One-component (1K) curable adhesive composition

Abstract

The present invention relates to a curable, electrochemically peelable one-component (1K) adhesive composition comprising, based on the weight of the composition, 40-90 wt. % of i) at least one ethylenically unsaturated nonionic monomer; 0.1-30 wt. % of ii) a non-polymerizable electrolyte; 0.1-10 wt. % of iii) at least one radical-generating thermal initiator; 0-20 wt. % of iv) a filler; and 0-20 wt. % of v) a toughening agent.

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition that can be peeled off a specific substrate to which it is applied. More specifically, the present invention relates to a one-component (1K) curable and electrochemically peelable adhesive composition based on a (meth)acrylate monomer. [Background technology]

[0002] Adhesives and polymer coatings are commonly used in the assembly and finishing of manufactured goods. They are used as replacements for mechanical fasteners such as screws, bolts, and rivets, reducing machining costs and providing adhesion with greater adaptability in the manufacturing process. Adhesives evenly distribute stress, reduce the possibility of fatigue, and isolate joints from corrosive species.

[0003] Therefore, while adhesive bonding offers many advantages over mechanical fasteners, it tends to be difficult to disassemble bonded articles when required in practical applications. Removal of adhesive by mechanical processes such as sandblasting or wire brushing is often rejected, for one reason being that the adhesive is positioned between the substrates, making it difficult to access without damaging the substrate surface or difficult to polish. Disassembly by the application of chemicals and / or high temperatures, as disclosed in U.S. Patent No. 4,171,240 (Wong) and U.S. Patent No. 4,729,797 (Linde et al.), may be effective, but can be time-consuming and complex to implement. Furthermore, the aggressive chemicals and / or harsh conditions required may damage the substrate being separated, rendering it unsuitable for subsequent applications.

[0004] With these issues in mind, certain authors have attempted to develop electrochemically detachable adhesive compositions that act to break the adhesion at the interface between the adhesive and the substrate by passing an electric current through the cured composition.

[0005] International Publication No. 2007 / 142600 (Stora Enso AB) describes an electrochemically weakened adhesive composition that provides an adhesive bond to a conductive surface and provides sufficient ionic conductivity to allow weakening of the adhesive bond when a voltage is applied to the adhesive composition, wherein the composition comprises at least one ionic compound in an amount effective for giving the ionic conductivity, the ionic compound having a melting point of 120°C or less.

[0006] European Patent Application Publication No. 3363875 (Nitto Denko Corporation) provides an electrically peelable adhesive composition that forms an adhesive layer having high adhesion and that can be easily peeled off by short-time voltage application. The electrically peelable adhesive composition of the present invention comprises a polymer and 0.5 to 30% by weight of an ionic solution based on the weight of the polymer, wherein the anion of the ionic solution is a bis(fluorosulfonyl)imide anion.

[0007] International Publication No. 2017 / 133864 (Henkel AG & Co. KGaA) describes a method for reversibly bonding first and second substrates, wherein at least the first substrate is a non-conductive substrate, and the method comprises: a) coating the surface of the non-conductive substrate with a conductive ink; b) applying an electrically peelable hot-melt adhesive composition to the surfaces of the first and / or second substrates coated with the conductive ink; c) bringing the first and second substrates into contact such that the electrically peelable hot-melt adhesive composition is interposed between the two substrates; d) forming an adhesive bond between the two substrates to provide an adhesive substrate; and e) applying a voltage to the adhesive substrate to substantially weaken the adhesion at least one interface between the electrically peelable hot-melt adhesive composition and the substrate surface.

[0008] International Publication No. 2013 / 135677 (Henkel AG & Co. KGaA) describes a hot-melt adhesive comprising 20-90% by weight of at least one polyamide having a molecular weight (Mw) of 10,000-250,000 g / mol; 1-25% by weight of at least one organic or inorganic salt; and 0-60% by weight of further additives, wherein the adhesive has a softening point of 100°C-220°C.

[0009] U.S. Patent Application Publication No. 2007 / 0269659 (Gilbert) describes a peelable adhesive composition at two interfaces, wherein the composition (i) comprises a polymer and an electrolyte, (ii) facilitates bonding of two surfaces, and (iii) peels from both the anode and cathode surfaces in response to a voltage applied to both surfaces to form an anode interface and a cathode interface.

[0010] U.S. Patent Application Publication No. 2008 / 0196828 (Gilbert) describes a hot-melt adhesive composition comprising a thermoplastic component and an electrolyte, wherein the electrolyte provides sufficient ionic conductivity to the composition, enabling a Faraday reaction in the bond formed between the composition and a conductive surface, thereby allowing the composition to be peeled from the surface.

[0011] U.S. Patent No. 7,465,492 (Gilbert) describes an electrochemically detachable composition comprising a matrix functionality containing a monomer selected from the group consisting of acrylics, methacrylics, and combinations thereof, a free radical initiator, and an electrolyte, wherein the electrolyte provides the composition with sufficient ionic conductivity to support a Faraday reaction in the adhesion formed between the composition and a conductive surface, thereby allowing the composition to be detached from the surface. In this reference, the electrolyte is solvable in the composition and is ammonium (NH4) + ), including salts that are part of the group consisting of alkali metal salts, alkaline earth salts or rare earth salts of perchlorates, tetrafluoroborates, hexafluorophosphates, triflates and triflimido anions. [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] International Publication No. 2007 / 142600 [Patent Document 4] European Patent Application Publication No. 3363875 [Patent Document 5] International Publication No. 2017 / 133864 [Patent Document 6] International Publication No. 2013 / 135677 [Patent Document 7] U.S. Patent Application Publication No. 2007 / 0269659 Specification [Patent Document 8] U.S. Patent Application Publication No. 2008 / 0196828 [Patent Document 9] U.S. Patent No. 7,465,492 [Overview of the project] [Problems that the invention aims to solve]

[0013] There remains a need in the art to provide a curable one-component (1K) adhesive composition that can be conveniently applied to the surface of the substrate to be bonded, provides efficient adhesion within the composite structure including the substrate during curing, and can be efficiently peeled off from the substrate by simply applying an electric potential to the cured adhesive. [Means for solving the problem]

[0014] According to a first aspect of the present invention, based on the weight of the composition, At least one i) ethylenically unsaturated nonionic monomer in an amount of 40-90% by weight, preferably 60-90% by weight, and more preferably 70-90% by weight; ii) Nonpolymerizable electrolyte in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight; iii) at least one radical-generating thermal initiator in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight; iv) filler in 0-20% by weight, preferably 0.5-10% by weight; and v) 0-20% by weight, preferably 0.5-20% by weight, more preferably 0.5-15% by weight of a reinforcing agent A curable and electrochemically peelable one-component (1K) adhesive composition is provided.

[0015] In certain embodiments of the composition, the (meth)acrylate monomer constitutes at least 60 mol%, preferably at least 75 mol%, of the total molar amount of the ethylenically unsaturated nonionic monomers. The (meth)acrylate monomer preferably comprises a C1-C6 hydroxyalkyl ester of (meth)acrylic acid. Independent of or supplementary to this preference, the (meth)acrylate monomer preferably comprises one or more oligomers selected from the group consisting of urethane (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. A particular preference for the inclusion of at least one urethane (meth)acrylate oligomer in the composition may be mentioned.

[0016] In this specification, several electrolytes are considered suitable, but good results have been obtained when the electrolyte is selected from the group consisting of 1-ethyl-3-methyl-1H-imidazole-3-ium methanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methyl-1H-imidazole-3-ium methyl sulfate and mixtures thereof.

[0017] In important embodiments, the compositions of the present invention may include at least one of iv) the filler or v) the reinforcing agent. The presence of both the filler and the reinforcing agent can, for example, enhance the adhesion of the composition to the substrate surface.

[0018] According to a second aspect of the present invention, A first material layer having a conductive surface, and An adhesive structure comprising a second material layer having a conductive surface, An adhesive structure is provided in which a cured electrochemically peelable one-component (1K) adhesive composition, as defined in the foregoing and appended claims of this specification, is placed between the first and second material layers.

[0019] A third aspect of the present invention is a method for peeling off the adhesive structure as defined in the foregoing and appended claims of this specification, i) A step of applying a voltage to both surfaces to form an anode interface and a cathode interface, and ii) Step of peeling off the surface A method including this is provided.

[0020] Step i) of this method is preferably a) Applied voltage of 0.5 to 200V; and b) characterized by at least one of the voltages applied for a period of time from 1 second to 60 minutes.

[0021] The adhesive strength of the composition is broken when a potential is applied across the bonding line between the composition and the conductive surface. While not intended to be theoretically bound, it is thought that a Faraday reaction occurring at the interface between the adhesive composition and the conductive surface breaks the interaction between the adhesive and the substrate, thereby weakening the bond between them. This interfacial breakdown may be the result of one or more processes, such as chemical degradation of the peelable material due to a change in the crosslinking density of the adhesive composition, gas generation at the interface, and / or embrittlement of the material. [Brief explanation of the drawing]

[0022] [Figure 1a] Figure 1a illustrates the adhesive structure of the first embodiment of the present invention. [Figure 1b] Figure 1b illustrates an adhesive structure according to a second embodiment of the present invention. [Figure 2a] Figure 2a illustrates the initial delamination of the structure when an electric current is passed through the structure of the first embodiment. [Figure 2b] Figure 2b illustrates the initial delamination of the structure when an electric current is passed through the structure of the second embodiment. [Modes for carrying out the invention]

[0023] definition As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly indicates otherwise.

[0024] As used herein, the terms “comprising,” “comprises,” and “comprised of” are synonymous with “including,” “includes,” “containing,” or “contains,” and are inclusive or open-ended, not excluding any additionally described components, elements, or process steps.

[0025] As used herein, the term "consists of" excludes any components, elements, parts, or methods or processes that are not specifically identified.

[0026] When quantities, concentrations, dimensions, and other parameters are expressed in the form of a range, preferred range, upper limit, lower limit, or preferred upper limit, it should be understood that the range obtained by combining any upper limit or preferred value with any lower limit or preferred value is also specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

[0027] Furthermore, according to a standard understanding, the weight range expressed as "from 0 to x" specifically includes 0% by weight, meaning that the components defined by the range may or may not be present in the composition, or may be present in the composition in amounts up to a maximum of x% by weight.

[0028] The terms “preferred,” “preferably,” “desirably,” and “particularly” are frequently used herein to refer to embodiments of the disclosure that, under certain circumstances, may offer particular advantages. However, the description of one or more preferred, preferred, desirable, or particular embodiments does not imply that other embodiments are unhelpful, nor is it intended to exclude those other embodiments from the scope of the disclosure.

[0029] The word "may" used throughout this application is used in an acceptable sense, meaning it is possible, rather than in a compulsory sense.

[0030] When used in this specification, room temperature is 23°C ± 2°C.

[0031] The molecular weights mentioned herein to describe the polymers, oligomers, and polymer components of curable compositions can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, as performed in accordance with ASTM 3536.

[0032] The viscosity of the compositions described herein is measured using a Brookfield viscometer under 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 as appropriate according to the manufacturer's instructions for the composition being measured.

[0033] As used herein, the term “electrochemically peelable” means that after curing the adhesive, applying a potential of 30V for 20 minutes can reduce the adhesive strength by at least 50%. The cured adhesive is applied between the two substrates to be bonded so that an electric current can flow through the adhesive bond line. The adhesive strength is measured by a tensile lap shear (TLS) test based on ASTMD 3163-01, “Standard test method for determining the shear strength of lap shear joints of adhesively bonded rigid plastics under tensile load,” performed at room temperature. The overlapping area of ​​the bond was 25 mm × 10 mm (1 inch × 0.4 inches) with an adhesive thickness of 0.15 cm (60 mil).

[0034] As used herein, the term “monomer” refers to a substance that can undergo polymerization reactions to provide building blocks for the chemical structure of a polymer. The term “monofunctional” as used herein means having one polymerizable site. As used herein, the term “polyfunctional” means having multiple polymerizable sites.

[0035] The term “electrolyte” is used herein in accordance with the standard meaning in the art as a substance containing free ions capable of conducting electricity through the movement of charged carrier species. This term is intended to encompass molten electrolytes, liquid electrolytes, semi-solid electrolytes, and solid electrolytes in which at least one of the cationic or anionic components of their electrolyte structure is essentially free to move and thus acts as a charge carrier.

[0036] The curable adhesive composition of the present invention and the cured adhesive obtained therefrom have "electrolyte functionality" in that the adhesive material enables the conduction of anionic, cationic, or both ions. Electrolyte functionality is understood to derive from the ability of the composition and the cured adhesive to solvate at least one polar ion.

[0037] The term "Faraday reaction" refers to an electrochemical reaction in which a substance is oxidized or reduced.

[0038] As used herein, “(meth)acrylic” is an abbreviation for “acrylic” and / or “methacrylic.” Therefore, the term “(meth)acrylate” refers collectively to acrylate and methacrylate.

[0039] When used herein, "C1-C n The "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, is an alkane radical, and includes linear and branched organic groups. Therefore, "C1-C 18 An alkyl group refers to a monovalent group containing 1 to 18 carbon atoms, is an alkane radical, and includes linear and branched organic groups. Examples of 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 halogens. Where applicable to a given site (R), the tolerance for one or more non-halogen substituents within the alkyl group is described in the specification.

[0040] The term "C1-C" is used in this specification. 18 A "hydroxyalkyl" refers to an HO-(alkyl) group having 1 to 18 carbon atoms, where the substituent bond is via an oxygen atom, and alkyl groups are defined as described above.

[0041] An "alkoxy group" refers to a monovalent group represented by -OA (where A is an alkyl group), and non-limiting examples include the methoxy group, ethoxy group, and iso-propyloxy group. The term "C1-C" as used herein is... 18 "Alkoxyalkyl" refers to an alkyl group having an alkoxy substituent as defined above (where the (alkyl-O-alkyl) part contains a total of 1 to 18 carbon atoms), and examples of such groups include methoxymethyl (-CH2OCH3), 2-methoxyethyl (-CH2CH2OCH3), and 2-ethoxyethyl.

[0042] As used herein, the term "C2-C4 alkylene" is defined as a saturated divalent hydrocarbon radical having 2 to 4 carbon atoms.

[0043] The term “C3-C 18 "Cycloalkyl" is understood to mean a saturated, monocyclic, or polycyclic hydrocarbon group having 3 to 18 carbon atoms. In the present invention, such cycloalkyl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given site (R), the tolerance for one or more non-halogen substituents within the cycloalkyl group is described in the specification. Examples of cycloalkyl groups include cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

[0044] When used herein, "C6-C" is used alone or as part of a larger group, such as "aralkyl group". 18 The "aryl" group refers to monocyclic, bicyclic, and tricyclic ring systems in which the monocyclic ring system is aromatic, or in which at least one of the rings of a bicyclic or tricyclic ring system is aromatic. Examples of bicyclic and tricyclic ring systems include benzo-condensed 2-3 membered carbon rings. In the present invention, such aryl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given site (R), the tolerance for one or more non-halogen substituents in the aryl group is described in the specification. Examples of aryl groups include phenyl; (C1-C4) alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. It should also be noted that phenyl groups are preferred.

[0045] As used herein, "C2-C 24"Alkenyl" refers to a hydrocarbyl group having 2 to 24 carbon atoms and at least one unit of ethylenic unsaturation. The alkenyl group can be linear, branched or cyclic and may optionally be substituted with one or more halogens. When applicable to a given site (R), the tolerance for one or more non-halogen substituents within the alkenyl group is described in the specification. The term "alkenyl" also includes radicals having "cis" and "trans" configurations, or alternatively "E" and "Z" configurations, as understood by those skilled in the art. However, generally, it should be noted that unsubstituted alkenyl groups containing 2 to 10 (C 2-10 ) or 2 to 8 (C 2-8 ) carbon atoms are preferred. Examples of the C2-C 12 alkenyl group 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=CHCH2CH3; -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.

[0046] As used herein, “alkylaryl” refers to an alkyl-substituted aryl group, and “substituted alkylaryl” refers to an alkylaryl group having one or more further substituents such as halo, nitro, cyano, amide, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, and hydroxy. Furthermore, as used herein, “aralkyl” means an alkyl group substituted with an aryl radical as defined above.

[0047] As used herein, the term “hetero” refers to a group or site containing one or more heteroatoms such as N, O, Si, and S. Thus, for example, “heterocyclic” refers to a cyclic group having N, O, Si, or S as part of its ring structure. The “heteroalkyl,” “heterocycloalkyl,” and “heteroaryl” moieties are alkyl, cycloalkyl, and aryl groups, respectively, that contain N, O, Si, or S as part of their structure, as defined above herein.

[0048] This composition may be defined herein as “substantially free” of certain compounds, elements, ions, or other similar components. The term “substantially free” is intended to mean that the compounds, elements, ions, or other similar components are not knowingly added to the composition, and are present at most in trace amounts that do not (adversely) affect the desired properties of the coating. An exemplary trace amount is less than 1000 ppm by weight of the composition. The term “substantially free” encompasses embodiments in which certain compounds, elements, ions, or other similar components are completely absent from the composition or are absent in amounts measurable by techniques commonly used in the art.

[0049] Detailed description of the invention 1. Nonionic matrix monomers The composition of the present invention comprises, based on the weight of the composition, 40 to 90% by weight of at least one ethylenically unsaturated nonionic monomer, and its (co)polymerization produces a peelable adhesive matrix. Preferably, the composition contains 60 to 90% by weight, for example, 70 to or 75 to 90% by weight of the at least one ethylenically unsaturated nonionic monomer. In principle, such monomers can be any ethylenically unsaturated nonionic monomer. However, the present invention is particularly applicable to compositions in which the (meth)acrylate monomer constitutes at least 60 mol%, preferably at least 75 mol%, of the total molar amount of the ethylenically unsaturated nonionic monomer present.

[0050] 1.1 (Meth)acrylate monomers In this specification, there is no particular intention to limit the useful (meth)acrylate esters, and (meth)acrylate monomers can be any ester of acrylic acid or methacrylic acid known in the art. However, exemplary (meth)acrylic monomers include, but are not limited to, the following.

[0051] • C1-C of (meth)acrylic acid 18 Alkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate (all isomers), hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and n-stearyl (meth)acrylate, etc. • C3-C of (meth)acrylic acid 18 Cycloalkyl esters, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; • C6-C of (meth)acrylic acid 18Aryl esters, such as phenyl(meth)acrylate and tolyl(meth)acrylate; • C7-C of (meth)acrylic acid 24 Aralkyl esters, such as benzyl (meth)acrylate; • C1-C of (meth)acrylic acid 18 Alkoxyalkyl esters, such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 3-methoxybutyl (meth)acrylate; • Fluorine-containing C1-C of (meth)acrylic acid 18 Alkyl esters, such as trifluoromethylmethyl(meth)acrylate, 2-trifluoromethylethyl(meth)acrylate, 2-perfluoroethylethyl(meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate, 2-perfluoroethyl(meth)acrylate, perfluoromethyl(meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl(meth)acrylate, 2-perfluorohexylethyl(meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, and 2-perfluorohexadecylethyl(meth)acrylate, etc. • C1-C of (meth)acrylic acid 18 Hydroxyalkyl esters, particularly C1-C6 hydroxyalkyl esters of (meth)acrylic acid, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; • Di / polyfunctional alcohol di / polyesters, such as ethylene glycol di(meth)acrylate, 1,3 or 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate; • C1-C of (meth)acrylic acid 18Aminoalkyl esters, such as 2-aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and (meth)acryloxyethoxyethylamine; • C1-C of (meth)acrylic acid 18 Alkoxysilyl-containing alkyl esters, such as γ-(methacryloyloxypropyl)trimethoxysilane; • Ethylene oxide or propylene oxide adducts of (meth)acrylic acid; and • (meth)acrylate esters formed by alcohols with other functional groups, such as tetrahydrofurfuryl (meth)acrylate.

[0052] For completeness, we do not exclude the inclusion of macromonomer components comprising one or more oligomers selected from the group consisting of urethane (meth)acrylates, polyester (meth)acrylates, and polyether (meth)acrylates. However, such oligomer compounds—which may be monofunctional or polyfunctional with respect to polymerizable (meth)acrylate functionality, but are based on repeating urethane, ester, and ether subunits—should not typically constitute more than 30% by weight of the total (meth)acrylate monomers in the composition.

[0053] As is known in the art, urethane (meth)acrylate oligomers can be prepared by the reaction of a polyfunctional (meth)acrylate having a hydroxyl group as defined above herein with a polyisocyanate. In particular, the polyfunctional (meth)acrylate having a hydroxyl group can be selected from the group consisting of 2-hydroxyethyl (meth)acrylate; 2-hydroxyisopropyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; hydroxyethyl caprolactone (meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate; dipentaerythritol hexa(meth)acrylate; and combinations thereof.

[0054] Suitable polyester (meth)acrylate oligomers can be obtained by reacting (meth)acrylic acid with a polyester prepared from a polybasic acid or its anhydride and a polyhydric alcohol. Examples of polybasic acids include, but are not limited to, phthalic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, isosebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, trimellitic acid, pyromellitic acid, pimelic acid, and azelaic acid. Examples of polyhydric alcohols include, but are not limited to, 1,6-hexanediol, diethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol.

[0055] As is known in the art, polyether (meth)acrylate oligomers can be obtained by transesterification reactions of polyethers with (meth)acrylic acid esters, such as ethyl methacrylate. Exemplary polyethers include polyethers obtained from ethoxylated or propoxylated trimethylolpropane, pentaerythritol, etc., or polyethers obtained by polyetherizing 1,4-propanediol, etc.

[0056] In a preferred embodiment, the composition comprises at least one (meth)acrylate monomer selected from the group consisting of: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; tert-butyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; cyclohexyl (meth)acrylate; n-heptyl (meth)acrylate; n-octyl (meth)acrylate. (T)Acrylate; 2-Ethylhexyl (meth)acrylate; Nonyl (meth)acrylate; Decyl (meth)acrylate; Dodecyl (meth)acrylate; Phenyl (meth)acrylate; Tolyl (meth)acrylate; Benzyl (meth)acrylate; 2-Methoxyethyl (meth)acrylate; 3-Methoxybutyl (meth)acrylate; 2-Hydroxyethyl (meth)acrylate; 2-Hydroxypropyl (meth)acrylate; Stearyl (meth)acrylate; Glycidyl (meth)acrylate; Isobornyl (meth)acrylate; 2 -aminoethyl (meth)acrylate; y-(meth)acryloyloxypropyltrimethoxysilane; (meth)acrylic acid-ethylene oxide adduct; trifluoromethylmethyl (meth)acrylate; 2-trifluoromethylethyl (meth)acrylate; 2-perfluoroethylethyl (meth)acrylate; 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate; 2-perfluoroethyl (meth)acrylate; perfluoromethyl (meth)acrylate; diperfluoromethylmethyl (meth)acrylate; 2-per Fluoromethyl-2-perfluoroethylmethyl (meth)acrylate; 2-perfluorohexylethyl (meth)acrylate; 2-perfluorodecylethyl (meth)acrylate; 2-perfluorohexadecylethyl (meth)acrylate; ethoxylated trimethylolpropane triacrylate; trimethylolpropane trimethacrylate; dipentaerythritol monohydroxypentaacrylate; pentaerythritol triacrylate; ethoxylated trimethylolpropane triacrylate; 1,6-hexanediol diacrylate;Neopentyl glycol diacrylate; pentaerythritol tetraacrylate; 1,2-butylene glycol diacrylate; trimethylolpropane ethoxylate tri(meth)acrylate; glyceryl propoxylate tri(meth)acrylate; trimethylolpropane tri(meth)acrylate; dipentaerythritol monohydroxypenta(meth)acrylate; tripropylene glycol di(meth)acrylate; neopentyl glycol propoxylate di(meth)acrylate; 1,4-butanediol di(meth)acrylate; triethylene glycol di(meth)acrylate; butylene glycol di(meth)acrylate; and ethoxylated bisphenol A di(meth)acrylate.

[0057] Good results have been obtained when the composition contains at least one (meth)acrylate monomer selected from the group consisting of C1-C6 hydroxyalkyl esters of (meth)acrylic acid.

[0058] 1.2 Copolymerizable acids As described above, the composition may optionally contain at least one copolymerizable acid. If used, the acid can be added in an amount of up to 40 mol%, for example, up to 20 mol%, of the total molar amount of the ethylenically unsaturated nonionic monomers present. For example, the at least one copolymerizable acid may constitute 0 to 15 mol% of the total molar amount of the ethylenically unsaturated nonionic monomers. For completeness, such monomers should usually be used in the form of free acids, but this does not preclude the partial or complete neutralization of the constituent acid groups of the monomers with a suitable base, provided that their participation in copolymerization is not impaired.

[0059] Without intending to limit the present invention, copolymerizable acid monomers should be selected from ethylenically unsaturated carboxylic acids; ethylenically unsaturated sulfonic acids; and vinylphosphonic acids. Suitable ethylenically unsaturated sulfonic acids include, for example, vinylsulfonic acid, styrenesulfonic acid, and acrylamidemethylpropanesulfonic acid.

[0060] Preferably, the at least one copolymerizable acid in the composition comprises or comprises an ethylenically unsaturated carboxylic acid selected from the group consisting of α,β-monoethylenically unsaturated monocarboxylic acid; α,β-monoethylenically unsaturated dicarboxylic acid; C1-C6 alkyl half-esters of α,β-monoethylenically unsaturated dicarboxylic acid; α,β-monoethylenically unsaturated tricarboxylic acid; C1-C6 alkyl esters of α,β-monoethylenically unsaturated tricarboxylic acid having at least one free carboxylic acid group; and mixtures thereof. In particular, the at least one copolymerizable acid in the composition comprises or comprises an ethylenically unsaturated carboxylic acid selected from the group consisting of methacrylic acid; acrylic acid, itaconic acid; maleic acid; aconitic acid; crotonic acid; fumaric acid; and mixtures thereof.

[0061] 1.3 Further monomers The present invention can copolymerize with (meth)acrylate monomers, including styrene monomers such as styrene, vinyltoluene, α-methylstyrene and chlorostyrene; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and fluorinated vinylidene; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and sil It should be noted that the presence of vinyl monomers selected from the group consisting of chlorohexylmaleimide, nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile, amide group-containing vinyl monomers such as acrylamide and methacrylamide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate, alkenes such as ethylene and propylene, conjugated dienes such as butadiene and isoprene, and vinyl monomers in compositions is not excluded.

[0062] 2. Non-polymerizable electrolyte The composition contains 0.1 to 30% by weight of a nonpolymerizable electrolyte, based on the weight of the composition. The nonpolymerizable electrolyte may preferably constitute 1 to 20% by weight of the composition, for example, 1 to 15% by weight.

[0063] The non-polymerizable electrolyte preferably comprises at least one salt having a formula selected from the group consisting of: [ka] (R in the formula 1 , R 2 , R 3 , R 4 , R 5 and R 6 Independently, hydrogen, C1-C 18 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 24 Aralkil, C2C 20 Alkenyl, -C(O)R q Selected from -C(O)OH, -CN, and -NO2; R q (These are C1-C6 alkyl groups.)

[0064] When an ammonium salt is used, it is the group R 1 ~R 4 The condition is that at most three, and preferably at most two, of these atoms are hydrogen.

[0065] For completeness, terminology C1-C 18 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 24 Aralkil, C2C 20 Alkenyls are composed of one or more hydrogen atoms that are connected to a halogen atom (e.g., C1-C 18 Haloalkyl) or hydroxyl group (e.g., C1-C) 18 It explicitly includes groups substituted with hydroxyalkyl groups. In particular, R 1 , R 2 , R3 , R 4 , R 5 and R 6 Preferably independently of hydrogen, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Hydroxyalkyl and C3-C 12 It is selected independently of cycloalkyl groups. For example, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 This can be independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 hydroxyalkyl.

[0066] There is no particular intention to limit the counter-anions (X-) that can be used in non-polymerizable electrolytes. Exemplary anions can be selected from the following: • Halides; · Formula PF6 - CF3SO3 - , (CF3SO3)2N - CF3CO2 - and CCl3CO2 - Pseudohalides and halogen-containing compounds; · CN - SCN - , and OCN - ; • Fenate; · General formula SO4 2- HSO4 - , SO3 2- HSO3 - , R a OSO3 - and R a SO3 - Sulfates, sulfites, and sulfonates; · General formula PO4 3- HPO4 2- H2PO4 - , R a PO4 2- , HR a PO4 - and Ra R b Phosphate of PO4; · General formula R a HPO3 - 、R a R b PO2 - and R a R b PO3 - phosphonates and phosphinates; · General formula PO3 3- 、HPO3 2- 、H2PO3 - 、R a PO3 2- 、R a HPO3 - and R a R b PO3 - phosphites; · General formula R a R b PO2 - 、R a HPO2 - 、R a R b PO - and R a HPO - phosphonites and phosphinites; · General formula R a COO - carboxylate anions; · Hydroxycarboxylate anions and saccharate anions; · Saccharinate (salt of o-benzoic acid sulfimide); · General formula BO3 3- 、HBO3 2- 、H2BO3 - 、R a R b BO3 - 、R a HBO3 - 、R a BO3 2- 、B(OR a )(OR b )(OR c )(OR d - 、B(HSO4) - and B(R​a SO4) - borate; · General formula R a BO2 2- and R a R b BO - boronate; · General formula HCO3 - CO3 2- and R a CO3 - Carbonates and carbonate esters of; · General formula SiO4 4- HSiO4 3- H2SiO4 2- H3SiO4 - , R a SiO4 3- , R a R b SiO4 2- , R a R b R c SiO4 - , HR a SiO4 2- H2R a SiO4 - and HR a R b SiO4 - silicates and silicates; · General formula R a SiO3 3- , R a R b SiO2 2- , R a R b R c SiO - , R a R b R c SiO3 - , R a R b R c SiO2 - and R a R b SiO3 2- Alkyl- and arylsilanolates; • Pyridinates and pyrimidinates; · General formula: [ka] Carboxylic acid imides, bis(sulfonyl)imides, and sulfonylimides; · General formula: [ka] Methido; · General formula R a O - Alkoxides and aryl oxides of; and · General formula S 2- HS - [S v ] 2- [HS v ] - and [R a S] - Sulfides, hydrogen sulfide, polysulfides, hydrogen polysulfides and thiolates (In the general formula, v is a positive integer between 2 and 10, R a , R b , R c and R d Independently, hydrogen, C1-C 12 Alkyl, C5-C 12 Cycloalkyl, C5-C 12 Heterocycloalkyl, C6-C 18 Aryl and C5-C 18 (Selected independently of heteroaryls).

[0067] Based on the definitions in the list above, preferred anions are selected from the group consisting of halides, pseudohalides and halogen-containing compounds as defined above; carboxylic acid anions, especially formates, acetates, propionates, butyrates and octanoates; hydroxycarboxylic acid anions, such as lactates; pyridinates and pyrimidinates; carboxylic acid imides, bis(sulfonyl)imides and sulfonylimides; sulfates, especially methyl sulfate and ethyl sulfate; sulfites; sulfonates, especially methanesulfonates; and phosphates, especially dimethyl phosphate, diethyl phosphate and di-(2-ethylhexyl)-phosphate.

[0068] The nonpolymerizable electrolyte of the composition is preferably selected from the following group: 1-ethyl-3-methyl-1H-imidazole-3-ium methanesulfonate, 1-ethyl-3-methyl-1H-imidazole-3-ium methyl sulfate, 1-hexyl-3-methylimidazolium 2-(2-fluoroanilino)-pyridinate, 1-hexyl-3-methylimidazolium imide, 1-butyl-1-methylpyrrolidinium 2-(2-fluoroanilino)-pyridinate, 1-butyl-1-methylpyrrolidinium imide, trihexyl(T Tradecyl)phosphorium 2-(2-fluoroanilino)-pyridinate, cyclohexyltrimethylammonium bis(trifluoromethylsulfonyl)imide, di(2-hydroxyethyl)ammonium trifluoroacetate, N,N-dimethyl(2-hydroxyethyl)ammonium octanoate, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, N-ethyl-NNNN-tetramethylguanidinium trifluoromethanesulfonate, guanidinium trifluoromethanesulfonate, 1-butyl- 4-methylpyridinium bromide, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-hydroxymethylpyridinium ethyl sulfate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-ethyl-methylimidazolium bromide, 1-butyl-3-methyl Midazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-propyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanesulfate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium trifluoromethanesulfate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butylimidazole, 1-methylimidazolium tetrafluoroborate, tetrabutylphosphonium tris(pentafluoroethyl)trifluorophosphate, trihexyl(tetradecyl)phosphonium tetrafluoroborate, and mixtures thereof. A preference for the use of at least one of 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methyl-1H-imidazole-3-ium methanesulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfate, and 1-ethyl-3-methyl-1H-imidazole-3-ium methyl sulfate can be mentioned.

[0069] 3. Thermal initiator The composition of the present invention comprises at least one radical-generating thermal initiator. As will be understood by those skilled in the art, a thermal initiator is a compound that can be activated by thermal energy to generate radicals when heated or irradiated, for example, in the infrared or microwave wavelength range. The composition should typically contain 0.1 to 10% by weight, for example, 0.1 to 5% by weight or 0.1 to 2.5% by weight of the at least one radical-generating thermal initiator, based on the total weight of the composition.

[0070] Without intending to limit the present invention, exemplary classifications of radical-generating thermal initiators suitable for use herein include, for example, organic peroxides selected from cyclic peroxides; diacyl peroxides; dialkyl peroxides; hydroperoxides; peroxy carbonates; peroxy dicarbonates; peroxy esters; and peroxy ketals.

[0071] Certain peroxides, such as dialkyl peroxides, are disclosed as useful initiators, particularly in U.S. Patent No. 3,419,512 (Lees) and U.S. Patent No. 3,479,246 (Stapleton), and may indeed be useful herein, but hydroperoxides represent the preferred classification of initiators of the present invention. Furthermore, hydrogen peroxide itself can also be used, but the most desirable 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 organic peroxides and organic peresters are cyclohexyl and hydroxycyclohexyl peroxides and t-butyl perbenzoate, respectively.

[0072] In one embodiment of the present invention, the radical-generating thermal initiator is of formula: R p OOH (In the formula, R p is an aliphatic or aromatic group containing up to 18 carbon atoms, preferably R p C1-C 12 Alkyl alkyl group, C6-C 18 Aryl group or C7-C 18 (It is an aralkyl group.) It comprises or consists of at least one hydroperoxide compound represented by .

[0073] Exemplary 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; benzoyl peroxide; dibenzoyl peroxide Oxides; 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-butylperoxyhex-3-yne; and 4-methyl-2,2-di-t-butylperoxypentane can be mentioned.

[0074] Without intending to limit the present invention, further exemplary classifications of radical-generating thermal initiators suitable for use herein include, for example, azopolymerization initiators selected from azonitriles; azoesters; azoamides; azoamidines; azoimidazolines; and macroazo initiators.

[0075] Representative 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-carbonnitrile); 4,4'-azobis(4-cyanovaleric acid); dimethyl2,2'-azobis(2-methylpropionate); 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]; 2,2'-azobis(N-butyl-2-methylpropionamide); 2,2'-azobis[2-(2-Imi The following can be mentioned: dazolin-2-yl)propane dihydrochloride; 2,2'-azobis[2-(2-imidazolin-2-yl)propane]; 2,2'-azobis(2-melpropionamidine) dihydrochloride; 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate; polymers with 4,4-azobis(4-cyanovaleric acid) and α,ω-bis(3-aminopropyl) polydimethylsiloxane (VPS-1001, available from Fujifilm Wako Pure Chemical Industries, Ltd.); and 4,4'-azobis(4-cyanopentanoic acid) polyethylene glycol polymer (VPE-0201, available from Fujifilm Wako Pure Chemical Industries, Ltd.).

[0076] 4. Curing accelerator This composition may contain at least one curing accelerator in an amount of 0 to 5% by weight, preferably 0.1 to 2.5% by weight of the composition. Non-limiting examples of useful curing accelerators that may be present in the composition alone or in combination include: (i) General formula: [ka] (In the formula, R1 ’ This is an optionally substituted aryl group, in particular an optionally alkyl-substituted phenyl group, R2' is a linear or branched alkyl group that has the same meaning as R1', or may be substituted. R3' is a linear or branched alkyl group which may be substituted and contains at least one hydrogen atom at the α-position relative to nitrogen. Any two of R1' to R3' may together form a monocyclic or polycyclic ring structure, which may also be a fused ring structure, and can be substituted for each other in turn. arylamines; (ii) General formula: [ka] (In the formula, R4' is a phenyl compound substituted with a C1-C4 alkyl group, R5' is hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl, amino and the following groups: [ka] (R7 in the formula ’ (The alkyl group is selected from alkyl groups containing 1 to 10 carbon atoms.) Compounds containing; (iii) Sulfonylhydrazine; or (iv) Hydropyridine These are some examples.

[0077] Further specific non-limiting examples of curing accelerators include saccharin; toluidines, such as N,N-diethyl-p-toluidine (DE-pT) and N,N-dimethyl-o-toluidine (DM-oT); acetylphenylhydrazine (APH); and maleic acid. Further exemplary curing accelerators include sulfimides, such as those described in U.S. Patent No. 6,958,368 (Klemarczyk), and their oxygen and sulfur derivatives; phenylglycine and its derivatives; 1,4-aminobenzoyl compounds; phenylpyrazolinone, sulfonimide derivatives, and sulfonamide derivatives disclosed in U.S. Patent No. 7,411,025 (Messana); trithiadiazapentalene, as described in U.S. Patent No. 6,583,289 (McCardle); reaction products (SPH) of succinic anhydride and phenylhydrazine, which can be prepared according to U.S. Patent No. 6,835,782 (Morita); and compounds disclosed in U.S. Patent No. 6,835,762 (Klemarczyk) that contain a -C(=O)-NH-NH- bond together with an organic acid functional group on the same molecule.

[0078] 5. Solubilizer The composition of the present invention may optionally contain a solubilizer. For example, the composition may contain 0 to 10% by weight or 0 to 5% by weight of the solubilizer, based on the weight of the composition. The solubilizer has the function of promoting the miscibility of electrolyte ii) in the adhesive composition. That is, the solubilizer promotes ion movement within the polymer matrix, although it is unclear whether it forms part of the polymer matrix formed when the adhesive composition is cured. For this reason, the solubilizer is preferably a polar compound and preferably a liquid at room temperature.

[0079] Suitable solubilizers include polyphosphazenes; polymethylene sulfides; polyoxyalkylene glycols; polyethyleneimines; silicone surfactants, including but not limited to polyalkylsiloxanes and poly(C2-C3)oxyalkylene-modified polydimethylsiloxanes; polyoxyalkylene-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 polysilanes, are intended to be included within the term silicone surfactants.

[0080] 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 bonded to the remaining benzene carbon atom, isosorbide, isomannide, isoidide, glycerol, cyclohexane-1,2,4-triol, 1,3,5-cyclohexanetriol, pentane-1,2,3-triol, hexa n-1,3,5-triol, erythritol, 1,2,4,5-tetrahydroxybenzene, treitol, 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, etc.

[0081] It should be noted that among polyoxyalkylene glycols, the use of polyoxy(C2-C3)alkylene glycols having an average molecular weight (Mw) of 200 to 10,000 g / mol, for example, 200 to 2,000 g / mol, is particularly preferred. For completeness, the term polyoxy(C2-C3)alkylene refers to polyether radicals derived from ethylene oxide, propylene oxide, or both ethylene oxide and propylene oxide.

[0082] Additives and auxiliary components The compositions obtained in the present invention typically further include auxiliary agents and additives that can impart improved properties to these compositions. For example, auxiliary agents and additives can impart one or more of the following: improved elastic properties, improved elastic recovery, longer processing time, faster curing time, and lower residual tack. Such auxiliary agents and additives include: reinforcing agents; conductive particles; non-conductive fillers; plasticizers; abrasion-imparting additives such as thermoplastic polyurethanes; stabilizers such as UV stabilizers; antioxidants; reactive diluents; drying agents; adhesion promoters; bactericides; flame retardants; rheological auxiliary agents; coloring pigments or coloring pastes; and / or optionally, slightly non-reactive diluents.

[0083] These auxiliaries and additives can be used in any desired combination and proportion, provided that they do not adversely affect the properties and essential characteristics of the composition. While exceptions may exist, these auxiliaries and additives as a whole should not constitute more than 30% by weight of the total composition, preferably more than 20% by weight.

[0084] The presence of a reinforcing agent in this composition may be advantageous for peeling cured adhesives. While not intended to be theoretically bound, reinforcing agents promote phase separation within cured adhesives under applied potential. In particular, good peeling results have been obtained when the composition of the present invention contains at least one reinforcing agent selected from elastomer adducts and reinforcing rubbers in the form of core-shell particles dispersed in a matrix polymer at a concentration of 0 to 20% by weight, for example, 0.5 to 20% by weight or 0.5 to 15% by weight, based on the weight of the composition.

[0085] The term "core-shell rubber" or CSR is used in accordance with the standard meaning in the art to refer to a rubber particle core formed of a polymer primarily composed of an elastic or rubbery polymer, and a shell layer formed of a polymer graft-polymerized onto the core. The shell layer partially or completely covers 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 particles.

[0086] The core polymer material has a glass transition temperature (T) of 0°C or lower. g ), preferably -20°C or lower, more preferably -40°C or lower, and even more preferably -60°C or lower glass transition temperature (T g The polymer of the shell must have the following properties: The polymer of the shell is an inelastic, thermoplastic or thermosetting polymer having a glass transition temperature (Tg) above room temperature, preferably above 30°C, and more preferably above 50°C.

[0087] Without intending to limit the present invention, the core may consist of a diene homopolymer, such as a homopolymer of butadiene or isoprene; a diene copolymer, such as a copolymer of butadiene or isoprene with one or more ethylenically unsaturated monomers, such as vinyl aromatic monomers, (meth)acrylonitrile or (meth)acrylate; a polymer based on (meth)acrylic acid ester monomers, such as polybutyl acrylate; and a polysiloxane elastomer, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0088] Similarly, and without intending to limit the present invention, the shell may consist of a polymer or copolymer of one or more monomers selected from (meth)acrylates, e.g., methyl methacrylate; vinyl aromatic monomers, e.g., styrene; vinyl cyanides, e.g., acrylonitrile; unsaturated acids and anhydrides, e.g., acrylic acid; and (meth)acrylamide. The polymer or copolymer used for the shell may have acidic groups that are ionically crosslinked through metal carboxylate formation, particularly through salt formation of divalent metal cations. The shell polymer or copolymer may be covalently crosslinked by monomers having two or more double bonds per molecule.

[0089] Preferably, all included core-shell rubber particles have an average particle size (d50) of 10 nm to 300 nm, for example, 50 nm to 250 nm. That is, particle size refers to the diameter or maximum dimension of the particles in the particle distribution and is measured by dynamic light scattering. For completeness, this application does not exclude the presence of two or more core-shell rubber (CRS) particles having different particle size distributions in the composition in order to provide a balance of important properties of the resulting cured product, such as shear strength, peel strength, and resin fracture toughness.

[0090] Core-shell rubber can be selected from commercially available products, including Paraloid EXL2650A, EXL2655, and EXL2691A from Dow Chemical; Clearstrength® XT100 from Arkema; ​​Kane Ace® MX series from Kaneka, particularly MX120, MX125, MX130, MX136, MX551, and MX553; and METABLEN SX-006 from Mitsubishi Rayon.

[0091] As described above, the composition of the present invention comprises 0 to 20% by weight, for example, 0.5 to 10% by weight, of filler. The filler can be used independently of or in combination with the reinforcing agent. The use of conductive fillers and / or non-conductive fillers is envisioned, but in one embodiment, the filler included in the composition comprises or essentially consists of non-conductive particulate fillers.

[0092] Accordingly, as described above, the composition of the present invention may contain conductive particulate fillers. The composition may contain, for example, 0 to 10% by weight or 0.5 to 5% by weight of conductive particles, based on the weight of the composition.

[0093] In general, there is no particular intention to limit the shape of the particles used as conductive fillers; needle-shaped, spherical, ellipsoidal, cylindrical, bead-shaped, cubic, or platelet-shaped particles can be used alone or in combination. Furthermore, the use of aggregates of multiple particle types is also envisioned. Similarly, there is no particular intention to limit the size of the particles used as conductive fillers. However, these conductive fillers typically have an average volume particle size of 0.1 to 1500 μm, for example, 1 to 1250 μm, as measured by conventional laser diffraction / scattering methods.

[0094] Exemplary conductive particulate fillers include, but are not limited to, silver; copper; gold; palladium; platinum; nickel; gold or silver-coated nickel; carbon black; carbon fiber; 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; antimond-doped tin oxide; conductive nanospheres; nanosilver; nanoaluminum; nanocopper; nanonickel; carbon nanotubes; and mixtures thereof. The use of particulate silver and / or carbon black as conductive fillers is preferred.

[0095] The composition of the present invention may further contain non-conductive particulate fillers. The composition may contain, for example, 0 to 10% by weight or 0.5 to 10% by weight of non-conductive particles based on the weight of the composition.

[0096] In general, there is no particular intention to limit the shape of the particles used as non-conductive fillers, and needle-shaped, spherical, ellipsoidal, cylindrical, bead-shaped, cubic, or platelet-shaped particles can be used alone or in combination. Furthermore, it is conceivable that aggregates of multiple particle types may be used. Similarly, there is no particular intention to limit the size of the particles used as non-conductive fillers. However, these non-conductive fillers typically have an average volume particle size of 0.1 to 1500 μm, for example, 1 to 1250 μm, as measured by conventional laser diffraction / scattering methods.

[0097] Examples of nonconductive fillers include, but are not limited to, calcium carbonate, calcium oxide, calcium hydroxide (lime powder), fumed silica, amorphous silica, precipitated and / or exothermic silicic acid, zeolite, bentonite, wollastonite, magnesium carbonate, diatomaceous rock, barium sulfate, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass beads, glass powder, and other pulverized mineral materials. Organic fillers may also be used, particularly wood fibers, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, shredded straw, rice husks, crushed walnut shells, and other shredded fibers. Short fibers, such as glass fibers, glass filaments, polyacrylonitrile, and short fibers, such as carbon fibers, Kevlar® fibers, or polyethylene fibers, may also be added.

[0098] Exothermic and / or precipitated silica is advantageously 10-90 m 2 They have a BET specific surface area of ​​ / g. When used, they contribute to strengthening the cured composition rather than causing a further increase in the viscosity of the composition of the present invention.

[0099] Similarly, a larger betting surface area as filler, advantageously 100-250m² 2It is also conceivable to use exothermic and / or precipitated silica with a weight of / g. In other words, for a larger BET surface area, the strengthening effect of the cured composition is achieved with a smaller weight ratio of silica.

[0100] Hollow spheres having a mineral or plastic shell are also suitable as non-conductive fillers. These are, for example, hollow glass spheres commercially available under the trade name Glass Bubbles®. Plastic-based hollow spheres, such as ExpanseL® or Dualite®, may also be used, as described in European Patent No. 0520426. They are composed of inorganic or organic material and each has a diameter of 1 mm or less, preferably 500 μm or less.

[0101] Non-conductive fillers that impart thixotropy to a composition may be preferred for many applications. Such fillers are also described as rheological additives, such as hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.

[0102] The desired viscosity of the curable composition to be formed may be determined by the amount of filler used. Considering the latter consideration, the total amount of filler (both conductive and nonconductive) present in the composition should not prevent the composition from being easily applied to a substrate by a chosen application method. For example, a curable composition intended to be extruded from a suitable dispensing device such as a tube must have a viscosity of 1,000 to 150,000 mPas, preferably 10,000 to 100,000 mPas.

[0103] For the purposes of the present invention, the “plasticizer” is a substance that reduces the viscosity of a composition and thus facilitates its processability. In this specification, the plasticizer may constitute up to 10% by weight or up to 5% by weight based on the total weight of the composition, and is preferably a diurethane; monofunctional, linear or branched C4-C 16The following are selected from the group consisting of alcohol ethers, such as Cetiol OE (obtained from Cognis Deutschland GmbH, Duesseldorf); 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 fatty acids having an OH group 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 glycols; polystyrenes; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. In principle, phthalate esters can be used as plasticizers, but it should be noted that these are undesirable due to their toxicological potential.

[0104] For the purposes of the present invention, “stabilizer” is understood to mean an antioxidant, a heat stabilizer, or a hydrolysis stabilizer. In this specification, the stabilizer may constitute up to 10% by weight or up to 5% by weight overall, based on the total weight of the composition. Typical commercially available examples of stabilizers suitable for use herein include sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; hindered amine light stabilizer (HALS) type amines; phosphorus; sulfur; and mixtures thereof.

[0105] It should be noted that using compounds having metal chelating properties in the composition of the present invention can promote improved adhesion of the cured adhesive to the substrate surface. Furthermore, acetacetate functionalized modified resin, sold by King Industries under the trade name K-FLEX XM-B301, is also suitable for use as an adhesion promoter.

[0106] To further extend the shelf life, it is often desirable to stabilize the composition of the present invention against moisture penetration using a desiccant. Occasionally, it is also necessary to reduce the viscosity of the adhesive composition of the present invention for specific applications by using a reactive diluent. The total amount of reactive diluent present is typically 0 to 10% by weight, for example, 0 to 5% by weight, based on the total weight of the composition.

[0107] The presence of solvents and non-reactive diluents in the compositions of the present invention is not excluded if their viscosity can be usefully adjusted. For example, for illustrative purposes only, a composition 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-butyl ether; propylene glycol Dipropyl 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; diisopropylnaphthalene; petroleum fractions, e.g., Solvesso® products (available from Exxon Inc.); alkylphenols, e.g., tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecatrienylenylphenol; styrene phenols; bisphenols; aromatic hydrocarbon resins, especially phenol group-containing resins such as ethoxylated or propoxylated phenols; adipates; sebacates; phthalates; benzoates; organophosphate esters or organosulfonic acid esters; and sulfonamides.

[0108] Setting aside the above, it is preferable that the non-reactive diluent constitutes less than 10% by weight overall, and more particularly less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0109] Method and application The components are mixed together to form a defined curable composition. It is important that the mixing uniformly distributes the electrolyte, i.e., the nonpolymerizable compound (2 above), within the adhesive composition. Such thorough and effective mixing can determine the uniform distribution of charged species within the polymer matrix obtained after curing, thereby providing sufficient ionic conductivity to support electrochemical reactions at the interface with the conductive substrate.

[0110] As is known in the art, to form a one-component (1K) curable composition, the elements of the composition are mixed together uniformly under conditions that suppress or prevent the reaction of the reactive components. These conditions will be readily understood by those skilled in the art. Therefore, it is often preferable to mix the curable elements in predetermined amounts under anhydrous conditions without intentional light irradiation, using a machine such as a static or dynamic mixer, rather than mixing them manually.

[0111] According to the most broad process embodiment of the present invention, the composition described above is applied to a material layer and then cured in situ. It is often desirable to pre-treat the relevant surface before applying the composition to remove any foreign matter. Where applicable, this step facilitates the subsequent adhesion of the composition to the relevant surface. Such treatments are known in the art and can be carried out in a single-stage or multi-stage method consisting of the use of one or more of the following: etching with an acid and optionally an oxidizing agent suitable for the substrate; ultrasonic treatment; plasma treatment such as 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 acetone, carbon tetrachloride or trichloroethylene; and preferably rinsing with deionized or demineralized water. When using an aqueous alkaline degreasing bath, if any degreasing agent remains on the surface, it should preferably be removed by rinsing the substrate surface with deionized or demineralized water.

[0112] In some embodiments, adhesion of the coating composition of the present invention to a preferably pre-treated substrate may be facilitated by applying a primer to the substrate. Indeed, a primer composition may be necessary to ensure effective fixation and / or curing time of the adhesive composition on an inert substrate. A person skilled in the art will be able to select a suitable primer, but useful references regarding primer selection include, but are not limited to, U.S. Patent Nos. 3,855,040, 4,731,146, 4,990,281, 5,811,473, UK Patent Application Publication No. 2502554, and U.S. Patent No. 6,852,193.

[0113] The composition is then applied to a preferably pre-treated and optionally undercoated substrate surface by conventional application methods, such as brush application, roll coating, doctor blade application, printing, and spraying methods, including but not limited to air atomization spraying, air-assisted spraying, aerosol spraying, and high-volume low-pressure spraying.

[0114] As described above, the present invention provides an adhesive structure comprising a first material layer having a conductive surface; and a second material layer having a conductive surface, wherein the cured electrochemically peelable adhesive composition, as defined in the foregoing and appended claims of this specification, is positioned between the first and second material layers. To produce such a structure, the adhesive composition is applied to at least one inner surface of the first material layer and / or the second material layer such that the electrochemically peelable adhesive composition is interposed between the two layers, and the two layers can then be brought into contact, optionally under pressure.

[0115] The composition is recommended to be applied to surfaces with a wet film thickness of 10 to 500 μm. Applying thinner layers within this range is more economical and reduces the possibility of harmful thick cured areas. However, significant control is required when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0116] Given that the composition contains a thermal initiator, curing must be achieved by raising the temperature of the composition to a temperature above the activation temperature of the initiator. The activation temperature, of course, depends on the specific compound present, but the temperature required to ensure the desired curing rate can be determined on a case-by-case basis by those skilled in the art, using simple preliminary tests as needed. Without intending to limit the present invention, complete curing of the applied curable composition must typically occur at temperatures in the range of 20°C to 150°C, preferably 20°C to 120°C, and particularly 45°C to 100°C. Where applicable, the temperature of the curable composition can be raised to a temperature above the mixing temperature and / or application temperature using conventional means such as microwave induction.

[0117] The present invention will be described with reference to the accompanying drawings. Figure 1a illustrates the adhesive structure of the first embodiment of the present invention. Figure 1b illustrates an adhesive structure according to a second embodiment of the present invention. Figure 2a illustrates the initial delamination of the structure when an electric current is passed through the structure of the first embodiment. Figure 2b illustrates the initial delamination of the structure when an electric current is passed through the structure of the second embodiment.

[0118] As depicted in the attached Figure 1a, a bonded structure is provided in which a layer of cured adhesive (10) is placed between two conductive substrates (11). As depicted in Figure 1b, a more complex bonded structure can be formed by placing a layer of non-conductive material (12) on the conductive substrates (11). Each layer of the conductive substrates (11) is electrically in contact with a power source (13), which may be a battery or a direct current (DC) or alternating current (AD) power source. The positive and negative terminals of the power source (13) are shown in one fixed position, but those skilled in the art will naturally recognize that the polarity of the system can be reversed.

[0119] The two conductive substrates (11) are shown in particular in the form of layers which may consist of a metal film, a metal mesh or grid, vapor-deposited metal particles, a resin material made conductive by conductive elements placed inside, or a conductive oxide layer. Exemplary conductive elements include silver filaments, single-walled carbon nanotubes, and multi-walled carbon nanotubes. Exemplary conductive oxides include doped indium oxide such as indium tin oxide (ITO); doped zinc oxide; antimony tin oxide; cadmium stannate; and zinc stannate. Regardless of the choice of conductive material, those skilled in the art will recognize that if the conductive substrate (11) is in a grid or mesh form, contact with the layer of cured adhesive (10) may be limited, the effectiveness of the peeling operation may be reduced.

[0120] When a voltage is applied between each conductive substrate (11), an electric current is supplied to the adhesive composition (10) placed between them. This induces an electrochemical reaction at the interface between the substrate (11) and the adhesive composition, which is understood to be oxidative at the positively charged or anode interface and reductive at the negatively charged or anode interface. This reaction is thought to weaken the adhesive bond between the substrates, making it possible to easily remove the composition that can be peeled off the substrates.

[0121] As depicted in Figures 2a and 2b, delamination occurs at the positive interface, which is the interface between the adhesive composition (10) electrically in contact with the positive electrode and the conductive surface (11). By reversing the direction of the current before separating the substrates, the adhesive bond can be weakened at both substrate interfaces.

[0122] However, it should be noted that the composition of the adhesive layer (10) can be adjusted so that delamination occurs simultaneously from either the positive interface, the negative interface, or both. In some embodiments, applying a voltage to both surfaces to form an anode interface and a cathode interface causes simultaneous delamination at the anode and cathode adhesive / substrate interfaces. In alternative embodiments, if the composition does not respond to DC at both interfaces, both substrate / adhesive interfaces can be delaminated simultaneously using reverse polarity. The current can be applied in any suitable waveform, provided that a sufficient total time is allowed for delamination at each polarity. Sine, square, and triangular waveforms may be suitable in this regard and can be applied from a control voltage or control current source.

[0123] Without intending to limit the present invention, it is believed that the peeling operation can be effectively carried out when at least one, preferably both, of the following conditions are met. a) an applied voltage of 0.5 to 200V, for example, 10 to 100V; and b) a voltage applied for a period of 1 second to 120 minutes, for example, 1 second to 60 minutes. If the peeling of the conductive substrate from the cured adhesive can be accelerated by applying force, for example, through a weight or spring, the potential may only need to be applied for a few seconds.

[0124] The following examples illustrate the present invention and are not intended to limit the scope of the invention in any way. [Examples]

[0125] The following materials were used in the examples.

[0126] TIFF0007881597000007.tif100170

[0127] Examples 1-3 The compositions were prepared according to Table 1 below. The specified components were mixed in a speed mixer (1200 rpm; 1 minute) to ensure that a homogeneous mixture was formed.

[0128] [Table 1]

[0129] The test substrate was aluminum (AA6016) whose surface had been wiped clean with ethyl acetate. The substrate was prepared to a thickness of 0.1 inches and cut into six 2.5 cm × 10 cm (1 inch × 4 inch) samples for tensile testing. Tensile lap shear (TLS) tests were performed at room temperature according to ASTM D3163-01, "Standard test method for determining the shear strength of lap shear joints of adhesively bonded rigid plastics under tensile load." The overlapping area of ​​the adhesive bond for each substrate was 2.5 cm × 1.0 cm (1 inch × 0.4 inches) with an adhesive thickness of 0.15 cm (60 mil).

[0130] The applied adhesive composition cured in the overlapping areas by applying a temperature of 100°C for 30 minutes. The bonded structure was stored at 25°C and 20% relative humidity for 24 hours prior to the initial tensile test.

[0131] For each adhesive substrate, the tensile lap shear strength was measured before and after applying a constant potential of 30V to the adhesive layer for 20 minutes, following the 24-hour storage period. The average results are shown in Table 2 below.

[0132] [Table 2]

[0133] In light of the above description and examples, it will be apparent to those skilled in the art that equivalent modifications can be made without departing from the claims. Preferred embodiments of the present invention include the following: [1] Based on the weight of the composition, i) at least one ethylenically unsaturated nonionic monomer in 40-90% by weight; ii) Nonpolymerizable electrolytes in an amount of 0.1 to 30% by weight; iii) at least one radical-generating thermal initiator in an amount of 0.1 to 10% by weight; iv) filler of 0-20% by weight; and 0-20% by weight of v) Reinforcement A curable and electrochemically peelable one-component (1K) adhesive composition containing [the specified ingredient]. [2] The composition is, based on the weight of the composition, i) at least one ethylenically unsaturated nonionic monomer in an amount of 60-90% by weight, preferably 70-90% by weight; ii) the nonpolymerizable electrolyte in an amount of 1-20% by weight; iii) at least one radical-generating thermal initiator in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight; iv) the filler in an amount of 0-20% by weight, preferably 0.5-20% by weight; and v) the reinforcing agent in an amount of 0-20% by weight, preferably 0.5-20% by weight A curable and electrochemically peelable one-component (1K) adhesive composition according to [1], comprising: [3] The curable and electrochemically peelable one-component (1K) adhesive composition according to claim 1 or 2, wherein the (meth)acrylate monomer constitutes at least 60 mol%, preferably at least 75 mol%, of the total molar amount of the ethylenically unsaturated nonionic monomers. [4] The (meth)acrylate monomer is C of (meth)acrylic acid. 1 -C 6 A curable and electrochemically peelable one-component (1K) adhesive composition containing a hydroxyalkyl ester, as described in any one of [1] to [3]. [5] The curable and electrochemically peelable one-component (1K) adhesive composition according to any one of [1] to [4], wherein the (meth)acrylate monomer comprises one or more oligomers selected from the group consisting of urethane (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. [6] The curable and electrochemically peelable one-component (1K) adhesive composition according to [5], comprising at least one urethane (meth)acrylate oligomer. [7] The nonpolymerizable electrolytes are 1-ethyl-3-methyl-1H-imidazole-3-ium methanesulfate, 1-ethyl-3-methyl-1H-imidazole-3-ium methyl sulfate, 1-hexyl-3-methylimidazolium 2-(2-fluoroanilino)-pyridinate, 1-hexyl-3-methylimidazolium imide, 1-butyl-1-methylpyrrolidinium 2-(2-fluoroanilino)-pyridinate, 1-butyl-1-methylpyrrolidinium imide, and trihexyl(tetradecyl)phospholium 2-(2-fluoroanilino)-pyridinate, cyclohexyltrimethylammonium bis(trifluoromethylsulfonyl)imide, di(2-hydroxyethyl)ammonium trifluoroacetate, N,N-dimethyl(2-hydroxyethyl)ammonium octanoate, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, N-ethyl-NNNN-tetramethylguanidinium trifluoromethanesulfonate, guanidinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium bromide, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-hydroxymethylpyridinium ethyl sulfate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-methylpyrrolidinium tris(pentafluoro Ethyl) trifluorophosphate, 3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-ethylmethylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-propyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of [1] to [6], selected from the group consisting of 3-dimethylimidazolium hexafluorophosphate, 1-butylimidazole, 1-methylimidazolium tetrafluoroborate, tetrabutylphosphonium tris(pentafluoroethyl)trifluorophosphate, trihexyl(tetradecyl)phosphonium tetrafluoroborate, and mixtures thereof. [8] The electrolyte is selected from the group consisting of 1-ethyl-3-methyl-1H-imidazole-3-ium methanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methyl-1H-imidazole-3-ium methyl sulfate and mixtures thereof, as described in [7], a curable and electrochemically peelable one-component (1K) adhesive composition. [9] The at least one radical-generating thermal initiator is 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; benzoyl peroxide; dibenzoyl peroxide; 1,3-bis(t-butylperoxyisopropyl)benzyl A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of [1] to [8], selected from the group consisting of n; 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-butylperoxyhex-3-yne; and 4-methyl-2,2-di-t-butylperoxypentane.

[10] A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of [1] to [9], further comprising up to 5% by weight of at least one curing accelerator based on the weight of the composition.

[11] A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of [1] to

[10] , further comprising 0.5 to 10% by weight of non-conductive fine particle fillers based on the weight of the composition.

[12] A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of [1] to

[11] , comprising 0.5 to 15% by weight of v) the reinforcing agent.

[13] A first material layer having a conductive surface; A second material layer having a conductive surface; An adhesive structure including, An adhesive structure in which a cured electrochemically peelable one-component (1K) adhesive composition, as defined in any one of (1) to (12), is placed between the first material layer and the second material layer.

[14] 1) A step of applying a voltage to both surfaces to form an anode interface and a cathode interface, and 2) Step of peeling off the surface A method for peeling off the bonded structure described in

[13] , including, The method wherein the voltage applied in step 1 is preferably 0.5 to 200V and is applied for preferably 1 second to 60 minutes.

Claims

1. Based on the weight of the composition, i) at least one ethylenically unsaturated nonionic monomer in 40-90% by weight; 1-30% by weight of ii) non-polymerizable electrolyte; 0.1 to 10% by weight of iii) at least one radical-generating thermal initiator; 0-20% by weight of iv) filler; and 0-20% by weight of v) Reinforcement Includes, The (meth)acrylate monomer constitutes at least 60 mol% of the total molar amount of the ethylenically unsaturated nonionic monomer, wherein the (meth)acrylate monomer includes a C1-C6 hydroxyalkyl ester of (meth)acrylic acid. A curable and electrochemically peelable one-component (1K) adhesive composition.

2. The composition is determined based on the weight of the composition, i) at least one ethylenically unsaturated nonionic monomer in an amount of 60-90% by weight; ii) the nonpolymerizable electrolyte in an amount of 1 to 20% by weight; 0.1 to 10% by weight of the iii) at least one radical-generating thermal initiator; 0 to 20% by weight of the filler (iv); and v) The reinforcing agent, 0 to 20% by weight A curable and electrochemically peelable one-component (1K) adhesive composition according to claim 1, comprising the above.

3. The curable and electrochemically peelable one-component (1K) adhesive composition according to claim 1 or 2, wherein the (meth)acrylate monomer constitutes at least 75 mol% of the total molar amount of ethylenically unsaturated nonionic monomers.

4. The composition is, based on the weight of the composition, i) at least one ethylenically unsaturated nonionic monomer in an amount of 70-90% by weight; ii) the nonpolymerizable electrolyte in an amount of 1 to 20% by weight; 0.1 to 5% by weight of the iii) at least one radical-generating thermal initiator; 0.5 to 20% by weight of the filler (iv); and 0.5 to 20% by weight of the reinforcing agent A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of claims 1 to 3, comprising:

5. The curable and electrochemically peelable one-component (1K) adhesive composition according to any one of claims 1 to 4, wherein the (meth)acrylate monomer comprises one or more oligomers selected from the group consisting of urethane (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

6. A curable and electrochemically peelable one-component (1K) adhesive composition according to claim 5, comprising at least one urethane (meth)acrylate oligomer.

7. The non-polymerizable electrolytes are 1-ethyl-3-methyl-1H-imidazole-3-ium methanesulfate, 1-ethyl-3-methyl-1H-imidazole-3-ium methyl sulfate, 1-hexyl-3-methylimidazolium 2-(2-fluoroanilino)-pyridinate, 1-hexyl-3-methylimidazolium imide, 1-butyl-1-methylpyrrolidinium 2-(2-fluoroanilino)-pyridinate, 1-butyl-1-methylpyrrolidinium imide, and trihexyl(tetradecyl)phospholium. 2-(2-fluoroanilino)-pyridinate, cyclohexyltrimethylammonium bis(trifluoromethylsulfonyl)imide, di(2-hydroxyethyl)ammonium trifluoroacetate, N,N-dimethyl(2-hydroxyethyl)ammonium octanoate, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, N-ethyl-N-N-N-N-tetramethylguanidinium trifluoromethanesulfonate, guanidinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium bromide, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-hydroxymethylpyridinium ethyl sulfate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-methylpyrrolidinium tris(pentafluoro) Roethyl) trifluorophosphate, 3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-ethylmethylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-propyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of claims 1 to 6, selected from the group consisting of 3-dimethylimidazolium hexafluorophosphate, 1-butylimidazole, 1-methylimidazolium tetrafluoroborate, tetrabutylphosphonium tris(pentafluoroethyl)trifluorophosphate, trihexyl(tetradecyl)phosphonium tetrafluoroborate, and mixtures thereof.

8. The electrolyte is selected from the group consisting of 1-ethyl-3-methyl-1H-imidazole-3-ium methanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methyl-1H-imidazole-3-ium methyl sulfate and mixtures thereof, as described in claim 7, for a curable and electrochemically peelable one-component (1K) adhesive composition.

9. The at least one radical-generating thermal initiator is 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; benzoyl peroxide; dibenzoyl peroxide; 1,3-bis(t-butylperoxyisopropyl)benzyl A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of claims 1 to 8, selected from the group consisting of n; 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-butylperoxyhex-3-yne; and 4-methyl-2,2-di-t-butylperoxypentane.

10. A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of claims 1 to 9, further comprising at least one curing accelerator in an amount up to 5% by weight based on the weight of the composition.

11. A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of claims 1 to 10, further comprising 0.5 to 10% by weight of non-conductive fine particle fillers based on the weight of the composition.

12. A curable and electrochemically peelable one-component (1K) adhesive composition according to any one of claims 1 to 11, comprising 0.5 to 15% by weight of v) the reinforcing agent.

13. A first material layer having a conductive surface; A second material layer having a conductive surface; An adhesive structure including, An adhesive structure in which a cured electrochemically peelable one-component (1K) adhesive composition as defined in any one of claims 1 to 12 is disposed between the first material layer and the second material layer.

14. 1) A step of applying a voltage to both surfaces to form an anode interface and a cathode interface, and 2) Step of peeling off the surface A method for peeling off the bonded structure according to claim 13, which includes: The method involves applying a voltage of 0.5 to 200V in step 1 for 1 second to 60 minutes.

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