0.4 in), and the adhesive thickness was 0.1 cm (40 mil). The term "electrolyte" is used herein in accordance with its standard meaning in the art as a material containing free ions capable of conducting electricity by substitution of charge carrier species. This term is intended to encompass molten, liquid, semi-solid, and solid electrolytes in which at least one of the cation or anion components of the electrolyte structure is essentially free to substitute and function as a charge carrier. The curable adhesive compositions of the present invention and the resulting cured adhesives have "electrolyte functionality" in that the adhesives allow for the conduction of anions, cations, or both ions. The electrolyte functionality is understood to result from the ability of the composition and cured adhesive to solvate ions of at least one polarity. The term "Faradaic reaction" refers to an electrochemical reaction in which a substance is oxidized or reduced.

[0032] As used herein, the term "monomer" refers to a substance that can undergo a polymerization reaction to contribute a building block to the chemical structure of a polymer. As used herein, the term "monofunctional" refers to having one polymerizable moiety. As used herein, the term "multifunctional" refers to having two or more polymerizable moieties. As used herein, the term "ethylenically unsaturated monomer" refers to any monomer containing a terminal double bond polymerizable under the usual conditions of radical addition polymerization. As used herein, the term "equivalents (eq.)," as is usual in chemical notation, refers to the relative number of reactive groups present in a reaction. As used herein, "(meth)acrylic" is an abbreviation for "acrylic" and / or "methacrylic." Thus, the term "(meth)acrylate" refers collectively to acrylate and methacrylate. As used herein, "C1-C n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, i.e., an alkane group, and includes straight-chain and branched-chain organic groups. 30An "alkyl" group refers to a monovalent group, i.e., an alkane group, containing 1 to 30 carbon atoms, and includes straight-chain and branched-chain organic groups. Alkyl groups include, but are not limited to, methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and 2-ethylhexyl. In the present invention, such alkyl groups may be unsubstituted or substituted with one or more substituents selected from halogen, hydroxy, nitrile (-CN), amido, and amino (-NH). Where applicable, preferences for the listed substituents are indicated in the specification. However, in general, alkyl groups having 1 to 18 carbon atoms (C1-C2) are preferred. 18 alkyl), such as alkyl groups having 1 to 12 carbon atoms (C1-C 12 It should be noted that alkyl) or alkyl groups having 1 to 6 carbon atoms (C1-C6 alkyl) are preferred. As used herein, "C1-C 18 The term "hydroxyalkyl" refers to an HO-(alkyl) group having 1 to 18 carbon atoms, where the point of attachment of the substituent is through the oxygen atom and the alkyl group is as defined above. An "alkoxy group" refers to a monovalent group represented by -OA, where A is an alkyl group, non-limiting examples of which are methoxy, ethoxy, and isopropyloxy.

[0033] The term "C1-C6 alkylene," as used herein, is defined as a saturated divalent hydrocarbon radical having straight, branched, or cyclic moieties or combinations thereof, having from 1 to 6 carbon atoms. "C3-C 30 The term "cycloalkyl" is understood to mean an optionally substituted saturated monocyclic, bicyclic or tricyclic hydrocarbon group having 3 to 30 carbon atoms. Generally, cycloalkyl groups having 3 to 18 carbon atoms (C3-C 18It should be noted that cycloalkyl groups are preferred. Examples of cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane. In the present invention, such cycloalkyl groups may be unsubstituted or substituted with one or more substituents selected from halogen, C1-C6 alkyl, and C1-C6 alkoxy. As used herein, "C-C alkyl" used alone or as part of a larger group, such as in "aralkyl group" 18 "Aryl" refers to optionally substituted monocyclic, bicyclic, and tricyclic ring systems, in which the monocyclic ring system is aromatic, or in which at least one of the rings of the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic ring systems include benzo-fused 2- to 3-membered carbocyclic rings. In the present invention, such aryl groups can be unsubstituted or substituted with one or more substituents selected from halogen, C1-C6 alkyl, and C1-C6 alkoxy. Exemplary aryl groups include: phenyl; (C1-C4) alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. It may be noted that the phenyl group is preferred. As used herein, "C2-C 20 "Alkenyl" refers to a hydrocarbyl group having from 2 to 20 carbon atoms and having at least one unit of ethylenic unsaturation. The alkenyl group may be straight, branched, or cyclic and may be optionally substituted. The term "alkenyl" encompasses groups having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations, as understood by those skilled in the art. However, generally, groups having from 2 to 10 (C 2-10 ) or 2 to 8 pieces (C 2-8 It should be noted that unsubstituted alkenyl groups having carbon atoms of C2-C are preferred. 12Examples of alkenyl groups include, but are not limited to, -CH=CH2; -CH=CHCH3; -CH2CH=CH2; -C(=CH2)(CH3); -CH=CHCH2CH3; -CH2CH=CHCH3; -CH2CH2CH=CH2; -CH=C(CH3)2; -CH2C(=CH2)(CH3); -C(=CH2)CH2CH3; -C(CH3)=CHCH3; -C(CH3)CH=CH2; -CH=CHCH2CH2CH3; -CH2CH=CHCH2C H3; -CH2CH2CH=CHCH3; -CH2CH2CH2CH=CH2; -C(=CH2)CH2CH2CH3; -C(CH3)=CHCH2CH3; -CH(CH3)CH=CHCH; -CH(CH3)CH2CH=CH2; -CH2CH=C(CH3)2; 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohexyl-3-enyl.

[0034] As used herein, "alkylaryl" refers to an alkyl-substituted aryl group, "substituted alkylaryl" refers to an alkylaryl group further bearing one or more of the above substituents, and "aralkyl" refers to an alkyl group substituted with an aryl group as defined above. The term "hetero," as used herein, means a group or moiety that includes one or more heteroatoms selected from N, O, Si, P, and S. For example, a "heterocycle" refers to a cyclic group having N, O, Si, P, or S as part of the ring structure. "Heteroalkyl," "heterocycloalkyl," and "heteroaryl" groups are "alkyl," "cycloalkyl," and "aryl" groups, respectively, as used herein that contain N, O, Si, P, or S as part of their structure. For completeness, "C2-C 30 The term "heteroalkyl" refers to an "alkyl" group having a total of 2 to 30 carbon atoms, where at least one carbon atom is replaced with a heteroatom. Specific examples of such heteroalkyl groups are "C2-C 18and "alkoxyalkyl" [which refers to an alkyl group having an alkoxy substituent as described above, wherein the (alkyl-O-alkyl) portion has a total of 1 to 18 carbon atoms]; such groups include methoxymethyl (-CHOCH), 2-methoxyethyl (-CHCHOCH), and 2-ethoxyethyl (-CHCHOCHCH). Another example of a heteroalkyl group is "C-C 30 "aminoalkyl" [which contains a total of 2 to 30 carbon atoms and is selected from the group consisting of -NH(R'), -N(R')(R") or -N + (R')(R")(R"'), where R', R" and R"' are C1-C6 alkyl; such groups include 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl and 2-(trimethylamino)ethyl. The term "C1-C9 heteroaryl" refers to an aromatic group having 1 to 9 carbon atoms and 1 to 4 heteroatoms, which may be attached via a heteroatom or carbon atom, if possible. The heteroaryl ring can be fused to or attached to one or more heteroaryl, aromatic, or non-aromatic hydrocarbon or heterocycloalkyl rings. Examples of heteroaryl groups include, but are not limited to, pyridine; furan; thiophene; 5,6,7,8-tetrahydroisoquinoline; pyrimidine; thienyl; benzothienyl; pyridyl; quinolyl; pyrazinyl; pyrimidyl; imidazolyl; benzimidazolyl; furanyl; benzofuranyl; thiazolyl; benzothiazolyl; isoxazolyl; oxadiazolyl; isothiazolyl; benzisothiazolyl; triazolyl; tetrazolyl; pyrrolyl; indolyl; pyrazolyl; and benzopyrazolyl.

[0035] The term "C2-C8 heterocycloalkyl" refers to a saturated cyclic hydrocarbon group having 2 to 8 carbon atoms and 1 to 4 heteroatoms, which can be attached via a heteroatom or carbon atom, if possible. The heterocycloalkyl ring can optionally be fused or otherwise attached to other heterocycloalkyl rings and / or non-aromatic hydrocarbon rings. Preferred heterocycloalkyl groups are 3- to 7-membered rings. Examples of heterocycloalkyl groups include, but are not limited to, piperazine; morpholine; piperidine; tetrahydrofuran; pyrrolidine; pyrazole; piperidinyl; piperazinyl; morpholinyl; and pyrrolidinyl. As used herein, the term "aliphatic" includes all saturated and unsaturated, non-aromatic, straight-chain, branched-chain, acyclic, or cyclic hydrocarbons, which may be optionally substituted with one or more functional groups, provided that such substitution results in the formation of a stable moiety. As would be understood by one of ordinary skill in the art, "aliphatic" is intended to include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl groups. As used herein, "aromatic" refers to a primary group of unsaturated cyclic hydrocarbons containing one or more rings, which may contain carbon (C), nitrogen (N), oxygen (O), sulfur (S), boron (B), or any combination thereof. At least some carbon is included. Aromatic includes both aryl and heteroaryl rings. The aryl or heteroaryl rings may be further substituted with additional aliphatic, aromatic, or other groups, provided that the substitution results in the formation of a stable moiety. As used herein, the term "free radical initiator" refers to any chemical species that, upon exposure to sufficient energy in the form of irradiation, heat, etc., decomposes into two uncharged parts, each having at least one unpaired electron. For completeness, the term "free radical initiator" encompasses free radical thermal initiators and free radical photoinitiators that can be activated by irradiation with an energy-carrying activation beam (e.g., electromagnetic radiation, etc.). In the present invention, the use of free radical thermal initiators is preferred. Molecular weights referred to herein (as described for the macromolecular, oligomeric, and polymeric components of the curable compositions) can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, as performed in accordance with ASTM 3536. The viscosity of the coating compositions described herein is measured using a Brookfield viscometer at standard conditions of 20° C. and 50% relative humidity (RH) unless otherwise specified. The calibration method, spindle type, and rotation speed of the Brookfield viscometer are selected according to the manufacturer's instructions to suit the composition being measured.

[0036] a) Non-ionic matrix monomers The composition of the present invention comprises at least one ethylenically unsaturated nonionic monomer, the (co)polymerization of which results in the matrix of the releasable adhesive. Monomer a) can essentially be any ethylenically unsaturated nonionic monomer. However, the present invention is particularly applicable to compositions in which the (meth)acrylic monomer constitutes at least 50 mol %, preferably at least 75 mol %, of the total molar amount of ethylenically unsaturated nonionic monomers present.

[0037] a1) Aliphatic and alicyclic (meth)acrylate monomers In an important embodiment of the present invention, the composition of the present invention comprises 40 to 95% by weight, preferably 45 to 90% by weight, based on the weight of the composition, of a1) at least one compound of formula (I): H2C=CGCO2R 1 (I) wherein G is hydrogen, halogen, or a C1-C4 alkyl group; R 1 is C1-C 30 Alkyl; C2-C 30 Heteroalkyl; C3-C 30 Cycloalkyl; C2-C8 heterocycloalkyl; C2-C 20 alkenyl; and C2-C 12 alkynyl] The (meth)acrylate monomer is represented by the formula: For example, R 1 is C1-C 18 Alkyl, C2-C 18 Heteroalkyl, C3-C 18 It may be selected from cycloalkyl; C2-C8 heterocycloalkyl; C2-C8 alkenyl and C2-C8 alkynyl.

[0038] Preferably, the monomer a1) is R 1 But C1-C 18 Alkyl and C3-C 18 The description of this preferred embodiment is characterized in that R is selected from cycloalkyl. 1 is expressly intended to include embodiments where is C1-C6 hydroxylalkyl. Examples of (meth)acrylate monomers a1) represented by formula (I) include, but are not limited to, methyl (meth)acrylate; ethyl (meth)acrylate; butyl (meth)acrylate; hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; dodecyl (meth)acrylate; lauryl (meth)acrylate; cyclohexyl (meth)acrylate; isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate (HEMA); 2-hydroxypropyl (meth)acrylate; ethylene glycol monomethyl ether (meth)acrylate; ethylene glycol monoethyl ether (meth)acrylate; ethylene glycol monododecyl ether (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; trifluoroethyl (meth)acrylate; and perfluorooctyl (meth)acrylate.

[0039] a2) Aromatic (meth)acrylate monomers The composition of the present invention may comprise 0 to 30 wt. %, for example 0.1 to 30 wt. %, 0.1 to 25 wt. %, or 0.1 to 15 wt. %, based on the weight of the composition, of a2) at least one hydroxybenzoate of formula (II): H2C=CQCO2R 2 (II) wherein Q can be hydrogen, halogen, or a C1-C4 alkyl group; R 2 is C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 Alkaryl and C7-C 18 aralkyl] The copolymer may further contain a (meth)acrylate monomer represented by the following formula: Examples of (meth)acrylate monomers a2) represented by formula (II) include, but are not limited to, the following, which may be used alone or in combination: benzyl (meth)acrylate; phenoxyethyl (meth)acrylate; phenoxydiethylene glycol (meth)acrylate; phenoxypropyl (meth)acrylate; and phenoxydipropylene glycol (meth)acrylate.

[0040] a3) (Meth)acrylate-functionalized oligomers In an important embodiment of the present invention (which is not intended to mutually exclude the inclusion of aliphatic and cycloaliphatic monomers (a1) and aromatic monomers (a2)), the compositions of the present invention should contain 0 to 50 wt. %, preferably 5 to 25 wt. %, based on the weight of the composition, of a3) at least one (meth)acrylate-functionalized oligomer. The oligomer may have one or more acrylate and / or methacrylate groups attached to the oligomer backbone, and the (meth)acrylate functional groups may be located at the end of the oligomer and / or distributed along the oligomer backbone.

[0041] Preferably, the at least one (meth)acrylate-functionalized oligomer i) has two or more (meth)acrylate functional groups per molecule; and / or ii) has a weight average molecular weight (Mw) of 300 to 1000 Daltons.

[0042] Examples of such oligomers include, but are not limited to, the following, which may be used alone or in combination: (meth)acrylate-functionalized urethane oligomers, such as (meth)acrylate-functionalized polyester urethanes and (meth)acrylate-functionalized polyether urethanes; (meth)acrylate-functionalized polyepoxide resins; (meth)acrylate-functionalized polybutadienes; (meth)acrylic polyol (meth)acrylates; polyester (meth)acrylate oligomers; polyamide (meth)acrylate oligomers; and polyether (meth)acrylate oligomers. Such (meth)acrylate-functionalized oligomers and methods for their preparation are disclosed, inter alia, in U.S. Pat. Nos. 4,574,138; 4,439,600; 4,380,613; 4,309,526; 4,295,909; 4,018,851; 3,676,398; 3,770,602; 4,072,529; 4,511,732; 3,700,643; 4,133,723; 4,188,455; 4,206,025; and 5,002,976. Among the polyether (meth)acrylate oligomers, specific examples include, but are not limited to, PEG 200 DMA (n≈4); PEG 400 DMA (n≈9); PEG 600 DMA (n≈14); and PEG 800 DMA (n≈19), where the assigned number (e.g., 400) represents the weight average molecular weight of the glycol portion of the molecule.

[0043] The present invention does not exclude the presence of additional ethylenically unsaturated nonionic monomers that do not fit the definitions of a1), a2), and a3). However, the addition of such additional monomers should be limited by the condition that the total amount of ethylenically unsaturated nonionic monomers does not exceed 95% by weight based on the total weight of the composition. Preferably, the total amount of ethylenically unsaturated nonionic monomers does not exceed 90% by weight based on the total weight of the composition.

[0044] While not intending to limit the invention, such additional ethylenically unsaturated nonionic monomers may include: silicone (meth)acrylate monomers, such as those taught and claimed in U.S. Pat. No. 5,605,999 (Chu); α,β-ethylenically unsaturated monocarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid; C1-C2 of crotonic acid; 18 Alkyl esters; α,β-ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and the anhydrides, monoesters, and diesters of these acids; vinyl esters, such as vinyl acetate, vinyl propionate, and VEOVA available from Shell Chemical Company. TM vinyl ethers such as vinyl ethyl ether; vinyl ketones including alkyl vinyl ketones, cycloalkyl vinyl ketones, aryl vinyl ketones, aryl alkyl vinyl ketones, and aryl cycloalkyl vinyl ketones; aromatic or heterocyclic aliphatic vinyl compounds; poly(meth)acrylates of alkane polyols, such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ... (meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; poly(meth)acrylates of oxyalkane polyols, such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dibutylene glycol di(meth)acrylate, di(pentamethylene glycol) dimethacrylate; polyethylene glycol di(meth)acrylate; and bisphenol A di(meth)acrylates, such as ethoxylated bisphenol A (meth)acrylate (EBIPMA).

[0045] Typical examples of other ethylenically unsaturated polymerizable nonionic monomers include, but are not limited to, ethylene glycol dimethacrylate (EGDMA); monoesters and diesters of fumaric, maleic, and itaconic anhydrides with C1-C4 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol. Typical examples of vinyl monomers include, but are not limited to, vinyl acetate; vinyl propionate; vinyl ethers such as vinyl ethyl ether; and vinyl ethyl ketone. Typical examples of aromatic or heterocyclic aliphatic vinyl compounds include, but are not limited to, compounds such as styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene, 2-vinylpyrrolidone, 5-ethylidene-2-norbornene, and 1-, 3-, and 4-vinylcyclohexene.

[0046] b) Electrolytes The composition of the present invention comprises 0.9 to 50 wt. %, for example 5 to 50 wt. % or 10 to 45 wt. % of b) at least one polymerizable ionic compound, the polymerizable ionic compound being b1) at least one compound of general formula IV: The compound represented by TIFF0007804594000004.tif2280, and / or b2) at least one compound of general formula V: TIFF0007804594000005.tif2369[where, R 7 is C1-C 30 Alkyl; C2-C8 Alkenyl; C1-C 30 Heteroalkyl; C3-C 30 Cycloalkyl; C6-C 18 Aryl; C1-C9 Heteroaryl; C7-C 18 Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is a C1-C6 alkylene group, and R b is a C1-C6 alkyl group; Each R8 are independently H, C1-C 18 Alkyl, C1-C 18 Heteroalkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 selected from alkylaryl or C2-C5 heterocycloalkyl; R 9 is H or C1-C4 alkyl; Each R 10 are independent, C1-C 30 Alkyl; C1-C 30 Heteroalkyl; C3-C 30 Cycloalkyl; C6-C 18 Aryl; C1-C9 Heteroaryl; C7-C 18 Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is a C1-C6 alkylene group, and R b is a C1-C6 alkyl group; A is a non-polymerizable anion; T is an ethylenically unsaturated anion; d and m are each an integer of at least 1; e and n are values ​​such that the compound is electrically neutral; TIFF0007804594000006.tif52 is a covalent bond, C1-C2 alkylene, -CH2OC(=O)-, -CH2CH2OC(=O)-, p-benzyl, or p-tolyl. The compound comprises a compound represented by the formula:

[0047] In the above formula, R 7 is preferably C1-C 12 Alkyl; C2-C6 Alkenyl; C1-C 12 Heteroalkyl; C3-C 18 Cycloalkyl; C6-C 18 Aryl; C1-C9 Heteroaryl; C7-C 18Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is a C1-C6 alkylene group, and R b is a C1-C6 alkyl group. 7 is more particularly C1-C8 alkyl; C2-C4 alkenyl; C1-C8 heteroalkyl; C3-C 12 Cycloalkyl; C6-C 18 Aryl; C1-C9 Heteroaryl; C7-C 18 Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is a C1-C4 alkylene group, and R b is a C1-C4 alkyl group. 7 It should be noted that where may be an alkenyl group, the imidazolium group may have one or more ethylenically unsaturated groups: exemplary groups in this regard include 1-H-imidazolium, 1-3-diethenyl; and 1-H-imidazolium, 3-ethenyl-1-(2-propen-1-yl)-.

[0048] Each R 8 are preferably independently selected from H or C1-C6 alkyl, more particularly independently selected from H or C1-C2 alkyl. Preferably, at least one R 8 can be H. R 9 is preferably H or C1-C2 alkyl, more particularly H or methyl.

[0049] Each R 10 are preferably independently C1-C 12 Alkyl; C1-C 12 Heteroalkyl; C3-C 18 Cycloalkyl; C6-C 18 Aryl; C1-C9 Heteroaryl; C7-C 18 Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-Rb [where R a is a C1-C6 alkylene group, and R b is a C1-C6 alkyl group. 10 is more particularly C1-C8 alkyl; C1-C8 heteroalkyl; C3-C 12 Cycloalkyl; C6-C 18 Aryl; C1-C9 Heteroaryl; C7-C 18 Alkylaryl; C2-C5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is a C1-C4 alkylene group, and R b is a C1-C4 alkyl group.

[0050] For compounds of formula (IV), the anion A is typically selected from the group consisting of: fluoride; chloride; bromide; iodide; perchlorate; nitrate; nitrite; phosphate; sulfate; sulfite; carbonate; bicarbonate; hydrogen phosphate; hydrogen sulfate; hydrogen sulfite; dihydrogen phosphate; trifluorophosphate; hexafluorophosphate; methyl sulfate; ethyl sulfate; methyl carbonate; methyl sulfonate; ethyl sulfonate; 4-methylbenzenesulfonate; diethyl phosphate; formate; acetate; propionate; tartrate; octanoate; bis(2,4,4-trimethylpentyl)phosphinate; bis(malonato)borate; bis(oxalato)borate; bis(pentafluoroethyl)phosphinate; tetracyanoborate; tetrafluoroborate. phosphate; bis(phthalato)borate; bis(salicylate)borate; bis(trifluoromethylsulfonate)imide; bis(trifluoromethanesulfonyl)methane; bis(trifluoromethyl)imidate; tetrakis(hydrogen sulfate)borate; tetrakis(methylsulfonate)borate; trifluoromethylsulfonate; tris(heptafluoropropyl)trifluorophosphate; tris(nonafluorobutyl)trifluorophosphate; tris(pentafluoroethyl)trifluorophosphate; tris(pentafluoroethylsulfonyl)trifluorophosphate; trichlorozincate; trifluoroacetate; bromoaluminate; chloroaluminate; dichlorocuprate; thiocyanate; tosylate; and dicyanamide.

[0051] The anion A is preferably selected from the group consisting of fluoride; chloride; bromide; iodide; perchlorate; nitrate; formate; acetate; octanoate; tetrafluoroborate; trifluorophosphate; hexafluorophosphate; methyl sulfate; ethyl sulfate; methyl carbonate; methyl sulfonate; 4-methylbenzenesulfonate; trifluoromethyl sulfonate; bis(trifluoromethylsulfonate)imide, trifluorophosphate, trifluoroacetate; and tris(perfluoroethyl)trifluorophosphate.

[0052] More particularly, the anion A is selected from the group consisting of fluoride; chloride; bromide; iodide; tetrafluoroborate; hexafluorophosphate; methyl sulfate; ethyl sulfate; methyl sulfonate; 4-methylbenzenesulfonate; and bis(trifluoromethylsulfonate)imide.

[0053] The anion T is an ethylenically unsaturated carboxylate anion (R-COO-); an ethylenically unsaturated sulfonate anion (R-SO3 - ); Ethylenically unsaturated phosphonate anion (R-PO3 2- ); Ethylenically unsaturated phosphinate anion (RP(H)O2 - ); and ethylenically unsaturated phosphate anion (RO-PO3 2- ) wherein R is an organic group having ethylenic unsaturation which polymerizes under normal conditions, this group preferably being derived from (meth)acrylic acid, vinyl acid or allylic acid.

[0054] Typical anions T include: (meth)acrylate; itanconate; maleate; crotonate; isocrotonate; vinyl benzoate; 2-acrylamido-2-methylpropanesulfonate; sulfoethyl (meth)acrylate; sulfopropyl (meth)acrylate; sulfomethylated acrylamide; allyl sulfonate; vinyl sulfonate; 4-vinylbenzenesulfonate (4-styrenesulfonate); 4-isopropenylbenzenesulfonate (4-methylstyrenesulfonate); allyl phosphonate; and monoacryloxyethyl phosphate.

[0055] Examples of compounds b1) represented by formula (IV) include, but are not limited to, 1H-imidazolium, 3-ethenyl-1-methyl-, iodide; 1H-imidazolium, 3-ethenyl-1-methyl-, chloride; 1H-imidazolium, 3-ethenyl-1-methyl-, bromide; 1H-imidazolium, 3-ethenyl-1-methyl-, methanesulfonate; 1H-imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-methyl-, Hexafluorophosphate;1H-Imidazolium, 3-ethenyl-1-methyl-, 4-methylbenzenesulfonate;1H-Imidazolium, 3-ethenyl-1-methyl-, tetrafluoroborate;1H-Imidazolium, 3-ethenyl-1-ethyl-, iodide;1H-Imidazolium, 3-ethenyl-1-ethyl-, bromide;1H-Imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 3-ethenyl-1-ethyl-, hexafluorophosphate;1H-Imidazolium, 3-ethenyl-1-ethyl-, tetrafluoroborate;1H-Imidazolium, 1,3-diethenyl-, Chloride;1H-Imidazolium, 1,3-diethenyl-, tetrafluoroborate;1H-Imidazolium, 1,3-diethenyl-, hexafluorophosphate;1H-Imidazolium, 3-ethenyl-1-ethyl-2-methyl-, iodide;1H-Imidazolium, 3-ethenyl-1,2-dimethyl-, iodide;1H-Imidazolium, 3-ethenyl-1,2-dimethyl-, chloride;1H-Imidazolium, 3-ethenyl-2-ethyl-1-methyl-, iodide;1H-Imidazolium, 3-(aminomethyl)-1-ethenyl-, bromide;1H-Imidazolium, 3-ethenyl-1-(1-methylethyl)-, bromide1H-Imidazolium, 3-(1,1-dimethylethyl)-1-ethenyl-, bromide;1H-Imidazolium, 3-ethenyl-1-propyl-, bromide;1H-Imidazolium, 1-(2-aminoethyl)-3-ethenyl-, chloride;1H-Imidazolium, 1-(cyanomethyl)-3-ethenyl-, bromide;1H-Imidazolium, 1-[2-(diethylamino)ethyl]-3-ethenyl-, chloride;1H-Imidazolium, 3-ethenyl-1-(2-propen-1-yl)-, chloride;1H-Imidazolium, 3-ethenyl-1-(2-propen-1-yl)-, 1,1,1-Trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 3-ethenyl-1-(2-propen-1-yl)-, bromide;1H-Imidazolium, 3-ethenyl-1-(phenylmethyl)-, bromide;1H-Imidazolium, 1-ethenyl-3-(4-methylphenyl)-, chloride;1H-Imidazolium, 3-ethenyl-1-(2-hydroxyethyl)-, chloride;1H-Imidazolium, 3-ethenyl-1-(1-methylpropyl)-, chloride;1H-Imidazolium, 1-butyl-3-ethenyl-, bromide;1H-Imidazolium, 3-ethenyl-1-(2-ethoxyethyl)-, Bromide;1H-Imidazolium, 1-methyl-3-(2-propen-1-yl)-, iodide;1H-Imidazolium, 1-methyl-3-(2-propen-1-yl)-, chloride;1H-Imidazolium, 1-methyl-3-(2-propen-1-yl)-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 1-methyl-3-(2-propen-1-yl)-, hexafluorophosphate;1H-Imidazolium, 1-methyl-3-(2-propen-1-yl)-, tetrafluoroborate;1H-Imidazolium, 1-ethyl-3-(2-propen-1-yl)-, iodide;1H-Imidazolium, 2-Methyl-3-(2-propen-1-yl)-1-propyl-, bromide;1H-Imidazolium, 3-(2-propen-1-yl)-1-propyl-, bromide;1H-Imidazolium, 3-(2-hydroxyethyl)-1-(2-propen-1-yl)-, bromide;1H-Imidazolium, 1-butyl-3-(2-propen-1-yl)-, bromide;1H-Imidazolium, 1,3-di-2-propen-1-yl-, bromide;1H-Imidazolium, 1,3-di-2-propen-1-yl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 1,3-di-2-propen-1-yl-, tetrafluoroborate;1H-Imidazolium, 3-(2-hydroxyethyl)-1-(2-propen-1-yl)-, bromide;1H-Imidazolium, 1-(2-Cyanoethyl)-3-(2-propen-1-yl)-, bromide;1H-Imidazolium, 1-methyl-3-(2-oxopropyl)-, tetrafluoroborate;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, iodide;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, chloride;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, hexafluorophosphate;1H-Imidazolium, 3-[(4-Ethenylphenyl)methyl]-1-methyl-, tetrafluoroborate;1H-Imidazolium, 3-[(4-Ethenylphenyl)methyl]-1-ethyl-, chloride;1H-Imidazolium, 1-[(4-Ethenylphenyl)methyl]-3-ethyl-, salt of 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 1-(3-aminopropyl)-3-[(4-ethenylphenyl)methyl]-, chloride;1H-Imidazolium, 1-butyl-3-[(4-ethenylphenyl)methyl]-, chloride;1H-Imidazolium, 1-methyl-3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-, bromide;1H-imidazolium, 1-ethyl-3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-, iodide; and 1H-imidazolium, 1-butyl-3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-, iodide. For completeness, such compounds may be present alone or in combination of two or more in the compositions of the present invention.

[0056] While not intending to limit the invention, representative examples of compounds of formula (IV) include the following: TIFF0007804594000007.tif73155 TIFF0007804594000008.tif3021 TIFF0007804594000009.tif23101 TIFF0007804594000010.tif26107 TIFF0007804594000011.tif30107 TIFF0007804594000012.tif2494

[0057] For completeness, in the above formula, NTf2- denotes the bistrifluoromethanesulfonimidate anion.

[0058] Examples of compounds b2) of formula (V) include, but are not limited to, 1H-imidazolium, 3-(3-cyanopropyl)-1-methyl-, 2-propenoate; 1H-imidazolium, 3-hexyl-1-methyl-, 2-propenoate; 1H-imidazolium, 3-hexadecyl-1-methyl-, 2-propenoate; 1H-imidazolium, 3-ethyl-1-methyl-, 2-methyl-2-propenoate; 1H-imidazolium, 1-methyl-3-(phenylmethyl)-, 2-methyl-2-propenoate; 1H-imidazolium, 3-ethyl-1-methyl-, 1-[2-[(1-oxo-2-propen-1-yl)oxy]ethyl]1,2-benzenedicarboxylate;1H-Imidazolium, 3-ethyl-1-methyl-, 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-1-propanesulfonate;1H-Imidazolium, 3-butyl-1-methyl-, 3-sulfopropyl 2-methyl-2-propenoate;1H-Imidazolium, 3-ethyl-1-methyl-, 2-(phosphonooxy)ethyl 2-methyl-2-propenoate salt;1H-Imidazolium, 1-methyl-3-hexyl-, 4-ethenylbenzenesulfonate;1H-Imidazolium, 1-dodecyl-3-ethenyl-, 4-ethenylbenzenesulfonate 3-ethenyl-1-hexadecyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-methyl-3-propyl-, 4-ethenylbenzenesulfonate; and 1H-imidazolium, 3-ethyl-1-methyl-, 4-(1-methylethenyl)benzenesulfonate. For completeness, such compounds may be present in the compositions of the present invention alone or in combination of two or more.

[0059] While not intending to limit the invention, representative examples of compounds of formula (V) include the following: TIFF0007804594000013.tif43164 TIFF0007804594000014.tif25113 TIFF0007804594000015.tif2885 TIFF0007804594000016.tif26105

[0060] It should be noted that in one embodiment, the electrically releasable adhesive composition may comprise both b1) one or more compounds of formula (IV); and b2) one or more compounds of formula (V). When both are present, it is preferred that the ratio of b1) to b2) is 5:1 to 1:1, for example, 4:1 to 2:1.

[0061] c) Free Radical Initiators The composition of the present invention comprises c) at least one free radical initiator. The composition should typically comprise 0.1 to 10 wt. %, for example 0.1 to 5 wt. % or 0.1 to 2.5 wt. % of c) at least one free radical initiator, based on the total weight of the composition.

[0062] While not intending to limit the invention, exemplary types of free radical initiators suitable for use herein are organic peroxides selected from, for example, cyclic peroxides; diacyl peroxides; dialkyl peroxides; hydroperoxides; peroxycarbonates; peroxydicarbonates; peroxyesters; and peroxyketals.

[0063] While certain peroxides, such as dialkyl peroxides, are disclosed as useful initiators, inter alia, in U.S. Patent No. 3,419,512 (Lees) and U.S. Patent No. 3,479,246 (Stapleton), and may also be useful in the present invention, hydroperoxides represent a preferred type of initiator for the present invention. While hydrogen peroxide itself may also be used, the most preferred polymerization initiators are organic hydroperoxides. For completeness, the definition of hydroperoxide includes materials such as organic peroxides or organic peresters that decompose or hydrolyze to form organic hydroperoxides in situ; examples of such peroxides and peresters are cyclohexyl and hydroxycyclohexyl peroxide, and t-butyl perbenzoate, respectively.

[0064] In one embodiment of the present invention, the free radical initiator has the formula: R p OOH [In the formula, R P is an aliphatic or aromatic group having up to 18 carbon atoms, preferably: R P is C1-C 12 Alkyl, C6-C 18 Aryl or C7-C 18 an aralkyl group] The composition comprises or consists of at least one hydroperoxide compound represented by the formula:

[0065] Examples of peroxide initiators that can be used alone or in combination include cumene hydroperoxide (CHP); para-menthane hydroperoxide; t-butyl hydroperoxide (TBH); t-butyl perbenzoate; t-butyl peroxypivalate; di-t-butyl peroxide; t-butyl peroxyacetate; t-butyl peroxy-2-hexanoate; t-amyl hydroperoxide; 1,2,3,4-tetramethylbutyl hydroperoxide; and benzoyl peroxide. ;dibenzoyl peroxide;1,3-bis(t-butylperoxyisopropyl)benzene;diacetyl peroxide;butyl 4,4-bis(t-butylperoxy)valerate;p-chlorobenzoyl peroxide;t-butylcumyl peroxide;di-t-butyl peroxide;dicumyl peroxide;2,5-dimethyl-2,5-di-t-butylperoxyhexane;2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-ine;and4-methyl-2,2-di-t-butylperoxypentane.

[0066] While not intending to limit the invention, another exemplary type of free radical initiator suitable for use herein is an azo polymerization initiator selected from, for example, azonitriles; azoesters; azoamides; azoamidines; azoimidazolines; and macroazo initiators.

[0067] Typical examples of suitable azo polymerization initiators include: 2,2'-azobis(2-methylbutyronitrile); 2,2'-azobis(isobutyronitrile); 2,2'-azobis(2,4-dimethylvaleronitrile); 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); 1,1'-azobis(cyclohexane-1-carbonitrile); 4,4'-azobis(4-cyanovaleric acid); dimethyl 2,2'-azobis(2-methylpropionate); 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]; 2,2'-azobis(N-butyl-2-methylpropionamide); 2,2'-azobis[2 2,2'-Azobis[N-(2-imidazolin-2-yl)propane] dihydrochloride; 2,2'-Azobis(2-methylpropionamidine) dihydrochloride; 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate; 4,4-Azobis(4-cyanovaleric acid) polymer with α,ω-bis(3-aminopropyl)polydimethylsiloxane (VPS-1001, available from Wako Pure Chemical Industries, Ltd.); and 4,4'-Azobis(4-cyanopentanoic acid)·polyethylene glycol polymer (VPE-0201, available from Wako Pure Chemical Industries, Ltd.).

[0068] It is not excluded that the compositions of the present invention may comprise at least one free radical photoinitiator compound that initiates polymerization or hardening of the composition upon exposure to actinic radiation.

[0069] Typically, free radical photoinitiators are classified as those that form radicals by cleavage, known as "Norrish Type I," and those that form radicals by hydrogen abstraction, known as "Norrish Type II." Norrish Type II photoinitiators require a hydrogen donor to act as the source of free radicals: because initiation is based on a bimolecular reaction, Norrish Type II photoinitiators are generally slower than Norrish Type I photoinitiators, which are based on the unimolecular formation of radicals. On the other hand, Norrish Type II photoinitiators have better light absorption characteristics in the near-ultraviolet spectral region. One skilled in the art should be able to select an appropriate free radical photoinitiator based on the actinic radiation used for curing and the photoinitiator's sensitivity at that wavelength.

[0070] Preferred free radical photoinitiators are those selected from the group consisting of benzoylphosphine oxides, aryl ketones, benzophenones, hydroxylated ketones, 1-hydroxyphenyl ketones, ketals, and metallocenes. For the sake of completeness, combinations of two or more of these photoinitiators are not excluded in the present invention.

[0071] Particularly preferred free radical photoinitiators are benzoin dimethyl ether; 1-hydroxycyclohexyl phenyl ketone; benzophenone; 4-chlorobenzophenone; 4-methylbenzophenone; 4-phenylbenzophenone; 4,4'-bis(diethylamino)benzophenone; 4,4'-bis(N,N'-dimethylamino)benzophenone (Michler's ketone); isopropylthioxanthone; 2-hydroxy-2-methylpropiophenone (Daracur); 1173); 2-methyl-4-(methylthio)-2-morpholinopropiophenone; methylphenyl glyoxylate; methyl 2-benzoylbenzoate; 2-ethylhexyl 4-(dimethylamino)benzoate; ethyl 4-(N,N-dimethylamino)benzoate; phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; and ethylphenyl(2,4,6-trimethylbenzoyl)phosphinate. Again, combinations of two or more of these photoinitiators are not excluded in the present invention.

[0072] When the compositions of the present invention include a free-radical photoinitiator, irradiation of the curable composition generates active species from the photoinitiator that begin the curing reaction. Once the species is generated, the cure chemistry follows the same rules of thermodynamics as chemical reactions: reaction rates can be accelerated by heat. The use of thermal treatment to accelerate actinic curing of monomers is commonly known in the art.

[0073] As will be appreciated by those skilled in the art, a photosensitizer can be incorporated into the composition to improve the efficiency with which the photoinitiator c) uses the delivered energy. The term "photosensitizer" is used according to its standard meaning to refer to any substance that increases the rate of photoinitiated polymerization or shifts the wavelength at which polymerization occurs. Photosensitizers should be used in amounts of 0-25% by weight, based on the weight of the free radical photoinitiator.

[0074] The use of free radical (photo)initiators can result in residual compounds from the (photo)chemical reaction in the final cured product. The residues can be detected by conventional analytical techniques, such as infrared, ultraviolet, and NMR spectroscopy; gas or liquid chromatography; and mass spectroscopy. Thus, the present invention can contain a cured matrix (co)polymer and a detectable amount of residue from the free radical (photo)initiator. The residues are present in small amounts and typically do not interfere with the desirable physicochemical properties of the final cured product.

[0075] d) Solubilizer The compositions of the present invention may optionally contain a solubilizer. The compositions may contain, for example, 0.1 to 10 wt. % or 0.1 to 5 wt. % of the solubilizer based on the weight of the composition. The solubilizer functions to promote the miscibility of the electrolyte b) in the adhesive composition: the solubilizer may or may not form part of the polymer matrix formed upon curing of the adhesive composition, but serves to promote ion migration therein. The solubilizer is preferably a compound that is polar in itself and should preferably be liquid at room temperature.

[0076] Suitable types of solubilizers include: polyphosphazenes; polymethylene sulfides; polyoxyalkylene glycols; polyethyleneimines; silicone surfactants, such as polyoxyalkylene-modified polydimethylsiloxanes and polyalkylsiloxanes, including but not limited to poly(C2-C3)oxyalkylene-modified polydimethylsiloxanes; copolymers of functionalized polyalkylsiloxanes and epoxy resins, such as copolymers of polydimethylsiloxane (PDMS) and epoxy resins; polyhydric alcohols; and sugars. For completeness, fluorinated silicone surfactants, such as fluorinated polysiloxanes, are intended to be included in the term "silicone surfactant."

[0077] Polyhydric alcohols and sugars, such as ethylene glycol, 1,3-propanediol, cyclohexanediol, hydroquinone, catechol, resorcinol, phloroglucinol, pyrogallol, hydroxyhydroquinone, tris(hydroxymethyl)benzene, tris(hydroxymethyl)benzene with three methyl or ethyl substituents attached to the remaining benzene carbon atoms, isosorbide, isomannide, isoiodide, glycerol, cyclohexane-1,2,4-triol, 1,3,5-cyclohexanetriol, pentane-1,2,3-triol, Hexane-1,3,5-triol, erythritol, 1,2,4,5-tetrahydroxybenzene, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, inositol, fructose, glucose, mannose, lactose, 1,1,1-tris(hydroxymethyl)propane, 1,1,1-tris(hydroxymethyl)ethane, di(trimethylolpropane), trimethylolpropane ethoxylate, 2-hydroxymethyl-1,3-propanediol, pentaerythritol allyl ether, and pentaerythritol.

[0078] It may be noted that among the polyoxyalkylene glycols, it is particularly preferred to use polyoxy(C2-C3) alkylene glycols having a weight average molecular weight of 200 to 10000 g / mol, for example 200 to 2000 g / mol.

[0079] Additives and auxiliary ingredients The compositions obtained in the present invention may typically further comprise additives and auxiliary ingredients that can impart improved properties to these compositions. For example, the additives and auxiliary ingredients may provide one or more of the following: improved elastic properties, improved elastic recovery, extended processing time, reduced cure time, and reduced residual tack. Such additives and auxiliary ingredients include non-polymerizable electrolytes; reinforcing agents; conductive particles; electrically non-conductive fillers; catalysts; plasticizers; stabilizers, including UV stabilizers; antioxidants; reactive diluents; drying agents; adhesion promoters; fungicides; flame retardants; rheological aids; color pigments or color pastes; and / or, optionally, minor amounts of non-reactive diluents.

[0080] Such additives and auxiliary components may be used in any desired combination and proportion as long as they do not adversely affect the properties and essential characteristics of the composition. Although there may be exceptions in some cases, these additives and auxiliary components should not, in total, comprise more than 20% by weight of the entire composition, and preferably, should not comprise more than 10% by weight of the composition.

[0081] The presence of non-polymerizable electrolytes in the composition of the present invention is not excluded. Exemplary electrolytes include non-polymerizable salts of cations selected from the group consisting of ammonium, pyridinium, phosphonium, imidazolium, oxazolium, guanidinium, and thiazolium. The anions of such non-polymerizable salts are not particularly limited, and preferred anions include halides; - , CF3SO3 - , (CF3SO3)2N - , CF3CO2 - and CCl3CO2 -carboxylic acid anions, in particular formates, acetates, propionates, butyrates and lactates; hydroxycarboxylic acid anions; pyridinates and pyrimidinates; carboxylic acid imides, bis(sulfonyl)imides and sulfonyl imides; sulfates, in particular methyl sulfate and ethyl sulfate; sulfites; sulfonates, in particular methanesulfonate; and phosphates, in particular dimethyl phosphate, diethyl phosphate and di-(2-ethylhexyl)-phosphate.

[0082] If included in the composition, the non-polymerizable electrolyte should be present in an amount less than 10% by weight of the total weight of the polymerizable ionic compounds (part b)).

[0083] The presence of a toughening agent in the composition of the present invention may be beneficial for debonding of the cured adhesive. Without intending to be bound by theory, the toughening agent promotes phase separation within the cured adhesive under the application of an electric potential. Good debonding results have been obtained, particularly when the composition of the present invention includes at least one toughening agent selected from a toughened rubber in the form of core-shell particles dispersed in a matrix polymer; and an epoxy elastomer adduct.

[0084] The elastomer-containing adducts may be used individually, or two or more specific adducts may be used in combination. Each adduct may be independently selected from solid or liquid adducts at a temperature of 23°C. Typically, useful adducts may be characterized by an epoxy to elastomer weight ratio of 1:5 to 5:1, e.g., 1:3 to 3:1. References for suitable epoxy / elastomer adducts are also found in U.S. Patent Publication No. 2004 / 0204551. Exemplary commercially available epoxy / elastomer adducts for use in the present invention include, but are not limited to, HYPDX RK8-4, available from CVC Chemical, and B-Tough A3, available from Croda Europe Limited.

[0085] The term "core-shell rubber" or "CSR" is used according to its standard meaning in the art to refer to a rubber particle core formed by a polymer containing an elastomer or rubbery polymer as the primary component, and a shell layer formed by a polymer grafted onto the core. The shell layer covers some or all of the surface of the rubber particle core during the graft polymerization process. By weight, the core should constitute at least 50% by weight of the core-shell rubber particle.

[0086] The polymeric material of the core should have a glass transition temperature (Tg) of 0° C. or less, preferably −20° C. or less, more preferably −40° C. or less, and even more preferably −60° C. or less. The polymer of the shell is a non-elastomeric, thermoplastic or thermosetting polymer with a glass transition temperature (Tg) above room temperature, preferably above 30° C., and more preferably above 50° C.

[0087] Without limiting the invention, the core may be composed of diene homopolymers, such as homopolymers of butadiene or isoprene; diene copolymers, such as copolymers of butadiene or isoprene with one or more ethylenically unsaturated monomers (e.g., vinyl aromatic monomers, (meth)acrylonitrile, or (meth)acrylates); polymers based on (meth)acrylic acid ester monomers (e.g., polybutyl acrylate); and polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0088] Similarly, without limiting the invention, the shell may be comprised of a polymer or copolymer of one or more monomers selected from (meth)acrylates, such as methyl methacrylate; vinyl aromatic monomers, such as styrene; vinyl cyanides, such as acrylonitrile; unsaturated acids and anhydrides, such as acrylic acid; and (meth)acrylamide. The polymer or copolymer used in the shell may have acid groups that ionically crosslink via metal carboxylate formation, particularly via the formation of salts of divalent metal cations. The shell polymer or copolymer may also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0089] Any core-shell rubber particles present preferably have an average particle size (d50) of 10 nm to 300 nm, e.g., 50 nm to 250 nm, the particle size being the diameter or largest dimension of a particle in a distribution of particles, as measured by dynamic light scattering. For completeness, the present invention does not exclude the presence in the composition of two or more types of core-shell rubber (CSR) particles having different particle size distributions to provide a balance of important properties (including shear strength, peel strength, resin fracture toughness, etc.) in the resulting cured product.

[0090] The core-shell rubber may be selected from commercially available products, examples of which include: Paraloid EXL 2650A, EXL 2655, and EXL2691 A available from Dow Chemical Company; Clearstrength® XT100 available from Arkema Inc.; Kane Ace® MX series available from Kaneka Corporation, particularly MX 120, MX 125, MX 130, MX 136, MX 551, MX553; and METABLEN SX-006 available from Mitsubishi Rayon Co., Ltd.

[0091] The composition of the present invention may contain conductive particles. The composition may contain, for example, 0 to 10 wt % or 0.1 to 5 wt % of conductive particles based on the weight of the composition.

[0092] Generally, there is no intention to limit the shape of the particles used as conductive fillers: acicular, spherical, ellipsoidal, cylindrical, bead-like, cubic, or platelet-like particles may be used alone or in combination. It is also contemplated that aggregates of two or more particle types may be used. Similarly, there is no intention to limit the size of the particles used as conductive fillers. However, such conductive fillers may typically have an average volume particle size, as measured by laser diffraction and scattering, of 0.1 to 1500 μm, e.g., 1 to 1250 μm.

[0093] Examples of conductive particulate fillers include, but are not limited to, silver, copper, gold, palladium, platinum, nickel, gold- or silver-coated nickel, carbon black, carbon fibers, graphite, aluminum, indium tin oxide, silver-coated copper, silver-coated aluminum, metal-coated glass spheres, metal-coated fillers, metal-coated polymers, silver-coated fibers, silver-coated spheres, antimony-doped tin oxide, conductive nanospheres, nanosilver, nanoaluminum, nanocopper, nanonickel, carbon nanotubes, and mixtures thereof. Particulate silver and / or carbon black are preferably used as the conductive filler.

[0094] The compositions of the present invention may optionally include an electrically non-conductive filler, for example, 0 to 10 wt % or 0.1 to 5 wt % of electrically non-conductive particles based on the weight of the composition.

[0095] Generally, there is no intention to particularly limit the shape of the particles used as non-conductive fillers: particles that are acicular, spherical, ellipsoidal, cylindrical, bead-like, cubic, or platelet-like may be used alone or in combination. It is also contemplated that aggregates of two or more particle types may be used. Similarly, there is no intention to particularly limit the size of the particles used as non-conductive fillers. However, such non-conductive fillers may typically have an average volume particle size, as measured by laser diffraction and scattering, of 0.1 to 1500 μm, e.g., 1 to 1250 μm.

[0096] Exemplary non-conductive fillers include, but are not limited to, calcium carbonate, calcium oxide, calcium hydroxide (lime powder), precipitated and / or calcined silica, zeolite, bentonite, wollastonite, magnesium carbonate, diatomite, barium sulfate, alumina, clay, talc, titanium dioxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass beads, glass powder, and other ground mineral substances. Organic fillers, particularly wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, shredded straw, rice husks, crushed walnut shells, and other chopped fibers, can also be used. Short fibers, such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber, can also be added.

[0097] The precipitated and / or calcined silica is advantageously from 10 to 90 m 2 / g. When used, they do not further increase the viscosity of the compositions of the present invention, but contribute to the toughening of the cured composition.

[0098] As a filler, advantageously 100 to 250 m 2 It is also conceivable to use precipitated and / or calcined silicic acids with a higher BET surface area of ​​0.1g / g: due to the larger BET surface area, the effect of strengthening the setting composition is achieved with a smaller weight proportion of silicic acid.

[0099] Hollow spheres with inorganic or plastic shells are also suitable as non-conductive fillers. These can be, for example, hollow glass spheres commercially available under the trade name Glass Bubbles®. Plastic-based hollow spheres such as Expancel® or Dualite® can also be used and are described in EP 0 520 426 B1: they are made of inorganic or organic materials and each have a diameter of 1 mm or less, preferably 500 μm or less.

[0100] Non-conductive fillers that impart thixotropy to the composition may be suitable for many applications: such fillers are also called rheological aids, for example hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.

[0101] The desired viscosity of the resulting curable composition can be determined by the amount of filler used. With this latter consideration in mind, the total amount of filler (both conductive and non-conductive) present in the composition should not prevent the composition from being easily applied by the selected method of applying the composition to a substrate. For example, a curable composition intended to be extrudable from a suitable dispensing device, such as a tube, should have a viscosity of 1,000 to 150,000 mPas, preferably 10,000 to 100,000 mPas.

[0102] For purposes of the present invention, a "plasticizer" is a substance that reduces the viscosity of the composition and thus promotes its processability. In the present invention, the plasticizer may be present in an amount of up to 10% by weight or up to 5% by weight, based on the total weight of the composition, and is preferably selected from the following group: diurethanes; ethers of monofunctional linear or branched C4-C16 alcohols, such as Cetiol OE (available from Cognis Deutschland GmbH, Düsseldorf); esters of abietic acid, butyric acid, thiobutyric acid, acetic acid, propionic acid, and citric acid; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of OH-containing or epoxidized fatty acids; glycolic acid esters; benzoic acid esters; phosphate esters; sulfonic acid esters; trimellitic acid esters; polyether plasticizers, such as end-capped polyethylene or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. It should be noted that, although phthalates can be used as plasticizers, they are not preferred due to their toxicity.

[0103] For the purposes of the present invention, "stabilizer" should be understood as antioxidants, UV stabilizers, heat stabilizers, or hydrolysis stabilizers. In the present invention, the stabilizers may constitute up to 10% by weight or up to 5% by weight in total, based on the total weight of the composition. Typical commercial examples of stabilizers suitable for use in the present invention include: sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; amines of the hindered amine light stabilizer (HALS) type; phosphorus; sulfur; and mixtures thereof.

[0104] It should be noted that compounds having metal chelating properties may be used in the compositions of the present invention to help enhance the adhesion of the cured adhesive to the substrate surface. Also suitable for use as an adhesion promoter is an acetoacetate-functionalized modified resin sold by King Industries under the trade name K-FLEX XM-B301.

[0105] To further extend shelf life, it is often recommended to further stabilize the inventive composition against moisture penetration by using a desiccant. There is also often a need to reduce the viscosity of the inventive adhesive composition for specific applications by using a reactive diluent. The total amount of reactive diluent present may typically be 0 to 10 wt. %, for example 0.1 to 5 wt. %, based on the total weight of the composition.

[0106] The presence of solvents and non-reactive diluents in the compositions of the present invention is not excluded if they can effectively reduce its viscosity. For example, and by way of example only, the compositions may contain one or more of the following: xylene; 2-methoxyethanol; dimethoxyethanol; 2-ethoxyethanol; 2-propoxyethanol; 2-isopropoxyethanol; 2-butoxyethanol; 2-phenoxyethanol; 2-benzyloxyethanol; benzyl alcohol; ethylene glycol; ethylene glycol dimethyl ether; ethylene glycol diethyl ether; ethylene glycol dibutyl ether; ethylene glycol diphenyl ether; diethylene glycol; diethylene glycol monomethyl ether; diethylene glycol monoethyl ether; diethylene glycol mono-n-butyl ether; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; diethylene glycol di-n-butyryl ether; propylene glycol glycol butyl ether; propylene glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol di-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropyl naphthalene; petroleum fractions such as Solvesso® products (available from Exxon); alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, and 8,11,14-pentadecatrienylphenol; styrenated phenols; bisphenols; aromatic hydrocarbon resins, especially those containing phenolic groups, such as ethoxylated or propoxylated phenols; adipates; sebacates; phthalates; benzoates; organic phosphates or sulfonates; and sulfonamides.

[0107] Apart from the above, said non-reactive diluents preferably constitute in total less than 10% by weight, in particular less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0108] Methods and Uses To produce the composition, the above parts are mixed together. It is important that the mixing results in a uniform dispersion of the polymerizable electrolyte (compounds b1) and / or b2) in the adhesive composition: such thorough and effective mixing determines a uniform distribution of charged species within the resulting polymer matrix after curing, which can provide sufficient ionic conductivity to support electrochemical reactions at the interface with the conductive substrate.

[0109] As is known in the art, to produce a one-part (1K) curable composition, the components of the composition are mixed together uniformly under conditions that inhibit or prevent reaction of the reactive components; such conditions are readily understood by those skilled in the art. As such, it may often be preferable to mix the curable components mechanically, such as by a static or dynamic mixer, rather than by hand, in predetermined amounts under anhydrous conditions, e.g., without intentional light exposure.

[0110] For two-component (2K) compositions, the reactive components are combined and mixed in a manner that induces their curing. For both one-component (1K) and two-component (2K) compositions, the reactive compounds must be mixed under sufficient shear to obtain a homogeneous mixture. This is believed to be achievable without special conditions or special equipment. However, suitable mixing equipment may include static mixing devices; magnetic stir bar devices; wire whisk devices; augers; batch mixers; planetary mixers; CW Brabender or Banburry® style mixers; and high-shear mixers such as blade-style blenders and rotary impellers.

[0111] For small-scale liner applications, typically involving volumes of less than 2 liters, the preferred packaging for two-component (2K) compositions is a parallel double cartridge or coaxial cartridge, in which two tubular chambers are arranged side-by-side or nested within each other and sealed with pistons. The components can be extruded from the cartridge by driving these pistons, advantageously via a closely mounted static or dynamic mixer. For larger-volume applications, the two components of the composition can be advantageously stored in drums or buckets. In this case, they are extruded through a hydraulic press, particularly a follower plate, and delivered via a pipeline to a mixing device that ensures thorough and highly uniform mixing of the hardener and binder components. In either case, it is important that the binder component be placed with an airtight and moisture-proof seal to allow for long-term storage of both components, ideally for 12 months or more.

[0112] Non-limiting examples of two-part composition dispensing devices and methods that may be suitable for the present invention include those disclosed in US Pat. No. 6,129,244 and US Pat. No. 8,313,006.

[0113] Where applicable, two-component (2K) compositions should generally be prepared to exhibit an initial viscosity measured immediately after mixing, e.g., up to 2 minutes after mixing, without limiting the method of application of the composition to a substrate. Two-component (2K) compositions should also be prepared to exhibit a pot life of at least 30 minutes, usually at least 60 or 120 minutes. This "pot life" is the time required for the viscosity of the curable composition to reach twice the viscosity of the freshly mixed curable composition at 20°C and 50% relative humidity.

[0114] According to the broadest method embodiment of the present invention, the composition is applied to a substrate and then cured in situ. Prior to application, it is often recommended to pretreat the relevant surface to remove foreign matter, if applicable; this step can facilitate subsequent adhesion of the composition. Such treatments are known in the art and can be carried out in one or more steps, such as etching with an acid and optionally an oxidizing agent appropriate for the substrate; ultrasonic treatment; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric plasma treatment, and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent such as carbon tetrachloride or trichloroethylene; and rinsing, preferably with deionized or demineralized water. When an aqueous alkaline degreasing bath is used, any remaining degreaser on the surface is preferably removed by rinsing the substrate surface with deionized or demineralized water.

[0115] In some embodiments, adhesion of the coating composition of the present invention to a substrate, preferably pretreated, can be facilitated by applying a primer thereto. While those skilled in the art can select an appropriate primer, references regarding primer selection include, but are not limited to, U.S. Patent No. 3,671,483; U.S. Patent No. 4,681,636; U.S. Patent No. 4,749,741; U.S. Patent No. 4,147,685; and U.S. Patent No. 6,231,990.

[0116] The composition is then preferably applied to the surface of the pretreated, optionally primed, substrate by conventional application methods such as brushing; roll coating, for example, using a four-application roll apparatus if the composition is solvent-free, or a two-application roll apparatus if the composition is a solvent-borne composition; doctor blade application; printing methods; and spraying methods, including, but not limited to, air-atomized spraying, air-assisted spraying, airless spraying, and high volume, low pressure spraying.

[0117] As stated above, the present invention provides a bonded structure comprising a first material layer having an electrically conductive surface and a second material layer having an electrically conductive surface, with the above-described and claimed cured electrochemically releasable adhesive composition disposed between the first and second material layers. To produce such a structure, the adhesive composition may be applied to an initial surface of at least one of the first and / or second material layers, and the two layers may then be brought into contact, optionally with the application of pressure, so that the electrically releasable adhesive composition is disposed between the two layers.

[0118] It is recommended that the composition be applied to the surface at a wet film thickness of 10 to 5000 μm, e.g., 50 to 2500 μm. Applying thinner layers within this range is more economical and reduces the possibility of harmful thick cured areas. However, careful control must be exercised when applying thinner coatings or layers to avoid both the formation of discontinuous cured films and short contacts.

[0119] Curing of the applied compositions of the present invention typically occurs at temperatures ranging from 40°C to 200°C, preferably from 50°C to 190°C, and especially from 60°C to 180°C. The appropriate temperature will depend on the particular compounds present and the desired rate of cure, and can be determined in each case by those skilled in the art, using simple preliminary tests if necessary. Of course, curing at lower temperatures within the ranges mentioned above is advantageous, as it usually avoids the need to substantially heat or cool the mixture from prevailing ambient temperatures. However, where appropriate, the temperature of the mixture formed from the components of the composition may be elevated above the mixing and / or application temperatures using conventional means, including microwave induction.

[0120] The present invention will now be described with reference to the accompanying drawings. FIG. 1a shows a joint structure according to a first embodiment of the invention. FIG. 1b shows a joint structure according to a second embodiment of the invention. FIG. 2a shows the initial delamination of the structure of the first embodiment when a voltage is applied to the structure of the first embodiment. FIG. 2b shows the initial delamination of the structure of the second embodiment when a voltage is applied to the structure of the second embodiment.

[0121] As shown in accompanying Figure 1a, a bonded structure is provided in which a cured adhesive layer (10) is disposed between two conductive substrates (11). As shown in Figure 1b, a layer of non-conductive material (12) may be disposed on the conductive substrate (11) to form a more complex bonded structure. Each layer of conductive substrate (11) is in electrical contact with a power source (13), which may be a battery or a direct current (DC) or AC power source. The positive and negative terminals of this power source (13) are shown in one fixed position, but those skilled in the art will understand that the polarity of the system can be reversed.

[0122] The two conductive substrates (11) are shown in the form of layers that can be composed of, among other things, metal films; metal meshes or grids; deposited metal particles; resin materials rendered conductive by conductive elements disposed therein; or conductive oxide layers. Examples of conductive elements include silver filaments, single-walled carbon nanotubes, and multi-walled carbon nanotubes. Examples of conductive oxides include doped indium oxides such as indium tin oxide (ITO), doped zinc oxide, antimony tin oxide, cadmium stannate, and zinc stannate. Aside from the choice of conductive material, those skilled in the art will understand that the effectiveness of the peeling operation may be reduced if the conductive substrate (11) is in the form of a grid or mesh that limits contact with the cured adhesive layer (10).

[0123] When a voltage is applied between the conductive substrates (11), a current is supplied to the adhesive composition (10) disposed therebetween. This induces an electrochemical reaction at the interface between the substrates (11) and the adhesive composition. This electrochemical reaction is understood to be oxidative at the positively or anodic interface and reductive at the negatively or cathodic interface. This reaction is believed to weaken the adhesive bond between the substrates, facilitating easy removal of the release composition from the substrates.

[0124] As shown in Figures 2a and 2b, for illustrative purposes only, delamination occurs at the positive interface, which is the interface between the conductive surface (11) in electrical contact with the positive electrode and the adhesive composition (10). Reversing the direction of the current flow before separating the substrates may weaken the adhesive bond at both substrate interfaces.

[0125] It should be noted, however, that the composition of the adhesive layer (10) can be tailored to cause delamination at either the positive or negative interface, or both simultaneously. In some embodiments, a voltage applied to both surfaces to form an anodic and cathodic interface causes delamination at both the anodic and cathodic adhesive / substrate interfaces simultaneously. In another embodiment, if the composition does not respond to direct current at both interfaces, reverse polarity can be used to simultaneously delaminate both substrate / adhesive interfaces. The current can be applied in any suitable waveform, provided that sufficient total time is allowed at each polarity for delamination to occur. In this regard, sinusoidal, square, and triangular waveforms may be suitable and can be applied from a controlled voltage or controlled current source.

[0126] Without intending to limit the invention, it is believed that the peeling operation can be effectively carried out when at least one, and preferably both, of the following conditions are promoted: a) application of a voltage of 1 to 100 V, e.g., 20 to 50 V; and b) application of a voltage for a period of 1 second to 180 minutes, e.g., 1 second to 30 minutes. When peeling of the conductive substrate from the cured adhesive is promoted by application of a force (e.g., applied via a weight or spring), the potential may only need to be applied for a period of seconds.

[0127] The following examples are illustrative of the present invention and are not intended to limit the scope of the invention. [Example]

[0128] Example In the examples, the following materials and their abbreviations were used: MMA: Methyl methacrylate MAA: methacrylic acid EGDMA: Ethylene glycol dimethyl acrylate PEG-MEA: polyethylene glycol methyl ether acrylate BENZYL MA: Benzyl methacrylate HEMA: (hydroxyethyl) methacrylate IBOA: Isobornyl acrylate AIBN: Azobisisobutyronitrile, available from Sigma Aldrich BPO: Benzoyl peroxide, available from PanReac AppliChem HEXMIM StSO3: 1H-Imidazolium, 3-methyl-1-hexyl-4-ethenylbenzenesulfonate EMIM Acrylate: 1H-Imidazolium, 1-ethyl-3-methyl-acrylate ViEIM NTf2: 1H-Imidazolium, 3-ethenyl-1-ethyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide BMIM NTf2: 1H-Imidazolium, 3-methyl-1-butyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide PEG400: Polyethylene glycol, available from Sigma Aldrich CN966H90: Aliphatic polyester-based urethane diacrylate oligomer blended with 10% 2(2-ethoxyethoxy)ethyl acrylate, available from Sartomer SR9054: Acid acrylate adhesion promoter, available from Sartomer

[0129] Preparation of the first set of compositions: Compositions EDA1 to EDA14 and Controls 1, 2 and 3 described in Tables 1a and 1b below were prepared by mixing. TIFF0007804594000017.tif91149

[0130] TIFF0007804594000018.tif95135

[0131] The amounts in parentheses of the polymerizable electrolytes shown in Tables 1a and 1b are in millimoles (mmol). Controls 1, 2, and 3 contain no ionic species and are composed of adhesive-forming nonionic matrix monomers. Compositions EDA1-EDA7, EDA9-EDA11, and EDA13-EDA14 are based on the copolymerization of nonionic matrix monomers with polymerizable ionic compounds.

[0132] EDA8 is a mixture of non-ionic matrix monomer and cured polymerizable electrolyte (PE) copolymer, which was obtained by the following method: first, ViEIM NTf2 (0.359 g) and HexMIM StSO3 (0.104 g) were mixed with azobisisobutyronitrile (0.008 g) at 3600 rpm for 1 minute at high speed; then, the mixture was cured at 80 °C for 15 minutes and then at 120 °C for 2 hours; finally, the cured material was mixed with the non-ionic matrix monomer and azobisisobutyronitrile.

[0133] EDA12 is a reference and is based on a mixture of a non-ionic matrix monomer and a non-polymerizable ionic compound (BMIM NTf2).

[0134] The application substrate for the following compositions EDA1-EDA14 and the control was 1.25 mm thick aluminum (AA6016). The coating compositions were applied using 100-200 micron diameter glass beads as spacers. The substrates were cut into 2.5 cm x 10 cm samples for tensile testing. Tensile lap shear (TLS) tests were performed at room temperature according to ISO 4587 "Determination of Tensile Lap Shear Strength of Adhesive-Rigid Substrate Bonded Assemblies" (International Organization for Standardization, 2003). The bond overlap area for each substrate listed was 2.5 cm x 1.0 cm, and the adhesive thickness was 0.1 cm (40 mil). An Instron 3366 with a 10 kN cell was used.

[0135] The applied adhesive composition was cured in the overlap area by application at 80° C. for 15 minutes and 120 minutes at 120° C. The bonded structure was then stored at room temperature for 24 hours before the first tensile test.

[0136] Example 1 After the 24 hour storage period, the tensile lap shear strength was tested before and after applying a constant potential of 50 V to the adhesive layer for 30 minutes, the results of which are shown in Table 2 below. TIFF0007804594000019.tif101143 Compositions containing polymerizable ionic compounds exhibit increased initial bond strength. Compositions based on copolymerization of polymerizable ionic compounds and nonionic matrix monomers exhibit decreased bond strength after application of voltage.

[0137] Example 2 In this example, the electrical peeling behavior of the adhesive composition EDA5 is investigated by measuring the tensile lap shear strength before and after applying different constant potentials to the adhesive layer for 30 minutes after the 24-hour storage period, and the results are shown in Table 3 below. TIFF0007804594000020.tif29158

[0138] Example 3 In this example, the electrical peel behavior of the adhesive is investigated after the 24 hour and 2 month storage times by measuring the tensile lap shear strength before and after applying a constant potential of 50 V to the adhesive layer for 30 minutes, and the results are shown in Table 4 below. TIFF0007804594000021.tif47161 A composition based on the copolymerization of a polymerizable ionic compound and a non-ionic matrix monomer maintains the initial bond strength after two months and still shows a decrease in bond strength after application of voltage.

[0139] Preparation of a second set of compositions: Compositions EDA15 to EDA19 and Control 4 shown in Table 5 below were prepared by mixing. TIFF0007804594000022.tif71128 Control 4 is composed of a non-ionic matrix monomer that forms an adhesive without ionic species. Compositions EDA15 to EDA18 are based on the copolymerization of a polymerizable ionic compound with a non-ionic matrix monomer. EDA19 is a reference example and is based on a mixture of a non-polymerizable ionic compound (BMIM NTf2) and a non-ionic matrix monomer.

[0140] The substrates used for the following compositions EDA15-EDA19 and Control 4 were aluminum (AA6016) with a thickness of 1.25 mm and stainless steel (1.4301) with a thickness of 1.5 mm. Glass beads with a diameter of 100-200 microns were used as spacers to apply the coating compositions. For tensile testing, the substrates were cut into samples measuring 2.5 cm x 10 cm (1 in x 4 in). Tensile lap shear (TLS) tests were performed at room temperature based on ISO 4587 "Determination of Tensile Lap Shear Strength of Adhesive-to-Rigid Substrate Bonded Assemblies" (International Organization for Standardization, 2003). The bond overlap area for each substrate was 2.5 cm x 1.0 cm, and the adhesive thickness was 0.1 cm (40 mil). A Zwick Z020 with a 20 kN cell was used. The applied adhesive composition was cured in the overlap area by application of 15 minutes at 80° C. and 30 minutes at 120° C. The bonded structure was then stored at room temperature for 24 hours before the first tensile test.

[0141] Example 4 After the 24 hour storage period, the tensile lap shear strength was measured before and after applying a constant potential of 50 V to the adhesive layer for 30 minutes, and the results are shown in Table 6 below. TIFF0007804594000023.tif56159 Compositions EDA15–EDA18, which contain polymerizable ionic compounds, maintained their initial bond strength, while composition EDA17 exhibited a loss in initial strength. Composition EDA19, which contains a nonpolymerizable ionic liquid, exhibited a 50% loss in initial strength. The bond strength of compositions based on the copolymerization of polymerizable ionic compounds and nonionic matrix monomers decreased after the application of voltage.

[0142] Example 5 In this example, the electrical peeling behavior of the adhesives (EDA15 compared to EDA19) is investigated by measuring the tensile lap shear strength after the 24 hour storage period, as well as after 1 week, 1 month, 2 months, and 3 months of storage, before and after applying a constant potential of 50 V to the adhesive layer for 30 minutes. A climate chamber set at 23°C and 50% relative humidity was used. The results are shown in Tables 7 and 8 below. TIFF0007804594000024.tif56161

[0143] TIFF0007804594000025.tif55162 Composition EDA15, based on the copolymerization of a polymerizable ionic compound and a non-ionic matrix monomer, shows a slight decrease in bond strength (12%) after 3 months. Compositions based on a mixture of a non-polymerizable ionic liquid and a non-ionic matrix monomer show a higher decrease in bond strength of 30% after 2 months for both aluminum and stainless steel. All compositions show a decrease in bond strength after the application of voltage.

[0144] In view of the above description and examples, it will be apparent to those skilled in the art that equivalent modifications can be made thereto without departing from the scope of the claims. Preferred aspects of the present invention include the following. [1] A curable, electrochemically releasable adhesive composition, the composition comprising, based on the weight of the composition: 40 to 99% by weight of a) at least one ethylenically unsaturated nonionic monomer; 0.9 to 50 wt. % of b) at least one polymerizable ionic compound; 0.1 to 10% by weight of c) at least one free radical initiator The polymerizable ionic compound comprises b1) at least one compound of general formula IV: TIFF0007804594000026.tif2280 and / or b2) at least one compound of general formula V: TIFF0007804594000027.tif2369 [In the formula, R 7 is C 1 -C 30 Alkyl; C 2 -C 8 Alkenyl; C 1 -C 30 Heteroalkyl;C 3 -C 30 Cycloalkyl; C 6 -C 18 Aryl;C 1 -C 9 Heteroaryl;C 7 -C 18 Alkylaryl;C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is C 1 -C 6 is an alkylene group, and R b is C 1 -C 6 an alkyl group; Each R 8 are independently H, C 1 -C 18 Alkyl, C 1 -C 18 Heteroalkyl, C 3 -C 18 Cycloalkyl, C 6 -C 18 Aryl, C 1 -C 9 Heteroaryl, C 7 -C 18 Alkylaryl or C 2 -C 5 heterocycloalkyl; R 9 is H or C 1 -C 4 is alkyl; Each R 10 independently, C 1 -C 30 Alkyl; C 1 -C 30 Heteroalkyl;C 3 -C 30 Cycloalkyl; C 6 -C 18 Aryl;C 1 -C 9 Heteroaryl;C 7 -C 18 Alkylaryl;C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is C 1 -C 6 is an alkylene group, and R b is C 1 -C 6 an alkyl group; A is a non-polymerizable anion; T is an ethylenically unsaturated anion; d and m are each integers having a value of at least 1; e and n are values ​​such that the compound is electrically neutral; TIFF0007804594000028.tif52 is a covalent bond, C 1 -C 2 Alkylene, -CH 2 OC(=O)-, -CH 2 CH 2 OC(=O)-, p-benzyl or p-tolyl] An adhesive composition comprising a compound represented by the formula: [2] 45 to 95 wt. % of a) the at least one ethylenically unsaturated nonionic monomer; 5 to 30 wt. % b) said at least one polymerizable ionic compound; 0.1 to 5 wt. % of c) said at least one free radical initiator; and 0 to 10% by weight of d) solubilizer The adhesive composition according to [1], comprising: [3] Part a) comprises 40 to 95 wt. % of a1) at least one compound of formula (I): H 2 C=CGCO 2 R 1 (I) [Wherein G is hydrogen, halogen or C 1 -C 4 is an alkyl group; R 1 is C 1 -C 30 Alkyl; C 2 -C 30 Heteroalkyl;C 3 -C 30 Cycloalkyl; C 2 -C 8 Heterocycloalkyl;C 2 -C 20 alkenyl; and C 2 -C 12 alkynyl] The adhesive composition according to [1] or [2], comprising a (meth)acrylate monomer represented by the following formula: [4] The adhesive composition according to any one of [1] to [3], wherein part a) comprises up to 50 wt. %, preferably 5 to 25 wt. %, of a3) at least one (meth)acrylate-functionalized oligomer, based on the weight of the composition. [5] The adhesive composition according to any one of [1] to [4], wherein part a) comprises at least one α,β-ethylenically unsaturated monocarboxylic acid having 3 to 5 carbon atoms. [6] In part b), R 7 is C 1 -C 8 Alkyl; C 2 -C 4 Alkenyl; C 1 -C 8 Heteroalkyl;C 3 -C 12 Cycloalkyl; C 6 -C 18 Aryl;C 1 -C 9 Heteroaryl;C 7 -C 18 Alkylaryl;C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is C 1 -C 4 is an alkylene group, and R b is C 1 -C 4 an alkyl group; Each R 8 are preferably independently H or C 1 -C 2 alkyl; R 9 is H or methyl; R 10 is C 1 -C 8 Alkyl; C 1 -C 8 Heteroalkyl;C 3 -C 12 Cycloalkyl; C 6 -C 18 Aryl;C 1 -C 9 Heteroaryl;C 7 -C 18 Alkylaryl;C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R a is C 1 -C 4 is an alkylene group, and R b is C 1 -C 4 an alkyl group; The adhesive composition according to any one of [1] to [5]. [7] Part b) is b1) 1H-Imidazolium, 3-ethenyl-1-methyl-, iodide; 1H-Imidazolium, 3-ethenyl-1-methyl-, chloride; 1H-Imidazolium, 3-ethenyl-1-methyl-, bromide; 1H-Imidazolium, 3-ethenyl-1-methyl-, methanesulfonate; 1H-Imidazolium, 3-ethenyl-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-Imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-Imidazolium, 3-ethenyl-1-methyl-, hexafluorophosphate; 1H-Imidazolium, 3-Ethenyl-1-methyl-, 4-methylbenzenesulfonate;1H-Imidazolium, 3-ethenyl-1-methyl-, tetrafluoroborate;1H-Imidazolium, 3-ethenyl-1-ethyl-, iodide;1H-Imidazolium, 3-ethenyl-1-ethyl-, bromide;1H-Imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 3-ethenyl-1-ethyl-, hexafluorophosphate;1H-Imidazolium, 3-ethenyl-1-ethyl-, tetrafluoroborate;1H-Imidazolium, 3-ethenyl-1-(1-methylethyl)-, bromide 3-(1,1-Dimethylethyl)-1-ethenyl-, bromide;1H-Imidazolium, 3-ethenyl-1-propyl-, bromide;1H-Imidazolium, 3-ethenyl-1-(phenylmethyl)-, bromide;1H-Imidazolium, 1-ethenyl-3-(4-methylphenyl)-, chloride;1H-Imidazolium, 3-ethenyl-1-(1-methylpropyl)-, chloride;1H-Imidazolium, 1-butyl-3-ethenyl-, bromide;3-[(4-ethenylphenyl)methyl]-1-methyl-, iodide;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, chloride;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, hexafluorophosphate;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, tetrafluoroborate;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-ethyl-, chloride;1H-Imidazolium, 1-[(4-ethenylphenyl)methyl]-3-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide salt;1H-Imidazolium, At least one compound selected from the group consisting of 1-(3-aminopropyl)-3-[(4-ethenylphenyl)methyl]-, chloride; 1H-imidazolium, 1-butyl-3-[(4-ethenylphenyl)methyl]-, chloride; and / or b2) at least one compound selected from the group consisting of 1H-imidazolium, 1-methyl-3-hexyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-dodecyl-3-ethenyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-methyl-3-propyl-, 4-ethenylbenzenesulfonate; and 1H-imidazolium, 3-ethyl-1-methyl-, 4-(1-methylethenyl)benzenesulfonate. The adhesive composition according to any one of [1] to [5], comprising: [8] The adhesive composition according to any one of [1] to [5], wherein part b) comprises at least one compound selected from the group consisting of 1H-imidazolium, 3-methyl-1-hexyl-4-ethenylbenzenesulfonate; 1H-imidazolium, 3-ethenyl-1-ethyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; and 1H-imidazolium, 3-methyl-1-butyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide. [9] The adhesive composition according to any one of [1] to [8], wherein part c) comprises at least one azo free radical initiator selected from the group consisting of azonitriles, azoesters, azoamides, azoamidines, azoimidazolines, and macroazo initiators.

[10] The adhesive composition according to any one of [1] to [9], wherein the composition comprises a solubilizer d) in an amount of up to 10 wt % based on the weight of the composition, the solubilizer being selected from the group consisting of polyoxyalkylene glycols; silicone surfactants; polyhydric alcohols; and sugars.

[11] The adhesive composition according to any one of [1] to

[10] , wherein the composition contains conductive particles in an amount of up to 10% by weight based on the weight of the composition.

[12] The adhesive composition according to

[11] , wherein the conductive particles are selected from the group consisting of silver, carbon black, and mixtures thereof.

[13] a first material layer having a conductive surface; and a second material layer having an electrically conductive surface; comprising [1] to

[12] , wherein the curable, electrochemically peelable adhesive composition according to any one of [1] to

[12] is disposed between a first material layer and a second material layer. bonded structure.

[14] 1) applying a voltage to both surfaces to form an anodic interface and a cathodic interface; and 2) A process of peeling off these surfaces The method for peeling a bonded structure according to

[13] , comprising:

[15] The method according to

[14] , wherein the voltage applied in step 1 is 0.5 to 200 V, and the voltage is preferably applied for 1 second to 30 minutes. [Explanation of symbols]

[0145] 10 Hardening Adhesive Layer 11. Conductive substrate 12 Non-conductive material layers 13 Power Supply

Claims

1. 1. A curable, electrochemically releasable adhesive composition comprising, based on the weight of the composition: 40 to 99 wt. % of a) at least one ethylenically unsaturated nonionic monomer; 0.9 to 50 wt. % of b) at least one polymerizable ionic compound; 0.1 to 10% by weight of c) at least one free radical initiator The polymerizable ionic compound comprises b1) at least one compound of general formula IV: and / or b2) at least one compound of the general formula V: [In the formula, R ７ is C 1 -C 30 Alkyl; C 2 -C 8 Alkenyl; C 1 -C 30 Heteroalkyl; C 3 -C 30 Cycloalkyl; C 6 -C 18 Aryl; C 1 -C 9 Heteroaryl; C 7 -C 18 Alkylaryl; C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R ａ is C 1 -C 6 is an alkylene group, and R ｂ is C 1 -C 6 an alkyl group; Each R ８ are independently H, C 1 -C 18 Alkyl, C 1 -C 18 Heteroalkyl, C 3 -C 18 Cycloalkyl, C 6 -C 18 Aryl, C 1 -C 9 Heteroaryl, C 7 -C 18 Alkylaryl or C 2 -C 5 heterocycloalkyl; R ９ is H or C 1 -C 4 is alkyl; Each R １０ independently, C 1 -C 30 Alkyl; C 1 -C 30 Heteroalkyl; C 3 -C 30 Cycloalkyl; C 6 -C 18 Aryl; C 1 -C 9 Heteroaryl; C 7 -C 18 Alkylaryl; C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R ａ is C 1 -C 6 is an alkylene group, and R ｂ is C 1 -C 6 an alkyl group; A is a non-polymerizable anion; T is an ethylenically unsaturated anion; d and m are each integers having a value of at least 1; e and n are values ​​such that the compound is electrically neutral; is a covalent bond, C 1 -C 2 Alkylene, -CH 2 OC(=O)-, -CH 2 CH 2 OC(=O)-, p-benzyl or p-tolyl. comprising a compound represented by The adhesive composition is based on the copolymerization of an ethylenically unsaturated nonionic monomer a) with a polymerizable ionic compound b).

2. 45 to 95 weight percent of a) said at least one ethylenically unsaturated nonionic monomer; 5 to 30 wt. % b) said at least one polymerizable ionic compound; 0.1 to 5 wt. % of c) said at least one free radical initiator; and 0-10% by weight of d) solubilizer The adhesive composition of claim 1 comprising:

3. Part a) comprises 40 to 95 wt. % of a1) at least one hydroxybenzoate of formula (I): H 2 C=CGCO 2 R 1 (I) wherein G is hydrogen, halogen or C 1 -C 4 is an alkyl group; R １ is C 1 -C 30 Alkyl; C 2 -C 30 Heteroalkyl; C 3 -C 30 Cycloalkyl; C 2 -C 8 Heterocycloalkyl; C 2 -C 20 alkenyl; and C 2 -C 12 alkynyl] The adhesive composition according to claim 1 or 2, comprising a (meth)acrylate monomer represented by the formula:

4. The adhesive composition of any of claims 1 to 3, wherein part a) comprises up to 50 wt. % of a3) at least one (meth)acrylate-functionalized oligomer, based on the weight of the composition.

5. An adhesive composition described in any of claims 1 to 4, wherein part a) comprises 5 to 25 wt% of a3) at least one (meth)acrylate-functionalized oligomer, based on the weight of the composition.

6. The adhesive composition of any of claims 1 to 5, wherein part a) comprises at least one α,β-ethylenically unsaturated monocarboxylic acid having from 3 to 5 carbon atoms.

7. In part b), R ７ is C 1 -C 8 Alkyl; C 2 -C 4 Alkenyl; C 1 -C 8 Heteroalkyl; C 3 -C 12 Cycloalkyl; C 6 -C 18 Aryl; C 1 -C 9 Heteroaryl; C 7 -C 18 Alkylaryl; C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R ａ is C 1 -C 4 is an alkylene group, and R ｂ is C 1 -C 4 an alkyl group; Each R ８ are independently H or C 1 -C 2 alkyl; R ９ is H or methyl; R １０ is C 1 -C 8 Alkyl; C 1 -C 8 Heteroalkyl; C 3 -C 12 Cycloalkyl; C 6 -C 18 Aryl; C 1 -C 9 Heteroaryl; C 7 -C 18 Alkylaryl; C 2 -C 5 heterocycloalkyl; or -R a -C(=O)-R b [where R ａ is C 1 -C 4 is an alkylene group, and R ｂ is C 1 -C 4 an alkyl group; The adhesive composition according to any one of claims 1 to 6.

8. Part b) is b1) 1H-Imidazolium, 3-ethenyl-1-methyl-, iodide; 1H-Imidazolium, 3-ethenyl-1-methyl-, chloride; 1H-Imidazolium, 3-ethenyl-1-methyl-, bromide; 1H-Imidazolium, 3-ethenyl-1-methyl-, methanesulfonate; 1H-Imidazolium, 3-ethenyl-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-Imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-Imidazolium, 3-ethenyl-1-methyl-, hexafluorophosphate; 1H-Imidazolium, 3-Ethenyl-1-methyl-, 4-methylbenzenesulfonate; 1H-Imidazolium, 3-ethenyl-1-methyl-, tetrafluoroborate; 1H-Imidazolium, 3-ethenyl-1-ethyl-, iodide; 1H-Imidazolium, 3-ethenyl-1-ethyl-, bromide; 1H-Imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-Imidazolium, 3-ethenyl-1-ethyl-, hexafluorophosphate; 1H-Imidazolium, 3-ethenyl-1-ethyl-, tetrafluoroborate; 1H-Imidazolium, 3-ethenyl-1-(1-methylethyl)-, bromide; 1H-Imidazolium, 3-(1,1-Dimethylethyl)-1-ethenyl-, bromide; 1H-Imidazolium, 3-ethenyl-1-propyl-, bromide; 1H-Imidazolium, 3-ethenyl-1-(phenylmethyl)-, bromide; 1H-Imidazolium, 1-ethenyl-3-(4-methylphenyl)-, chloride; 1H-Imidazolium, 3-ethenyl-1-(1-methylpropyl)-, chloride; 1H-Imidazolium, 1-butyl-3-ethenyl-, bromide; 3-[(4-ethenylphenyl)methyl]-1-methyl-, iodide; 1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, chloride;1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, hexafluorophosphate; 1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, tetrafluoroborate; 1H-Imidazolium, 3-[(4-ethenylphenyl)methyl]-1-ethyl-, chloride; 1H-Imidazolium, 1-[(4-ethenylphenyl)methyl]-3-ethyl-, salts of 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-Imidazolium, At least one compound selected from the group consisting of 1-(3-aminopropyl)-3-[(4-ethenylphenyl)methyl]-, chloride; 1H-imidazolium, 1-butyl-3-[(4-ethenylphenyl)methyl]-, chloride; and / or b2) at least one compound selected from the group consisting of 1H-imidazolium, 1-methyl-3-hexyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-dodecyl-3-ethenyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-methyl-3-propyl-, 4-ethenylbenzenesulfonate; and 1H-imidazolium, 3-ethyl-1-methyl-, 4-(1-methylethenyl)benzenesulfonate. The adhesive composition according to any one of claims 1 to 6, comprising:

9. 7. The adhesive composition of claim 1, wherein part b) comprises at least one compound selected from the group consisting of 1H-imidazolium, 3-methyl-1-hexyl-4-ethenylbenzenesulfonate; 1H-imidazolium, 3-ethenyl-1-ethyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; and 1H-imidazolium, 3-methyl-1-butyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide.

10. 10. The adhesive composition of claim 1, wherein part c) comprises at least one azo free radical initiator selected from the group consisting of azonitriles; azoesters; azoamides; azoamidines; azoimidazolines; and macroazo initiators.

11. 11. The adhesive composition of claim 1, wherein the composition comprises a solubilizer d) in an amount of up to 10 wt. % based on the weight of the composition, the solubilizer being selected from the group consisting of polyoxyalkylene glycols; silicone surfactants; polyhydric alcohols; and sugars.

12. The adhesive composition according to any one of claims 1 to 11, wherein the composition comprises conductive particles in an amount of up to 10% by weight based on the weight of the composition.

13. 13. The adhesive composition of claim 12, wherein the conductive particles are selected from the group consisting of silver, carbon black, and mixtures thereof.

14. a first layer of material having an electrically conductive surface; and a second layer of material having an electrically conductive surface; comprising The curable, electrochemically releasable adhesive composition according to any one of claims 1 to 13 is disposed between a first material layer and a second material layer. bonded structure.

15. 1) applying a voltage to both surfaces to form an anodic interface and a cathodic interface; and 2) peeling off these surfaces The method for peeling a bonded structure according to claim 14, comprising:

16. 16. The method of claim 15, wherein the voltage applied in step 1 is 0.5 to 200 V, and the voltage is applied for 1 second to 30 minutes.

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